Curable silicone composition, cured product thereof, and laminate

Abstract

[Problem] To provide a hot-melt curable silicone composition and applications therefor, said hot-melt curable silicone composition having excellent hot dispensing properties and storage stability, and being curable with an external energy stimulus as a trigger, and cured products thereof having excellent adhesiveness and mechanical properties. [Solution] A curable silicone composition, a cured product thereof, and use thereof in semiconductor applications, etc., the curable silicone composition including, in specific mass% ranges: (A) a non-hot-melt solid organopolysiloxane resin mixture; (B) a linear organopolysiloxane which has a curing-reactive functional group and is liquid at 25℃; (C) an organohydrogen polysiloxane; and (D) a hydrosilylation reaction catalyst that is inactive at room temperature but is provided with properties that are activated by an energy stimulus from an external source. The curable silicone composition has, as a whole, hot-melt properties and a melt viscosity at 100°C (as measured by a flow tester) of 50 Pa·s or less. In particular, the curable silicone composition of the present invention is suited for use as an adhesive agent / sealing agent 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, which is solid at room temperature but can be dispensed by a dispenser or the like when heated to, for example, 50°C or higher, while its curing reactivity is suppressed at the dispensing temperature, and which exhibits excellent curing properties when triggered by external energy stimuli such as irradiation with high-energy rays or exposure to temperatures of 130°C or higher, thereby providing a cured product with relatively high hardness and low tack. Furthermore, the present invention relates to the applications of the composition or cured product (particularly semiconductor components such as semiconductor device components and optoelectronic device components, and semiconductor devices having the cured product), and to a method for manufacturing a laminate using the composition, etc. [Background technology]

[0002] Curable silicone compositions are widely used in various industrial fields because they can cure into cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. These cured silicone products are generally less prone to discoloration and exhibit less deterioration of physical properties over time compared to other organic materials, making them suitable as encapsulants and adhesives for optical materials and semiconductor devices.

[0003] In recent years, hot-melt curable silicone compositions have become increasingly popular due to their ease of handling and cost reduction. For example, Patent Documents 1-3 propose hot-melt curable silicone compositions in tablet and sheet form. While these curable silicone compositions exhibit excellent meltability and curability / molding properties as encapsulants, recent semiconductor production processes often require liquid dispensing / application by dispensers as adhesives / sealants for semiconductors and electronic components. Tablet forms present the challenge of not being able to flexibly change the application form of the curable silicone composition to suit the bonding or sealing requirements.

[0004] On the other hand, Non-Patent Document 1 describes a hot-melt curable silicone composition product (DOWSIL TM A proposed usage method involves dispensing EA-4600 silicone adhesive using a heated dispenser. However, this curable silicone composition product is room temperature curable and requires a curing time of approximately 7 days, which presents challenges in adequately meeting the demands for short curing processes in semiconductor production and for cured products with high hardness and low tack. Furthermore, while hot-melt curable silicone compositions require a certain amount of heating during melting, the curing reaction begins to progress with heating, making it difficult to achieve curing at the desired timing, thus presenting challenges in controlling the reaction. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2016 / 136243 brochure [Patent Document 2] Japanese Patent Publication No. 2014-009322 [Patent Document 3] Special Publication No. 2017-512224 [Non-Patent Document 1] DOWSIL™ EA-4600 Silicone Adhesive Application Guide for PCB Device Assembly (Published by Dow & Toray Industries, Ltd., Form No. 11-3497-42-1120 S2D, 2020) [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention was made to solve the above problems, and the object of the present invention is to provide a hot-melt curable silicone composition, its cured product, and its uses, which is solid at room temperature but can be dispensed by a dispenser or the like when heated, while the curing reactivity is suppressed from room temperature to the dispensing temperature, providing excellent controllability of the reaction, can be cured at high speed at a desired timing, and whose cured product has practically sufficient adhesive and mechanical properties, as well as relatively high hardness and low tack. [Means for solving the problem]

[0007] As a result of diligent research, the present inventors have found that the above problems can be solved by a curable silicone composition containing a curable reactive functional group having a carbon-carbon double bond and an organopolysiloxane resin without such a curable reactive functional group, which is solid at 25°C; a linear organopolysiloxane having such a curable reactive functional group and which is liquid at 25°C; an organohydrogenpolysiloxane; and a hydrosilylation reaction catalyst (preferably selected from a photoactive hydrosilylation reaction catalyst and a hydrosilylation reaction catalyst-containing thermoplastic resin fine particles) that is inert at room temperature but exhibits activity in the composition upon external energy stimulation, in a specific range of parts, and the composition as a whole has hot-melt properties, and a melt viscosity at 100°C (measured by a flow tester: outlet nozzle diameter 1 mm, pressure 2.5 MPa) of 50 Pa·s or less, and by using the cured product thereof and its use in semiconductor applications, etc., and have completed the present invention. The composition may also contain a substantially non-volatile curing retarder for the hydrosilylation reaction. Furthermore, it is more preferable that the organopolysiloxane resin in the composition has a mass loss rate of 2.0% by mass or less when exposed to 200°C for 1 hour, in order to suppress the surface tack of the cured product and to give a relatively hard cured product.

[0008] From the standpoint of the technical effects of the present invention, the curable silicone composition is preferably used in the form of being filled into a dispensing cartridge, pail, or drum, and the cartridge, pail, or drum can be heated by a dispenser equipped with a heating unit and discharged onto a substrate to form a laminate which is a semiconductor precursor or an electronic component precursor. [Effects of the Invention]

[0009] In the present invention, a hot-melt curable silicone composition is provided, which is obtained by selectively combining a hydrosilylation reaction catalyst that is activated by external energy stimulation. Although it is solid at room temperature, it can be stably dispensed by a dispenser or the like at temperatures of 80°C or higher, while the curing reactivity is suppressed at this dispensing temperature, resulting in excellent controllability of the reaction. Furthermore, it can be rapidly cured triggered by irradiation with high-energy rays such as ultraviolet light and / or exposure to temperatures higher than the dispensing temperature (e.g., 130°C or higher), and the cured product has practically sufficient adhesive and mechanical properties, as well as relatively high hardness and low surface tack.

[0010] Here, if the hydrosilylation reaction catalyst is a photoactive hydrosilylation reaction catalyst that is activated by irradiation with high-energy rays, the composition after dispensing can be rapidly cured even at low temperatures of 100°C or below by irradiation with high-energy rays. On the other hand, compositions to which black or white pigments have been added may absorb or reflect high-energy rays, making it impossible to activate the reaction catalyst. In such cases, by using thermoplastic resin particles containing a hydrosilylation reaction catalyst as the catalyst, stable dispensing is possible at the dispensing temperature, while rapid curing can be achieved by heating to a temperature above the melting temperature of the thermoplastic resin (preferably 130°C or above). Needless to say, the hydrosilylation reaction catalyst and the type of energy stimulus used to activate the catalyst can be appropriately selected according to the composition and curing process, and both can also be used in combination.

[0011] In particular, the hot-melt curable silicone composition according to the present invention is suitably used as a sealant / encapsulant for protecting substrates. It can also be used for bonding applications between substrates where a relatively hard adhesive layer is required (double-sided bonding applications when there are two substrates). Furthermore, by connecting a heatable slot die to the outlet of a dispenser, it is possible to extrude the composition in a film or sheet shape with a controlled thickness and apply it to a substrate for precision coating. Since the curing reaction of the curable silicone composition of the present invention does not proceed at the time of heating and melting, it can be efficiently manufactured with only a simple mixing process, and can be provided in the desired shape, especially filled into dispenser cartridges, pails, or drums. Moreover, since the curable silicone composition of the present invention can be applied to a hot-dispensing process, it can be extruded into the desired shape on a substrate and cured by triggering external energy stimulation (such as irradiation with high-energy rays such as ultraviolet rays or exposure to temperatures of 130°C or higher) to be used as a sealant / encapsulant. It can also be used as an adhesive layer between substrates by curing it in close contact (including pressing) with the substrate to be adhered, as needed. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic diagram of the twin-screw extruder used in the example. [Modes for carrying out the invention]

[0013] Embodiments of the present invention will be described in detail below. In this specification, room temperature generally means a range of 15 to 30°C, particularly 18 to 25°C, and atmospheric pressure means the atmospheric pressure in the environment in which the curable silicone composition of the present invention is handled in a laboratory or factory, and usually means around 1 atmosphere (1013.25 hPa). In addition, in the present invention, unless otherwise specified, "having hot-melt properties" means that the entire composition has a high viscosity (including a raw rubber-like state in which plasticity can be measured) or solid form at 25°C to the extent that it can maintain its shape, and has a melt viscosity in the range described later at 100°C, and has the property of softening and becoming flowable when heated. Conversely, "not having hot-melt properties" means that the composition or constituent component (such as a solid organopolysiloxane resin) does not exhibit heating and melting behavior below 200°C on its own, and specifically means that it does not have a softening point and melt viscosity below 200°C.

[0014] [Curing silicone composition] A curable silicone composition according to the present invention, (A) 100 parts by mass of an organopolysiloxane resin that is solid at 25°C and contains the components (A1) and (A2) listed below in a mass ratio of 20:80 to 90:10, with each component not having hot-melt properties on its own. (A1) Having a hardening-reactive functional group containing a carbon-carbon double bond within the molecule, and RSiO 3 / 2 (R is a monovalent organic group, hydroxyl group, or alkoxy group) or SiO 4 / 2 An organopolysiloxane resin containing at least 20 mol% or more of the siloxane units represented by the formula, (A2) The molecule does not have a hardening-reactive functional group containing a carbon-carbon double bond, and SiO 4 / 2An organopolysiloxane resin containing at least 20 mol% or more of the siloxane units represented by the formula, (B) A linear organopolysiloxane having a curing-reactive functional group containing at least two carbon-carbon double bonds within the molecule, which is liquid at 25°C. (C) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, (D) A catalyst for hydrosilylation reactions that is inert at room temperature but exhibits activity in the composition upon external energy stimulation. The composition contains [a specific ingredient], and the entire composition has hot-melt properties, and is characterized by having a melt viscosity at 100°C (measured with a flow tester: outlet nozzle diameter 1 mm, pressure 2.5 MPa) of 50 Pa·s or less.

[0015] The composition may contain (E) a curing retarder for hydrosilylation reactions having a boiling point of 200°C or higher at atmospheric pressure, and other additives may be added as long as they do not impair the technical effects of the present invention.

[0016] [Organopolysiloxane resin having curing-reactive functional groups (A1)] The above component (A1) is one of the main components of this composition and has a curing-reactive functional group containing a carbon-carbon double bond in its molecule, SiO 4 / 2 The organopolysiloxane resin contains at least 20 mol% of the total siloxane units represented by (A1), and component (A1) alone does not have hot-melt properties. At 25°C, it is a solid in the solvent-free state. 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, a monovalent hydrocarbon group having 1 to 10 carbon atoms without a carbon-carbon double bond, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, as described later.

[0017] The curing reactive group having a carbon-carbon double bond may be a functional group having a carbon-carbon double bond, such as a (meth)acryloxy group, but it is particularly preferable that it is a hydrosilylation reactive functional group. Such a functional group can form a cured product in the presence of (C) organohydrogenpolysiloxane and (D) a photoactive hydrosilylation reaction catalyst, which will be described later. Examples of such curing reactive groups include alkenyl groups having 2 to 10 carbon atoms, and it is particularly preferable that they be vinyl groups or 1-hexenyl groups.

[0018] Preferably, the proportion of alkenyl groups among the organic groups bonded to all silicon atoms in component (A1) is in the range of 1 to 12 mol%, preferably 2 to 10 mol%. If the alkenyl group content is below the lower limit of the above range, the mechanical strength (hardness, etc.) of the resulting cured product may be insufficient. On the other hand, if the alkenyl group content is below the upper limit of the above range, the composition containing this component can achieve good hot-melt performance as a whole.

[0019] Component (A1) may contain other functional groups that do not have a carbon-carbon double bond, and it is particularly preferable to contain a functional group selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms that do not have a carbon-carbon double bond, especially alkyl groups having 1 to 10 carbon atoms such as methyl groups. On the other hand, the proportion of aryl groups such as phenyl groups in the total silicon-bonded organic groups of component (A1) is in the range of 0 to 5 mol%, more preferably in the range of 0 to 2 mol%, and it is most preferable that it contains no aryl groups at all (= 0 mol%). If a large amount of aryl groups such as phenyl groups are included, component (A1) itself will have hot-melt properties, which may prevent the achievement of the technical effects of the present invention, and in the cured product, SiO 4 / 2 The effect of reinforcing the hardened material, which is specific to the substrate, may be reduced.

[0020] Preferably, for component (A1), the functional groups bonded to silicon atoms are groups selected from methyl groups and alkenyl groups such as vinyl groups. 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, particularly preferably 88 to 98 mol% are methyl groups, and the other organic groups bonded to silicon atoms are alkenyl groups such as vinyl groups. Within this range, component (A1) does not have hot-melt properties when used alone, and is useful as a component particularly excellent in coloration resistance under high temperature of a cured product obtained from the curable silicone composition of the present invention. In addition, the component (A1) may contain a small amount of hydroxyl groups or alkoxy groups.

[0021] Component (A1) is a branched unit SiO 4 / 2 contains at least 20 mol% or more of the siloxane unit represented by based on all siloxane units, preferably contains at least 40 mol% or more, more preferably contains 50 mol% or more, and particularly preferably contains it in the range of 50 to 90 mol%. R is preferably a monovalent organic group, and particularly preferably a methyl group from the viewpoint of compatibility with other components. SiO 4 / 2 When the content of the siloxane unit represented by is less than the above lower limit, the technical effect of the present invention may not be achieved even if the organopolysiloxane resin contains a large amount of other branched siloxane units (for example, RSiO 3 / 2 ) in a large amount.

[0022] Preferably, component (A1) is (A1-1) the following average unit formula: (R 1 ₃SiO 1 / 2 ) a (R 1 ₂SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2)e (wherein each R 1R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, provided that the total R in one molecule 1 1 to 12 mole% of the group is an alkenyl group; each R 2 a is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; a, b, c, d, and e are numbers satisfying the following: 0.10 ≤ a ≤ 0.60, 0 ≤ b ≤ 0.70, 0 ≤ c ≤ 0.80, 0.2 ≤ d ≤ 0.65, 0 ≤ e ≤ 0.05, where c + d > 0.20 and a + b + c + d = 1. This is an organopolysiloxane resin represented by [formula].

[0023] In the above average unit formula, each R 1 The group is 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; an aralkyl group such as a benzyl group. Furthermore, the total R in one molecule 1 2 to 45 mol% of the total R in one molecule is an alkenyl group, preferably 2 to 45 mol% of the total R 1 2 to 35 mol% of the component is an alkenyl group, particularly preferably a vinyl group and / or a 1-hexenyl group. If the alkenyl group content is below the lower limit of the above range, the mechanical strength (hardness, etc.) of the resulting cured product may be insufficient. On the other hand, if the alkenyl group content is below the upper limit of the above range, a composition containing this component can form a cured product with excellent mechanical strength. Note that each R 1 It is preferable that R is a functional group selected from the alkyl and alkenyl groups, and from the viewpoint of the technical effects of the present invention, 1 It is preferable that the compound substantially does not contain aryl groups such as phenyl groups.

[0024] In the above formula, R 2 R is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms. 2 Base R including 2 O 1 / 2 This corresponds to a hydroxyl group or alkoxy group possessed by the organopolysiloxane resin of component (A1).

[0025] In the above formula, a is the general formula: R 1 3SiO 1 / 2 This number represents the proportion of siloxane units. 'a' satisfies 0.1 ≤ a ≤ 0.90, preferably 0.15 ≤ a ≤ 0.85. If 'a' is within the above range, the curable silicone composition containing this component will have good hot-melt properties and can impart excellent adhesive properties and mechanical strength (hardness, elongation, etc.) to the cured product.

[0026] In the above formula, b is the general formula: R 1 2SiO 2 / 2 This number represents the proportion of siloxane units. b satisfies 0 ≤ b ≤ 0.70, preferably 0 ≤ b ≤ 0.60. If b is less than or equal to the upper limit of the above range, the curable silicone composition containing this component has good hot-melt properties and provides a composition that is less sticky at room temperature. In the present invention, b may be 0, and it is preferable that b is 0.

[0027] In the above formula, c is the general formula: R 3 SiO 3 / 2 This is a number indicating the proportion of siloxane units. c satisfies 0 ≤ c ≤ 0.80, preferably 0 ≤ c ≤ 0.75. If c is less than or equal to the upper limit of the above range, the curable silicone composition containing this component has good hot-melt properties and provides a composition with low tack and low stickiness on the surface at room temperature. In the present invention, c may be 0, and it is preferable that c is 0.

[0028] In the above formula, d is the formula SiO 4 / 2 This number represents the proportion of siloxane units, and it is necessary that 0.20 ≤ d ≤ 0.65, preferably 0.25 ≤ d ≤ 0.65, and particularly preferably 0.40 ≤ d ≤ 0.65. If d is within the above numerical range, the composition containing this component as a whole can achieve good hot-melt performance, and the cured product obtained by curing the composition can be relatively hard and have sufficient flexibility for practical use.

[0029] In the present invention, it is necessary that c+d > 0.20 in the above formula. If the value of c+d is 0.20 or less, good hot-melt performance cannot be achieved for the composition as a whole, and the technical effects of the present invention may not be fully realized.

[0030] In the above formula, e is the general formula: R 2 O 1 / 2 This number represents the proportion of units, and these units refer to hydroxyl groups or alkoxy groups bonded to silicon atoms that may be contained in the organopolysiloxane resin. e satisfies 0 ≤ e ≤ 0.05, preferably 0 ≤ e ≤ 0.03. In the above formula, the sum of a, b, c, and d, which are the sums of each siloxane unit, is equal to 1.

[0031] Since component (A1) is a solid at room temperature, it is preferable to use it 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; silicones such as hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent used here can be efficiently removed in the process described later.

[0032] [Organopolysiloxane resin without curing-reactive functional groups (A2)] Component (A2) is one of the main components of this composition, and does not have a curing-reactive functional group containing a carbon-carbon double bond, and is SiO 4 / 2The organopolysiloxane resin contains at least 20 mol% of the total siloxane units represented by (A2), and component (A2) alone does not have hot-melt properties. It is solid in the solvent-free state at 25°C. By using component (A2) in combination with components (A1) and (B) within a predetermined quantitative range, it is a component that achieves hot-melt properties for the curable silicone composition as a whole and excellent stress relaxation properties for the cured product obtained by curing the curable silicone composition.

[0033] Component (A2) preferably does not contain any curing-reactive functional groups containing carbon-carbon double bonds, such as alkenyl groups, within its molecule, but rather contains monovalent hydrocarbon groups having 1 to 10 carbon atoms that do not have carbon-carbon double bonds, particularly alkyl groups having 1 to 10 carbon atoms such as methyl groups, and functional groups selected from aryl groups. On the other hand, component (A2) preferably has a proportion of aryl groups such as phenyl groups in the total silicon-bonded organic groups that is 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%). If the content of aryl groups in component (A2) exceeds the above upper limit, (if it contains a large amount of aryl groups such as phenyl groups, component (A2) itself will have hot-melt properties, which may prevent the achievement of the technical effects of the present invention, and in the cured product, SiO 4 / 2 The effect of reinforcing the cured product in a manner specific to the substrate may be reduced, and the color resistance of the cured product at high temperatures may deteriorate.

[0034] Preferably, 70 to 100 mol% of the organic groups bonded to the silicon atoms in component (A2) are methyl groups, more preferably 80 to 100 mol%, and particularly preferably 88 to 100 mol% are methyl groups. Within this range, component (A2) does not exhibit hot-melt properties on its own, and SiO 4 / 2 This component can be particularly excellent in reinforcing cured products containing siloxane units represented by [the formula shown]. The organopolysiloxane resin of component (A2) may also contain small amounts of hydroxyl groups or alkoxy groups.

[0035] Component (A2) is an organopolysiloxane resin that is solid at 25°C in the absence of a solvent, and contains branched siloxane units SiO2 within its molecule. 4 / 2 The product is characterized by containing at least 20 mol% or more of the siloxane units represented by . Preferably, the organopolysiloxane of component (A2) is SiO 4 / 2 The unit is at least 40 mol% of the total siloxane units, and is preferably 50 mol% or more, and particularly preferably in the range of 50 to 65 mol%.

[0036] Preferably, component (A2) is (A2-1) the following average unit formula: (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2)j (In the formula, each R 3 R is a monovalent hydrocarbon group that independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond; 2 The organopolysiloxane resin is represented as follows: (where is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; f, g, h, i, and j are numbers satisfying the following: 0.35 ≤ f ≤ 0.55, 0 ≤ g ≤ 0.20, 0 ≤ h ≤ 0.20, 0.45 ≤ i ≤ 0.65, 0 ≤ j ≤ 0.05, and f + g + h + i = 1).

[0037] In the above average unit formula, R 2 R is a group similar to those described above, preferably a hydrogen atom or a methyl group. 3 R is a monovalent hydrocarbon group that independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond, such as an alkyl group like methyl. Here, the total R in one molecule 3It is particularly preferable, from the standpoint of industrial production and the technical effects of the invention, that 70 mol% or more, more preferably 88 mol% or more, be alkyl groups having 1 to 10 carbon atoms, such as methyl groups, especially methyl groups. On the other hand, R 3 It is preferable that the compound substantially does not contain aryl groups such as phenyl groups.

[0038] In the above formula, f is the general formula: R 3 3SiO 1 / 2 This number represents the proportion of siloxane units. f satisfies 0.35 ≤ f ≤ 0.55, preferably 0.40 ≤ f ≤ 0.50. If f is within the above 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.

[0039] In the above formula, g is the general formula: R 1 2SiO 2 / 2 This number represents the proportion of siloxane units. g satisfies 0 ≤ g ≤ 0.20, preferably 0 ≤ g ≤ 0.10. If 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 that is not sticky at room temperature. In the present invention, g may be 0, and it is preferable that g is 0.

[0040] In the above formula, h is the general formula: R 1 SiO 3 / 2 This is a number indicating the proportion of siloxane units. h satisfies 0 ≤ h ≤ 0.20, preferably 0 ≤ h ≤ 0.10. If 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 tack and low stickiness at room temperature. In the present invention, h may be 0, and it is preferable that h is 0.

[0041] In the above formula, i is SiO 4 / 2i is a number indicating the proportion of siloxane units, preferably 0.30 ≤ i ≤ 0.65, and particularly preferably 0.50 ≤ i ≤ 0.65. When i is within this numerical range, the curable silicone composition containing this component can achieve good hot-melt performance as a whole, the cured product obtained by curing the curable silicone composition has excellent mechanical strength, and the composition as a whole is non-sticky and easy to handle.

[0042] In the above formula, j is the general formula: R 2 O 1 / 2 This number represents the proportion of units, where each unit refers to a hydroxyl group or alkoxy group bonded to a silicon atom that may be contained in the organopolysiloxane resin. j satisfies 0 ≤ j ≤ 0.05, preferably 0 ≤ j ≤ 0.03. In the above formula, the sum of the individual siloxane units, f, g, h, and i, is equal to 1.

[0043] Component (A2) is a solid at room temperature and is preferably used dissolved in a solvent or solvent mixture for physical mixing with component (B) described later. Here, the type of solvent is the same as that for component (A1).

[0044] [(A) component] The curable silicone composition according to the present invention contains, as component (A), the above-mentioned components (A1) and (A2) in a mass ratio of 20:80 to 90:10, preferably 35:65 to 90:10, and more preferably 50:50 to 90:10. Here, although each component of (A) does not have hot-melt properties on its own, by using it in combination with component (B), described later, within a predetermined ratio range, the composition as a whole can achieve hot-melt properties. In this composition, by using component (A1) in combination with component (A2), it is possible to adjust to some extent the storage modulus, loss modulus, and tanδ calculated from their ratios in the cured product obtained by curing this curable composition, thereby achieving suitable modulus, flexibility, and stress relaxation properties in the cured product.

[0045] Component (A), and its constituent components (A1) and (A2), preferably have a mass loss rate of 2.0% by mass or less when exposed to 200°C for 1 hour. These components are in units of M (R 3 3SiO 1 / 2 ) and Q units (SiO 4 / 2 The curable silicone composition of the present invention is an organopolysiloxane resin composed of ), and during its polymerization process, a volatile low molecular weight component, specifically the M4Q structure, is generated as a by-product. However, this structure significantly reduces the hardness of the cured product obtained from the curable silicone composition of the present invention. Furthermore, if the curable silicone composition containing the M4Q structure is integrally molded with a substrate such as a semiconductor and then exposed to high temperatures to remove the M4Q structure, a volume reduction and a significant increase in hardness occur in the cured product resulting from the curable silicone composition. This can cause changes in the dimensions of the molded product, warping, and an increase in the surface tackiness of the cured product. In addition, if a large amount of the M4Q structure remains in the composition or cured product, a significant increase in hardness can occur in the adhesive layer or sealing layer intended for double-sided bonding, and the elastic modulus may change significantly. For this reason, in order to apply the curable silicone composition of the present invention to applications in which it is laminated with a substrate such as a semiconductor, it is preferable to remove the M4Q structure from the organopolysiloxane resin at the raw material stage, preferably before the molding process in which the curable silicone composition is laminated with the substrate and cured, or even before the curable silicone composition is prepared.

[0046] However, the M4Q structure has high compatibility with organopolysiloxane resin, and under drying conditions that remove organic solvents, it is difficult to remove volatile low molecular weight components, specifically the M4Q structure, from component (A), etc. Therefore, since volatile components can be removed by treating the obtained crude raw material, the organopolysiloxane resin, at a high temperature of about 200°C for a short time, it is preferable to remove the volatile low molecular weight components in component (A) at the raw material stage before preparing the curable silicone composition by simultaneously removing organic solvents and volatile components such as the M4Q structure from components (A1) and (A2) using a twin-screw kneader set to a temperature of 200°C or higher, and more preferably, 1.0% by mass or less.

[0047] Furthermore, from the viewpoint of efficiently producing the curable hot-melt silicone composition of the present invention, it is preferable to add component (B), described later, to component (A) dissolved in an organic solvent, mix them in a liquid state, and feed the mixture to a twin-screw extruder set to 200°C or higher, thereby removing volatile components such as the M4Q structure along with the organic solvent. This method allows for obtaining a mixture of hot-melt component (A) and component (B), which can be used in the subsequent steps to knead it with the remaining components constituting the curable silicone composition.

[0048] [(B) Component] Component (B) is one of the main components of this curable silicone composition, and is a liquid linear organopolysiloxane at 25°C, having a curing-reactive functional group containing at least two carbon-carbon double bonds in its molecule. When such a curing-reactive linear organopolysiloxane is used in combination with the solid organopolysiloxane resin, which is component (A) mentioned above, the hot-melt properties of the entire composition can be achieved.

[0049] Component (B) must have a curing-reactive functional group having a carbon-carbon double bond within its molecule. Such a curing-reactive functional group has hydrosilylation reactivity and forms a cured product through crosslinking reactions with other components. Such a curing-reactive functional group is preferably an alkenyl group similar to that of component (A1), particularly a vinyl group or a hexenyl group.

[0050] Component (B) is a liquid or plastic, rubbery, chain-like organopolysiloxane at 25°C (room temperature), and when used in combination with component (A), it imparts hot-melt properties to the composition of the present invention. The chemical structure of the organopolysiloxane of component (B) may be linear or branched, and may have a polysiloxane structure branched by a small number of T units or Q units, but preferably, (B1) The following structural formula: R 4 3SiO(SiR 4 20) k SiR 4 3 (In the formula, each R 4 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, however, R in one molecule 4 A linear diorganopolysiloxane is represented by (at least two of which are alkenyl groups, and k is a number between 20 and 1,000). Preferably, a linear diorganopolysiloxane having one alkenyl group, particularly a vinyl group, at each end of the molecular chain is preferred.

[0051] In the above formula, each R 4 R is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group such as methyl, particularly preferably a methyl group; an alkenyl group such as vinyl, particularly preferably a vinyl group and / or a hexenyl group; an aryl group such as phenyl; or an aralkyl group such as benzyl. Furthermore, R in one molecule 4 At least two of them are alkenyl groups, preferably vinyl groups. Also, each R 4is preferably a functional group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms such as methyl groups, and alkenyl groups such as vinyl groups and hexenyl groups, all R 4 wherein at least two groups per molecule are alkenyl groups, and the remaining R 4 is preferably a methyl group. From the viewpoint of the technical effect of the present invention, R 4 preferably substantially does not contain aryl groups such as phenyl groups. When a large amount of aryl groups such as phenyl groups is contained, the coloration resistance at high temperatures of a cured product obtained from the curable silicone composition may deteriorate. Particularly preferably, the compound has one alkenyl group such as a vinyl group at each of both ends of the molecular chain, and the other R 4 is preferably a methyl group.

[0052] In the above formula, k is a number of 20 to 5,000, preferably 30 to 3,000, particularly preferably 45 to 800. When k is not less than the lower limit of the above range, a curable silicone composition with less stickiness at room temperature can be obtained. On the other hand, when k is not more than the upper limit of the above range, good hot melt performance can be achieved for the entire curable silicone composition.

[0053] The added amount of component (B) is in the range of 10 to 100 parts by mass, preferably in the range of 50 to 100 parts by mass, more preferably in the range of 70 to 100 parts by mass, relative to 100 parts by mass of component (A). When the content of component (B) is within the above range, the obtained curable silicone composition exhibits hot-melt properties suitable for a hot dispense process, has reduced stickiness at room temperature, so it is excellent in handling workability, and the mechanical strength of the cured product obtained by curing the composition is improved.

[0054] [Component (C)] 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 carbon-carbon double bonds in component (A1) and component (B) in the presence of component (D).

[0055] The structure of organohydrogenpolysiloxane as a crosslinking agent is not particularly limited, and may be linear, branched, cyclic or resinous. That is, component (C) is HR2SiO 1 / 2 hydrogen organosiloxy unit represented by (D H unit, each R is independently a monovalent organic group) as the main constitutional unit, and has HR2SiO at its terminal 1 / 2 hydrogen diorganosiloxy unit represented by (M H unit, each R is independently a monovalent organic group), and may be an organohydrogenpolysiloxane having the above D H units and the like, and may be a linear organohydrogenpolysiloxane.

[0056] On the other hand, when the present curable silicone composition is used in a molding step, the content of curing reactive functional groups containing carbon-carbon double bonds in the present composition is low. Therefore, from the viewpoints of curing rate, moldability and curability, the organohydrogenpolysiloxane is RSiO 3 / 2 monoorganosiloxy unit represented by (T unit, R is a monovalent organic group or a silicon-bonded hydrogen atom) or SiO 4 / 2 siloxy unit represented by (Q unit) which is a branched unit, and has at least two HR2SiO groups in the molecule 1 / 2 hydrogen diorganosiloxy unit represented by (M H unit, each R is independently a monovalent organic group), and has M at the molecular terminal H organohydrogenpolysiloxane resin having units is preferred.

[0057] Component (C) of the present invention is preferably a low-volatility organohydrogenpolysiloxane, and more specifically, it may have the characteristics of having a mass reduction rate of 10% by mass or less compared to before exposure after exposure at 100°C for 1 hour under atmospheric pressure, and having a low content of volatile low molecular weight components. As described later, in the production process of filling the curable silicone composition of the present invention into a cartridge, in order to obtain a composition that does not contain voids, etc., it is preferable to melt and knead each component of the curable silicone composition, and the composition obtained therefrom, under reduced pressure in a temperature range of 50 to 150°C. However, even with heating for a very short time, if a large amount of the components constituting the composition volatilizes under these kneading conditions, it may not be possible to obtain a composition with the properties as designed. In particular, since the amount of organohydrogenpolysiloxane, which is a crosslinking agent, added is small relative to the total mass of the curable silicone composition, the properties of the composition (curing properties, physical properties of the cured product, etc.) due to the volatilization of this component may vary significantly from the intended values. Therefore, it is especially preferable to select an organohydrogenpolysiloxane with low volatility for component (C), depending on its use and manufacturing method (especially filling into cartridges, pails, or drums).

[0058] Particularly suitable organohydrogenpolysiloxanes are: The following is the average unit formula (1): (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 This is an organohydrogen polysiloxane resin represented by [formula].

[0059] In the formula, each R 5R is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms and not having an aliphatic unsaturated carbon bond, or hydrogen atom, provided that there are at least two R in one molecule. 5 R is a hydrogen atom. 5 The monovalent hydrocarbon group is, for example, an alkyl group such as methyl; an aryl group such as phenyl; an aralkyl group such as benzyl; or other halogenated alkyl groups. From an industrial standpoint, a methyl group or a phenyl group is preferred.

[0060] In the formula, R 6 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated carbon bond, and examples of groups similar to the monovalent hydrocarbon group described above are given. On the other hand, R 2 R is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms, and R is in component (A1) or component (A2) above. 2 Similar groups are given as examples.

[0061] In the formula, l, m, n, and p are numbers such that 0.01 ≤ l ≤ 0.6, 0 ≤ m, 0 ≤ n ≤ 0.9, 0 ≤ p ≤ 0.9, and l + m + n + p = 1, preferably 0 ≤ q ≤ 0.05, and n + p ≥ 0.2. The organohydrogenpolysiloxane resin, which is component (C), is more specifically M H MT resin, M H T resin, M H MTQ resin, M H MQ resin, M H DQ resin, and M H Examples include Q resin. In the notation of the resin, M, D, T, and Q represent M units, D units, T units, and Q units, respectively. H This represents the M unit, which contains a hydrogen atom.

[0062] Component (C) is preferably an organohydrogenpolysiloxane containing Q units, as represented by the following average unit formula (2). Equivalent unit formula (2): (HR 6 2SiO 1 / 2 ) e (R 6 2SiO 2 / 2 )f (SiO 4 / 2 ) g In the formula, R 6 Each of these is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds, where e, f, and g are numbers satisfying the conditions 0.01 ≤ e ≤ 0.6, 0 ≤ f ≤ 0.9, 0.2 ≤ g ≤ 0.9, and e + f + g = 1. A specific example of this monovalent hydrocarbon group is R in the above average composition formula (1). 4 This is the same as the specific example of a monovalent hydrocarbon group represented by R. 6 Preferably, each of these groups is independently selected from a methyl group and a phenyl group.

[0063] Similarly, component (C) is preferably an organohydrogenpolysiloxane containing T units, represented by the following average unit formula (3). Average unit formula (3): (HR 7 2SiO 1 / 2 ) h (R 7 2SiO 2 / 2 ) i (R 8 SiO 3 / 2 ) j In the formula, R 7 and R 8 Each of these is 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% of the group is an aryl group, and h, i, and j are numbers that satisfy the following conditions: 0.01 ≤ h ≤ 0.6, 0 ≤ i ≤ 0.9, 0.2 ≤ j ≤ 0.9, and h + i + j = 1. The specific example of this monovalent hydrocarbon group is the same as the specific example of a monovalent hydrocarbon group shown in the average unit formula (1) above. 8 This applies to all R 8 Preferably, each group is independently selected from methyl groups and phenyl groups, provided that at least 10 mol% of them are phenyl groups.

[0064] The organohydrogen polysiloxane resins represented by the above average unit formulas (2) or (3) may be used individually or in combination.

[0065] The amount of organohydrogenpolysiloxane in component (C) of the curable silicone composition of the present invention is sufficient to cure the curable silicone composition, and it is preferable that the amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane of component (C) is such that, relative to the curing reactive functional groups containing carbon-carbon double bonds in components (A) and (B) (for example, alkenyl groups such as vinyl groups), the number of silicon-bonded hydrogen atoms per alkenyl group is 0.5 to 20.0, particularly in the range of 1.0 to 10, relative to the alkenyl groups bonded to silicon atoms in the entire curable silicone composition.

[0066] [(D) component] Component (D) is one of the characteristic components of the curable silicone composition according to the present invention. It is a catalyst for the hydrosilylation reaction to cure the curable silicone composition of the present invention by crosslinking the curing-reactive functional group containing a carbon-carbon double bond in components (A) / (B) with the silicon atom-bonded hydrogen atom (Si-H group) in component (C) through a hydrosilylation reaction. Specifically, it is an inert state that does not show catalytic activity unless external energy stimulation is applied at room temperature, but it is a catalyst for the hydrosilylation reaction that shows activity in the composition upon external energy stimulation. Here, external energy stimulation includes applying thermal energy such as high-temperature exposure, light energy such as high-energy ray irradiation, and physical energy such as vibration and shock to the composition from the outside. In the present invention, depending on the type of component (D), irradiation with high-energy rays and exposure to high temperatures (preferably 130°C or higher) are typical external energy stimuli. It is preferable that these energy stimuli trigger catalytic activity for the hydrosilylation reaction, and the curing reaction of the entire composition proceeds.

[0067] Such component (D) is not particularly limited as long as it possesses the properties described above, but in practice, one or more hydrosilylation catalysts selected from (D1) a hydrosilylation catalyst that is activated in the composition by irradiation with high-energy rays, and (D2) a hydrosilylation catalyst-containing thermoplastic resin fine particles are particularly preferred. Furthermore, component (D) can be appropriately selected depending on the composition of the curable silicone composition according to the present invention (for example, whether or not the composition before curing contains light-shielding or light-absorbing components) and the type of curing process, and both may be used in combination depending on the curing process.

[0068] Component (D1) is one form of component (D), and is known as a high-energy ray-activated catalyst or photoactivated catalyst, and is well known in the art. The photoactive hydrosilylation catalyst, which is component (D1), does not become activated even in a heated and melted state unless irradiated with high-energy rays such as ultraviolet rays, while after irradiation with high-energy rays, the curing reaction proceeds smoothly even at low temperatures such as room temperature without heating. Therefore, the composition as a whole according to the present invention can undergo rapid curing at low temperatures triggered by irradiation with high-energy rays, while also having excellent storage stability, making it suitable for hot dispensing processes that require exposure to temperatures of 50°C or higher, and offering excellent handling workability due to easy reaction control. Furthermore, since the catalytic activity of component (D1) is suppressed even in the heating and melting process for a short time, it is possible to melt and knead the curable silicone composition under reduced pressure in a temperature range of 50 to 150°C and fill it into a dispenser cartridge, pail, or drum without impairing its storage stability in the production process of filling the curable silicone composition of the present invention into a cartridge.

[0069] Furthermore, component (D1) has the property of being uniformly compatible with curable silicone compositions, making it possible to easily design compositions and cured products with excellent transparency (=light transmittance).

[0070] High-energy rays include ultraviolet rays, gamma rays, X-rays, alpha rays, and electron beams. In particular, ultraviolet rays, X-rays, and electron beams irradiated from commercially available electron beam irradiation devices are preferred. Among these, ultraviolet rays are preferred from the viewpoint of catalyst activation efficiency, and ultraviolet rays in the wavelength range of 280 to 380 nm are preferred from the viewpoint of industrial use. The irradiation dose varies depending on the type of high-energy ray activated catalyst, but in the case of ultraviolet rays, the cumulative irradiation dose at a wavelength of 365 nm is 100 mJ / cm². 2 ~100J / cm 2 It is preferable that it be within the range.

[0071] Specific examples of 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), and trimethyl(3,5- Examples include (butanedione) platinum(IV), trimethyl(methylacetoacetate) platinum(IV), bis(2,4-pentanedionato) platinum(II), bis(2,4-hexanedionato) platinum(II), bis(2,4-heptanedionato) platinum(II), bis(3,5-heptanedionato) platinum(II), bis(1-phenyl-1,3-butanedionato) platinum(II), bis(1,3-diphenyl-1,3-propanedionato) platinum(II), and bis(hexafluoroacetylacetonato) platinum(II). Among these, (methylcyclopentadienyl)trimethylplatinum(IV) and bis(2,4-pentanedionato) platinum(II) are preferred in terms of versatility and availability.

[0072] Component (D2) is another form of component (D), and may be either fine particles in which a hydrosilylation reaction catalyst, such as a platinum-based catalyst, is dissolved or dispersed in a thermoplastic resin, or microcapsule fine particles in which a platinum-based catalyst is contained as a nucleus within a thermoplastic resin shell. Here, the thermoplastic resin is a wall material for the hydrosilylation reaction catalyst, and at room temperature to low temperatures (around the dispensing temperature), the wall material inactivates the hydrosilylation reaction catalyst in the particles so as not to disperse in the system. However, at high temperatures (e.g., 130°C or higher), the thermoplastic resin wall material melts, the hydrosilylation reaction catalyst disperses in the system, becomes activated, and a curing reaction based on the hydrosilylation reaction proceeds.

[0073] Examples of platinum-based catalysts included in 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 does not substantially allow the platinum-based catalyst to permeate, at least during storage, and is substantially soluble in the organopolysiloxane, the main component of this composition, but preferably examples include silicone resins, polysilane resins, acrylic resins, methylcellulose, and polycarbonate resins. The softening point or glass transition point of this thermoplastic resin is preferably in the range of 40 to 200°C. This softening point is the temperature at which the resin begins to flow due to its own weight or surface tension, and can be measured by observing the pulverized particles with a microscope while raising the temperature at a constant rate. This glass transition point can also be measured by a DSC (differential scanning calorimeter). In the present invention, the curable silicone composition is exposed to a temperature of about 100°C for a short time by the production process described later, so it is preferable that either the softening point or the glass transition point is in the range of 100 to 200°C, and more preferably in the range of 130 to 200°C. This is because if the softening point or glass transition point of the thermoplastic resin is below 100°C, the catalyst tends to be activated during the production of the curable silicone composition, and the storage stability tends to decrease significantly. On the other hand, if it exceeds 200°C, it tends not to be possible to obtain a sufficient heat curing rate. Furthermore, the average particle size of the platinum-based catalyst-containing thermoplastic fine particles is not limited, but is preferably in the range of 0.1 to 500 μm, and more preferably in the range of 0.3 to 100 μm. This is because it is difficult to prepare hydrosilylation reaction catalyst-containing thermoplastic resin fine particles whose average particle size is below the lower limit of the above range, and on the other hand, if it exceeds the upper limit of the above range, the dispersibility in the curable silicone resin composition decreases.

[0074] In the present invention, it is preferable to use thermoplastic resin fine particles containing a catalyst for hydrosilylation reaction as component (D2), which has 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 containing polycarbonate resin in at least a portion thereof. In this case, since the melting of the thermoplastic resin that forms the wall material is suppressed below 130°C, the catalyst for hydrosilylation reaction remains in an inactive state during the normal melt-kneading process and dispensing temperature, resulting in particularly excellent storage stability and reaction controllability.

[0075] Furthermore, since (D2) hydrosilylation reaction catalyst-containing thermoplastic resin fine particles do not fundamentally dissolve with curable silicone compositions and a transparent composition cannot be obtained, it may be difficult to design a composition with excellent transparency and light transmittance when using component (D2).

[0076] The method for preparing such platinum-based catalyst-containing thermoplastic resin fine particles is not limited, and examples include conventionally known chemical methods such as interfacial polymerization and in-situ polymerization, and physical and mechanical methods such as coacervation and liquid-phase drying. In particular, liquid-phase drying and gas-phase drying are preferable because microcapsule fine particles with a narrow particle size distribution can be obtained relatively easily. The fine particles obtained by these methods can be used as is, but it is desirable to wash them with a suitable cleaning solvent to remove the platinum-based catalyst adhering to their surface in order to obtain a curable silicone composition with excellent storage stability. A suitable cleaning solvent is one that does not dissolve the thermoplastic resin but has the property of dissolving the platinum-based catalyst. Examples of such cleaning solvents include alcohols such as methyl alcohol and ethyl alcohol, 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 for producing the granular material, so it is not particularly limited, but it is preferable that the content of the platinum-based catalyst relative to the thermoplastic resin is 0.01% by mass or more. This is because if the platinum-based catalyst content is less than 0.01% by mass, the physical properties of the cured product will be impaired by this composition unless a large amount of platinum-based catalyst-containing thermoplastic resin fine particles are included in the composition.

[0077] As described above, component (D) can be appropriately selected depending on the composition of the curable silicone composition according to the present invention (for example, whether or not the composition before curing contains light-shielding or light-absorbing components) and the type of curing process. For example, if i) the composition itself contains a large amount of light-shielding / light-absorbing / reflective components (for example, white pigments, black pigments, UV protection agents, etc.), ii) it is difficult to irradiate the composition with high-energy rays 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 exposure to high temperature.

[0078] On the other hand, if i) a curing reaction triggered by irradiation with high-energy rays is permissible in the curing process, ii) high-temperature exposure is not permissible due to the type of substrate (heat resistance, high-temperature deformation, etc.) or the curing process, and / or iii) transparency (= light transmittance) is required for the composition and its cured product, then it is preferable to select component (D1) and cure it using irradiation with high-energy rays as the trigger. Needless to say, it is also possible to combine both and design a multi-stage curing process / step.

[0079] The amount of component (D) added is a catalytic amount, and specifically, it is an amount such that the amount of metal atoms in component (D) is in the range of 1 to 500 ppm by mass relative to the whole composition, and preferably an amount in the range of 2 to 200 ppm.

[0080] The compositions according to the present invention may optionally contain other curing agents (e.g., peroxides, photopolymerization initiators, photosensitizers, etc.) and hydrosilylation reaction catalysts other than photoactive types, as long as they do not impair the technical effects of the present invention. However, for the reasons mentioned above, such as the prevention of voids, it is preferable that these optional curing components are substantially non-volatile.

[0081] [Curing retarder for hydrosilylation reaction] The curable silicone composition of the present invention may further contain a curing retarder for the hydrosilylation reaction in addition to the above components (A) to (D). The structure of the curing retarder is not particularly limited, but from the viewpoint of the technical effects of the present invention, the use of (E) a curing retarder for the hydrosilylation reaction having a boiling point of 200°C or higher at atmospheric pressure is particularly preferred. This is because, when raw materials are melt-kneaded under reduced pressure during the production process of the curable silicone composition, if a compound with a low boiling point is used as a curing retarder, some or all of the curing retarder may volatilize during the melt-kneading process, and the target curing retardation effect for the curable silicone composition may not be obtained.

[0082] The curing retarder of the present invention is not particularly limited, but examples include alkyne alcohols such as 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexyne-3-ol, 2-phenyl-3-butyne-2-ol, and 1-ethynyl-1-cyclohexanol; enyne compounds such as 3-methyl-3-penten-1-yine and 3,5-dimethyl-3-hexen-1-yine; low molecular weight siloxanes containing alkenyl groups such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; and alkynyloxysilanes such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane. Of these, (E) it is particularly preferable to use a curing retarder with a boiling point of 200°C or higher at atmospheric pressure, and in practice, the use of alkynyloxysilanes such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane is preferred. The content of the curing retarder in the curable silicone composition is not particularly limited, but it is preferably in the range of 1 to 10,000 ppm by mass relative to the composition.

[0083] [(F) Other additives] In addition to the components (A) to (D) and any component (E) described above, the curable silicone composition of the present invention may also contain materials known in the art as additives that can be used in silicone compositions. The following are examples of additives that can be used, but are not limited to these. Furthermore, when melting and kneading the raw materials under reduced pressure during the production process of the curable silicone composition and the technical effects of the present invention, it is particularly preferable that the other additives are high-boiling point or substantially non-volatile components.

[0084] [(F1) Functional Filler] Functional fillers can be used as additives to improve the mechanical properties or flame retardancy of cured products made from the curable silicone composition of the present invention. Examples of such functional fillers include inorganic fillers, organic fillers, and mixtures thereof. Examples of inorganic fillers include reinforcing fillers, pigments (especially white and black pigments), thermally conductive fillers, conductive fillers, phosphors, and mixtures of at least two of these. Examples of organic fillers include silicone resin-based fillers, fluororesin-based fillers, and polybutadiene resin-based fillers. The shape of these fillers is not particularly limited and may be spherical, spindle-shaped, flattened, needle-shaped, amorphous, etc.

[0085] It is preferable to select and use the type and amount of functional filler within a range that allows for melt-kneading of the curable silicone composition of the present invention, and within a range where the influence on the technical effects of the present invention (e.g., curing characteristics, mechanical properties after curing, weather resistance, etc.) is acceptable.

[0086] One preferred embodiment of the curable silicone composition of the present invention is one that is substantially free of functional fillers. In particular, when the curing reaction is triggered by irradiation with high-energy rays using the above-mentioned component (D1), if a large amount of light-shielding or light-absorbing / reflective functional fillers, such as white pigments or black pigments, are included, the high-energy rays may be shielded, absorbed, or reflected on the surface of the composition, hindering the photoactivation of component (D1) and significantly degrading the curability of the composition.

[0087] On the other hand, if the curable silicone composition contains a light-shielding or light-absorbing / reflective functional filler (e.g., black pigment or white pigment) as component (F1), it is preferable to use the hydrosilylation reaction catalyst-containing thermoplastic resin fine particles, which are component (D2), as the catalyst. This is because, when such fillers are included, transparency or light transmittance is not generally required, and the composition containing these pigments can be rapidly cured by exposure to high temperatures (e.g., 130°C or higher).

[0088] [(F2) Adhesion-enhancing agent] The composition of the present invention may contain an adhesion promoter, provided that it does not impair the objectives of the present invention. Such adhesion promoters are common to the components suitably exemplified by the applicant in the international patent application (PCT / JP2020 / 12027), and include silane compounds such as 3-glycidoxypropyltrimethoxysilane, organosiloxane oligomers, alkyl silicates, as well as reaction mixtures of amino group-containing organoalkoxysilanes and epoxy group-containing organoalkoxysilanes disclosed in Japanese Patent Publication No. 52-8854 and Japanese Patent Application Publication No. 10-195085. In particular, carbasilatran derivatives having a silicon atom-bonded alkoxy group or a silicon atom-bonded alkenyl group in one molecule, and silatran derivatives having an alkoxysilyl group-containing organic group can be suitably used. The content of this adhesion promoter is not limited, but it is preferably in the range of 0.01 to 10 parts by mass per 100 parts by mass of the total composition.

[0089] [Other optional components] Furthermore, this composition may also contain other optional components such as heat-resistant agents including iron oxide (red iron oxide), cerium oxide, cerium dimethyl silanolate, cerium fatty acid salts, cerium hydroxide, and zirconium compounds; as well as dyes, pigments other than white, flame retardants, etc.

[0090] [Shape retention and melt viscosity of the composition] The curable silicone composition according to the present invention is a solid that retains its shape at 25°C, but as described above, it has hot-melt properties, and in particular, its melt viscosity at 100°C (measured by a flow tester: outlet nozzle diameter 1 mm, pressure 2.5 MPa) must be 50 Pa·s or less. Note that "retaining its shape" means that it does not substantially deform or become fluid in the absence of external force, and it may be a solid or natural rubber-like solid that can be deformed or its plasticity measured when an external force is applied.

[0091] The curable silicone composition according to the present invention has the property of rapidly melting and decreasing viscosity as the temperature rises under high temperature and high pressure during the manufacturing process of laminates and the like. Therefore, it is preferable to measure its melt viscosity under high pressure using a flow tester such as a high-pressure flow tester (manufactured by Shimadzu Corporation). Specifically, it is preferable that the melt viscosity of this composition at 100°C, measured using a high-pressure flow tester with an outlet nozzle diameter of 1 mm and a pressure of 2.5 MPa, is 50 Pa·s or less, more preferably 30 Pa·s or less. This is because a melt viscosity within the above range results in good dispensability at 100°C.

[0092] [Manufacturing method and filling form in cartridges, pails, or drums] The curable silicone composition of the present invention can be manufactured by heating and melting the above-mentioned components (A) to (D), component (E), and any other optional components to uniformly mix each component, and then cooling as necessary. However, the method is not limited to this method, and the composition may be manufactured by any method. The mixer that can be used in this manufacturing method is not particularly limited, but examples include batch-type kneaders, Banbury mixers, Henschel mixers, planetary mixers, 2-roll mills, 3-roll mills, Ross mixers, Laboplast mills, etc., equipped with heating and cooling functions, and continuous-type heating and kneading devices such as single-screw extruders and twin-screw extruders equipped with heating and cooling functions. The curable silicone composition of the present invention is particularly suitable for use in which it is filled into cartridges, pails, or drums, heated, and dispensed by a dispenser. Therefore, from the viewpoint of being able to continuously fill the containers, it is particularly preferable to manufacture it using a single-screw or twin-screw continuous mixer.

[0093] The curable silicone composition according to the present invention is particularly preferably used in a form filled in a dispensing cartridge, pail, or drum. Such a curable silicone composition-containing cartridge, pail, or drum is obtained by continuously filling the container with the curable silicone composition by a manufacturing method comprising the following steps P1 and P2. Step P1: A step of mixing the components of the curable hot melt silicone composition at a temperature of preferably 50°C or higher. Step P2: A process in which the heated and melted mixture obtained in Step P1 is discharged from a nozzle and continuously filled into a cartridge, pail, or drum.

[0094] [Process P1] Step P1 is a step in which the constituent components of the composition of the present invention are kneaded while being heated and melted. By heating and kneading a mixture that is meltable by heating at a temperature above its softening point, preferably in the temperature range of 50°C to 200°C, the entire composition is melted or softened and mixed, thereby uniformly mixing the components contained in the mixture. Since the mixture obtained in step P1 is a uniformly mixed composition, it can be filled into a cartridge, pail, or drum in step P2 to produce a cartridge, pail, or drum containing a curable silicone composition for hot dispensing. On the other hand, if the temperature at which the mixture is heated is below the lower limit, the softening of the mixture will be insufficient, and it may be difficult to obtain a melted or softened mixture in which each component is uniformly mixed throughout, even with mechanical force. 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 cannot be obtained, and problems such as poor curing or poor melting may occur during use. Conversely, if the heating temperature of the mixture exceeds the aforementioned upper limit, a hydrosilylation reaction may occur during mixing as an unintended side reaction of the photoactive hydrosilylation catalyst or the thermoplastic resin fine particles containing the platinum-based catalyst, which are component (D). This can cause the entire mixture to thicken significantly or harden, losing its hot-melt properties, or forming a cured product, which is undesirable. Furthermore, with respect to the photoactive hydrosilylation catalyst or the thermoplastic resin fine particles containing the hydrosilylation catalyst, which are component (D), it is preferable, in order to suppress unintended side reactions, to add component (D) after the mixture of other components has been thoroughly mixed, rather than mixing it with the other components from the beginning in step P1, or to lower the heating temperature to a range where mixing is possible when adding component (D).

[0095] As described above, the kneading equipment used in process P1 is not limited and can be selected according to the work efficiency in terms of processing time and the ability to control shear heat generation. In particular, continuous heating kneading equipment such as single-screw extruders or twin-screw extruders equipped with heating and cooling functions is preferred because it allows for short processing times and good work efficiency.

[0096] [Process P2] Step P2 is the process of filling the heated and melted mixture obtained in step P1 into a dispenser container. If a continuous mixing device is used in step P1, continuous filling can be performed, resulting in excellent production efficiency. In this case, a nozzle matching the inner diameter of the cartridge to be filled is attached to the outlet of the continuous mixing device, and by loading the nozzle into the cartridge, the uniformly mixed composition is discharged from the nozzle, automatically filling the cartridge. Once the cartridge is completely filled, it is removed from the nozzle, and the nozzle is continuously loaded into the next cartridge, allowing the filling process to be carried out one after another in accordance with the discharge speed of the composition.

[0097] Process P2 may be performed manually or automated. In the continuous method described above, the filling rate of the mixture obtained in process P1 in process P2 can be designed according to the scale of production. For example, the mixture obtained in process P1 can be continuously filled into cartridges at a supply rate of 1 to 10 kg / hour, but needless to say, the filling conditions are not limited to this. Alternatively, filling may be performed by directly receiving the composition continuously coming out of the kneader into a pail or drum.

[0098] [Dispensing cartridges and their use] The curable silicone composition according to the present invention can be filled into a dispensing cartridge in step P2 or the like, and is suitable for use in hot dispensing. The dispensing cartridge used in step P2 can and preferably be a heat-resistant type. Since the filling and dispensing processes are carried out at around 100°C, a plastic cartridge with heat resistance of around 120°C can be used. Alternatively, a metal cartridge, such as one made of aluminum, may also be used. On the other hand, if a cartridge that does not have heat resistance is used, problems such as deformation of the cartridge may occur when used at high temperatures of 100°C or higher during filling or the heated dispensing described below. Similarly, it is preferable to use a metal pail and drum, and it is preferable to select a type that can be used with the hot melter described later.

[0099] Dispensing cartridges filled with the curable silicone composition can be used with dispensers equipped with a heating unit (temperature control unit), which are commonly available. As described above, the curable silicone composition of the present invention has meltability at 50°C, so by heating the cartridge to 50°C or higher, preferably 50-150°C, and more preferably 80-120°C, using a temperature control unit, it can be smoothly dispensed at a discharge pressure of, for example, about 0.5 MPa, and can be used for hot dispensing. On the other hand, in the case of pails and drums, it is possible to extrude the composition at high temperatures and dispense it from a heat-resistant hose by using, for example, Nordson's hot melter.

[0100] [Other forms of the composition and variations in manufacturing methods] The curable silicone composition according to the present invention preferably takes the form of a dispenser cartridge, pail, or drum, but may take the form of a tablet, pellet, sheet, or film molded product as needed. These molded products, in particular sheets and films made of the curable silicone composition, can be used in a usage mode in which at least one surface of the uncured curable silicone composition sheet or film is brought into close contact with a part or all of a substrate which is an electronic component or its precursor by one or more means selected from a vacuum laminator, vacuum press, and compression molding, and then cured by irradiation with high-energy rays.

[0101] Furthermore, the curable silicone composition according to the present invention may be manufactured using organopolysiloxane resin fine particles as a raw material in step P1, etc. (Method A), or it may be manufactured using a hot-melt solid component obtained by dispersing a solid organopolysiloxane resin at room temperature and optionally a chain-like diorganopolysiloxane in an organic solvent and removing the organic solvent (Hot-Melt Bulk Method) (Method B).

[0102] Specifically, the former (Method A) involves the following steps: Step PA1: A step of mixing organopolysiloxane resin fine particles and other raw materials (which may optionally include functional fillers); Step PA2: A step in which the mixture obtained in Step PA1 is kneaded while being heated and melted at a temperature of 120°C or lower; This is a manufacturing method that includes [something].

[0103] Similarly, the latter (Method B) involves the following steps: Step PB1: A step in which a solution is obtained by dispersing or dissolving a solid organopolysiloxane resin (A) and a chain-like organopolysiloxane (B) in an organic solvent at room temperature, and then removing the organic solvent at a temperature of 150°C or higher to obtain a hot-melt solid; Step PB2: After adding the curing agent (C+D) components to the hot-melt solid obtained in Step PB1, the mixture is kneaded while being heated and melted at a temperature of 120°C or lower; This is a manufacturing method that includes [something].

[0104] The curable silicone composition obtained in the above process may be molded into a sheet or tablet shape, for example, by extruding it between release films, or it may be filled into a dispenser container by extruding the heated and melted mixture obtained in process PA2 or process PB2 from a nozzle and continuously filling it into the aforementioned container (process P2).

[0105] [Curing of curable silicone compositions and manufacture of laminates] When a photoactive hydrosilylation catalyst is used as component (D) of the curable silicone composition of the present invention, thermal curing can be triggered by irradiation with high-energy rays. Several curing methods can be described by combining the dispensing process and the high-energy ray irradiation process. In the dispensing process, the composition is heated to approximately 50-150°C. By irradiating the composition with high-energy rays while dispensing it or immediately after applying it to the substrate, thermal curing can be performed before the composition cools, and a certain degree of thermal curing can be advanced before natural cooling on the substrate. The curing speed of the composition can be precisely controlled by the amount of catalyst and curing retarder added and the amount of high-energy ray irradiation. This is suitable for cases where it is desired to cure the composition in the shape it was dispensed in, and specifically, it can be applied to sealing and encapsulating substrates. Since curing proceeds to a certain extent immediately after the composition is dispensed and adhesion to the substrate occurs, so-called immediate curing and shape fixing of the material can be achieved. If necessary, a completely cured product can be formed by post-curing by exposing the resulting laminate to a temperature of 10°C or higher.

[0106] Alternatively, the composition of the present invention may be dispensed onto a substrate using a dispenser, and then irradiated with high-energy rays after a period of time. In this case as well, since the composition of the present invention retains its shape at 25°C, the dispensed material will not drip or change shape. Furthermore, by pressing a second substrate onto the substrate on which the dispensed composition is placed (preferably by pressing it, i.e., applying external force to create adhesion), the shape of the composition can be changed to form an adhesive layer that connects the two substrates. If both substrates are made of materials that do not transmit light, it is necessary to irradiate them with high-energy rays before pressing them together with the second substrate. On the other hand, if one of the two substrates is a light-transmitting material such as glass, the two substrates may be bonded together before irradiating them with high-energy rays.

[0107] These methods of use produce a laminate having a structure in which at least some or all of the surfaces of two substrates are joined via a cured product made from the composition of the present invention, Step (I): A step of heating the curable silicone composition according to the present invention to 50°C or higher using a dispenser equipped with a heating unit to give it fluidity, and dispensing it onto part or all of the surface of at least one substrate. Step (II): Simultaneously with or after Step (I), a step of irradiating the curable silicone composition dispensed from the dispenser with high-energy rays, either directly or through another substrate, and as necessary. Step (III): A step after step (I) and before or after step (II) in which another substrate is attached to the curable silicone composition dispensed from the dispenser. A manufacturing method having the above characteristics is particularly preferred. Here, by connecting a heatable slot die to the dispenser outlet in step (I), it becomes possible to dispense the material in the form of a film or sheet of a desired thickness, and precision coating is also possible by applying it directly to a substrate. The curable silicone composition according to the present invention, after irradiation with high-energy rays, undergoes a curing reaction over time at room temperature or by heating to form a cured product. Therefore, it may be left at room temperature (around 25°C), or the composition may be cured by exposure to heat of 10°C or higher, preferably 50°C or higher, and more preferably 100°C or higher.

[0108] The above-described method of use and the substrate used in the laminate are components of electronic components, semiconductor devices, or optoelectronic devices, and a substrate having a cured product made from the curable silicone composition according to 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, semiconductor device, or optoelectronic device, or a component thereof.

[0109] In the curable silicone composition of the present invention, when a photoactive hydrosilylation catalyst (D1) is used as component (D), the catalyst can be activated by irradiation with high-energy rays such as ultraviolet light, and a hydrosilylation reaction in the composition can proceed, thereby forming a cured product. The type of high-energy ray is as described above. The irradiation dose varies depending on the type of high-energy ray-activated catalyst, but in the case of ultraviolet light, the cumulative irradiation dose at 365 nm is 100 mJ / cm². 2 ~100J / cm 2 It is preferably within the range of 500 mJ / cm². 2 ~50J / cm 2 It may be within the range of 500 mJ / cm². 2 ~20J / cm 2It may also be within the range of [specify range]. In other words, the curing reactive silicone composition of the present invention can initiate a curing reaction triggered by irradiation with high-energy rays such as ultraviolet light. Furthermore, the curing reaction rate can be controlled to some extent by changing the cumulative irradiation dose. Note that once the hydrosilylation catalyst, which is component (D1), is activated, the curing reaction will proceed over time at room temperature or by heating, even if the irradiation with high-energy rays is stopped, and a cured product will be formed.

[0110] The curing reaction can be carried out in a low-temperature range (15-100°C), including room temperature (25°C). In embodiments of the present invention, "low temperature" refers to, for example, a temperature of 100°C or lower, specifically a temperature range of 15°C to 100°C, and temperatures of 80°C or lower are also selectable. When the reaction of the composition of the present invention (including the semi-cured product) proceeds in the temperature range of 15-100°C, the composition may preferably be left at room temperature (a temperature range that can be reached without heating or cooling, particularly including the temperature range of 20-25°C), cooled to 15°C or lower than room temperature, or heated to 100°C or higher than room temperature. The time required for the curing reaction can be appropriately designed depending on the amount of irradiation with high-energy rays such as ultraviolet light and the temperature. Furthermore, depending on the tolerances in the process and as needed, heating above 100°C may be temporarily performed.

[0111] Furthermore, when (D2) platinum catalyst-containing thermoplastic resin fine particles are used as component (D) of the curable silicone composition of the present invention, the above applies except that the catalyst is activated and the hydrosilylation reaction begins by exposure to a high temperature, such as 130°C or higher, above the melting point or glass transition point of the thermoplastic resin, rather than irradiation with high-energy rays.

[0112] When using component (D2), a characteristic use other than that mentioned in the method of use of the photoactive catalyst-containing composition, which is component (D1), is the molding process. It is well known that liquid thermosetting compositions can be molded by transfer molding or compression molding, and the hot-dispensing composition of the present invention can also be applied to these molding processes as long as a heating unit is available. In these molding processes, the liquid composition is dispensed directly into the molding machine, making it unsuitable for compositions that cannot be cured without irradiation with high-energy rays. However, the curable silicone composition containing component (D2) has the advantage of being suitably usable in these molding processes because the hydrosilylation reaction catalyst is activated by exposure to high temperatures.

[0113] In the case of component (D2), due to its properties, the curing reaction upon exposure to high temperature and adhesion to the adherend proceed simultaneously. Therefore, when manufacturing a laminate having a structure in which at least part or all of the surfaces of two substrates are joined via a cured product made from the composition of the present invention, and component (D) of the curable silicone composition is (D2) platinum catalyst-containing thermoplastic resin fine particles, a manufacturing method having the following steps (I) to (III) is preferred. Step (I): A step of heating a curable silicone composition to 50°C or higher using a dispenser equipped with a heating unit to give it fluidity, and dispensing it onto part or all of the surface of at least one substrate. If necessary, step (II): After step (I), a step of adhering another substrate to the curable silicone composition dispensed from the dispenser, and Step (III): A step of heating the integrated product of the obtained substrate and the curable silicone composition to a temperature of 130°C or higher.

[0114] [Hardness of the cured product and suitable usage] The preferred hardness of the cured product obtained by curing the curable silicone composition of the present invention is classified into two categories depending on its application. When the curable silicone composition of the present invention is used to bond to an adherend on both sides (i.e., as an adhesive), it is preferable that the Type A durometer hardness specified in JIS K 7215-1986 "Durometer Hardness Test Method for Plastics" is 30 or higher. This is because if the hardness is below the above lower limit, the cured product tends to be too soft and brittle. On the other hand, when the application is for substrate sealing or sealing (i.e., as a sealant), it is preferable that the Type A durometer hardness is 40 or higher. This is because if the hardness is below the above lower limit, the surface of the cured product becomes sticky, reducing its handling properties.

[0115] [Uses of the composition / cured product] The curable silicone composition described above has a relatively low tack and low surface stickiness when cured. It can be used as a sealant or encapsulant by extruding it onto a substrate surface at a temperature of 50°C or higher using a hot dispenser and curing it in the manner described above. Furthermore, it can also be used as a bonding layer / adhesive layer between different substrates (components) by adhering it to another substrate (preferably by applying external force to press the substrate against the composition layer to deform the composition layer and cause adhesion) before the extruded composition cools, and then curing it in the manner described above. In other words, the curable silicone composition according to the present invention is suitable as a hot melt adhesive or hot melt encapsulant that has the property of curing triggered by high-energy ray irradiation or temperature. In particular, the uncured / semi-cured composition layer made of the curable silicone composition according to the present invention, and the cured product obtained by curing it, are useful as components for electronic components, semiconductor devices, or optoelectronic devices.

[0116] Specifically, the curable silicone composition according to the present invention has the aforementioned hot-melt properties, excellent handling and curability during melting (hot melting), and excellent color resistance at high temperatures in the cured product obtained by curing this composition. Therefore, it is useful for semiconductor components such as encapsulants and light reflectors for light-emitting / optical devices, and for optoelectronic semiconductors having the cured product. Furthermore, the cured product has excellent mechanical properties, is low-tack and relatively hard, making it suitable as a encapsulant for semiconductors; a encapsulant for power semiconductors such as SiC and GaN; and as an adhesive, potting agent, protective agent, coating agent, and sealing agent for electrical and electronic applications. In particular, it is suitable for use as a sealing agent that requires shape retention after dispensing and as a encapsulant for semiconductors that requires a thick layer. The composition (uncured or semi-cured composition layer) can be adhered to a substrate, and preferably crushed between two substrates by external force to form a film, which can be used as an adhesive layer or a stress buffer layer between two substrates with different coefficients of thermal expansion. Furthermore, the curable silicone composition of the present invention may be a sealant intended for single-sided sealing, or a sealant intended for double-sided sealing involving adhesion between two substrates, and possesses desirable properties suitable for these applications.

[0117] Furthermore, the curable silicone composition of the present invention can be flexibly adapted to desired applications and curing processes by selecting and optimizing component (D), and can therefore be applied to electronic components, semiconductor devices, or optoelectronic devices, or their precursors, in response to a wide range of functional and process requirements.

[0118] The cured product obtained by curing the curable silicone composition of the present invention is not particularly limited in its use, but it can be suitably used as a component for electronic components, semiconductor devices, or optoelectronic devices. It can be suitably used as a encapsulant for semiconductor elements and IC chips, and as an adhesive, bonding agent, or sealing agent for semiconductor devices, and is particularly suitable for applications requiring high heat resistance and light resistance.

[0119] The semiconductor device comprising a component made from a cured product obtained by curing the curable silicone composition of the present invention is not particularly limited, but is preferably a light-emitting semiconductor device such as a light-emitting / optical device, an optical component for a display, a component for a solar panel, and especially a sealing material, case material, or adhesive component used in such devices. Furthermore, since the cured product of the present invention has excellent color resistance at high temperatures, it can be more preferably used as a sealing material, case material, or adhesive component in electronic materials where transparency and light / heat resistance are important.

[0120] As described above, the curable silicone composition of the present invention may be in the form of a tablet, pellet, sheet, or film molded product, and may be arranged as a component for electronic components, semiconductor devices, or optoelectronic devices in a form other than hot dispensing, and used by curing or molding. [Examples]

[0121] The curable silicone composition and its manufacturing method of the present invention will be described in detail below with reference to examples and comparative examples. In the following description, Me, Vi, and Ph in the average unit formulas represent methyl group, vinyl group, and phenyl group, respectively. Furthermore, the melt viscosity, dispensability, 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 by the following method. The results are shown in Table 2.

[0122] [Melting viscosity at 100°C] 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) under a pressure of 2.5 MPa and with a nozzle diameter of 1.0 mm. [Hot dispensing properties (initial)] A cartridge filled with a curable silicone composition was placed in a temperature control unit (THERMO MASTER TCU-02, manufactured by Musashi Engineering Co., Ltd.) attached to a desktop coating robot (SHOTmini200Sx, manufactured by Musashi Engineering Co., Ltd.). The temperature control unit was set to 100°C to warm the cartridge. After the cartridge was sufficiently warmed, a test was conducted in which the cartridge was dispensed onto a glass plate at a pressure of 0.5 MPa using a digital dispenser (ML-606GX, manufactured by Musashi Engineering Co., Ltd.) to determine whether it could be dispensed smoothly. [Hot dispensing properties (100°C - after 5 hours) / Stability of composition during dispensing] A cartridge filled with a curable silicone composition was placed in a temperature control unit (THERMO MASTER TCU-02, manufactured by Musashi Engineering Co., Ltd.) attached to a desktop coating robot (SHOTmini200Sx, manufactured by Musashi Engineering Co., Ltd.). The temperature control unit was set to 100°C and left for 5 hours. After that, 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 Engineering Co., Ltd.) to determine whether or not it could be dispensed smoothly. [Hardness of hardened material] A curable silicone composition was cured under predetermined curing conditions to form a cured product. The hardness of this cured product was measured using a Type A durometer specified in JIS K 7215-1986 "Test Method for Durometer Hardness of Plastics".

[0123] [Reference Examples 1-7: Preparation of Hot-Melt Siloxane Mixtures] In each reference example, the organopolysiloxane resins (a1), (a2), (a') shown below were mixed with linear organopolysiloxanes (b), (b') {hereinafter referred to as components (a1), (a2), (a'), (b), (b')} to prepare hot-melt siloxane mixtures (hereinafter referred to as mixtures 1 to 7). The low molecular weight organopolysiloxane components removed by the method described in the reference example include M4Q structures, etc.

[0124] • Ingredients (a1): At 25°C, it is a white solid, with the average unit formula: (Me2ViSiO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.39 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02 Organopolysiloxane resin represented by (vinyl group content = 1.9% by mass) ·Ingredients (A2): At 25°C, it is a white solid, with the average unit formula: (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02 Organopolysiloxane resin represented by (vinyl group content = 0% by mass) • Component (a'): At 25°C, it is a white solid, with the average unit formula: (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02 Organopolysiloxane resins represented by ·Ingredient (b): Formula:ViMe2SiO(Me2SiO) 800 SiViMe2 Dimethylpolysiloxane with dimethyl vinylsiloxy groups sealed at both ends of the molecular chain (vinyl group content = 0.09% by mass), represented as [formula]. ·Component (b'): Formula: (OMe)3SiO(Me2SiO) 800 Si(OMe)3 Dimethylpolysiloxane with trialkoxysiloxy groups sealed at both ends of the molecular chain, represented as such.

[0125] In each reference example, the amounts (kg) of components (a1), (a2), (a'), (b), and (b') shown in Table 1 were dissolved in 4.00 kg of xylene in a pail using a three-one motor. The resulting solution was fed into a twin-screw extruder set to a maximum temperature of 230°C, and xylene and low molecular weight organopolysiloxane components were removed under a vacuum of -0.08 MPa, yielding hot-melt transparent mixtures 1-7. Mixtures 1-7 were collected in cylindrical pails and cooled to solidify. The amount of volatile components in each mixture was measured under conditions of 200°C for 1 hour, and the results are shown in Table 1 as "Amount of Volatile Components (mass%)". [Table 1]

[0126] [Examples 1-4, Comparative Examples 1-4] In the following examples and comparative examples, in addition to the above-mentioned mixtures 1 to 7 and component (b), the following compounds were used. A twin-screw extruder of the form shown in Figure 1 was used to prepare the compositions for each example. The properties of each curable silicone composition obtained are shown in Table 2. ·Component (c1): Formula: (PhSiO 3 / 2 ) 0.4 (HMe2SiO 1 / 2 ) 0.6 Organohydrogenpolysiloxane represented by (amount of volatile components, i.e., mass loss rate, after aging in an oven at 100°C under atmospheric pressure for 1 hour, is 3.4% by mass) ·Component (c2): Formula: (HMe2SiO 1 / 2 ) 0.52 (Me2SiO 2 / 2 ) 0.15 (SiO 4 / 2 ) 0.33 Organohydrogenpolysiloxane represented by (amount of volatile components, i.e., mass loss rate, after aging in an oven at 100°C under atmospheric pressure for 1 hour, is 2.9% by mass) ·Component (c'): Me3SiO(Me2SiO) 37(MeHSiO) 37 SiMe3 Organohydrogenpolysiloxane represented by (amount of volatile components, i.e., mass loss rate, after aging in an oven at 100°C under atmospheric pressure for 1 hour, is 2.6% by mass) ·Component (c''): Formula: M e3S iO (M e2S iO )29[M e(HS C3H6)S iO ]3S iM e3 Organopolysiloxane containing a 3-mercaptopropyl group, represented by [formula]. • Ingredients (d1): (Methylcyclopentadienyl)trimethylplatinum(IV) complex • Ingredients (d2): Polycarbonate resin particles containing 4000 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex as the platinum content. ·Component (d''): Platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in a 1,3-divinyltetramethyldisiloxane solution ·Ingredient (e): Methyltris-1,1-dimethyl-2-propynyloxysilane (boiling point = 245°C (1013.25 hPa)) • Components (f): Carbon black (Product name: Denka Black 100% Press, manufactured by Denka Co., Ltd.) • Components (f'): Titanium dioxide (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.)

[0127] [Example 1] Mixture 1 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 9.54 kg / hr. Next, a mixture consisting of component (c1) at a rate of 0.31 kg / hr and component (e) at a concentration of 500 ppm relative to the total composition was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) at a rate of 0.15 kg / hr and component (d1) (an amount equivalent to 10 ppm by mass of platinum metal relative to the entire composition) was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0128] [Example 2] Mixture 2 was fed at a rate of 9.52 kg / hr from a hot melter for cylindrical pails (Nordson VersaPail melter, labeled "1" in Figure 1) to a twin-screw extruder (labeled "2" in Figure 1) at 170°C. Next, a mixture consisting of component (c2) at a rate of 0.33 kg / hr and component (e) at a concentration of 500 ppm relative to the total composition was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) at a rate of 0.15 kg / hr and component (d1) (an amount equivalent to 10 ppm by mass of platinum metal relative to the entire composition) was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0129] [Example 3] Mixture 3 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 9.51 kg / hr. Next, a mixture consisting of component (c) at 10.34 kg / hr and component (e) at an amount of 500 ppm relative to the entire composition was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) at a rate of 0.15 kg / hr and component (d1) (an amount equivalent to 10 ppm by mass of platinum metal relative to the entire composition) was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0130] [Example 4] Mixture 4 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 9.41 kg / hr. Next, a mixture consisting of component (c2) at a rate of 0.440 kg / hr and component (e) at a concentration of 500 ppm relative to the total composition was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) 0.15 kg / hr and component (d1) (an amount equivalent to 10 ppm by mass of platinum metal relative to the entire composition) was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0131] [Example 5] Mixture 3 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 9.41 kg / hr. Next, a mixture consisting of component (c1) at 0.34 kg / hr, component (e) at an amount equivalent to 500 ppm of the total composition, and component (f) at 0.1 kg / hr was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) 0.15 kg / hr, component (d2) (an amount equivalent to 10 ppm by mass of platinum metal relative to the entire composition), and component (f) 0.1 kg / hr was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0132] [Example 6] Mixture 4 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 8.47 kg / hr. Next, a mixture consisting of component (b) 0.085 kg / hr, component (c2) 0.396 kg / hr, component (e) in an amount equivalent to 500 ppm of the total composition, and component (f') 1.0 kg / hr was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) at a rate of 0.05 kg / hr and component (d2) (an amount equivalent to 10 ppm by mass of platinum metal relative to the entire composition) was fed through pump 3-b in Figure 1 (the input temperature was set to 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0133] [Comparative Example 1] Mixture 5 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 9.40 kg / hr. Next, a mixture consisting of component (c') at a rate of 0.450 kg / hr and component (e) at a concentration of 500 ppm relative to the total composition was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) at a rate of 0.15 kg / hr and component (d) (an amount equivalent to 10 ppm by mass of platinum metal relative to the entire composition) was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0134] [Comparative Example 2] Mixture 1 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 9.54 kg / hr. Next, a mixture consisting of component (c1) at a rate of 0.310 kg / hr and component (e) at a concentration of 3500 ppm relative to the total composition was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) 0.15 kg / hr and component (d'') (an amount equivalent to 4 ppm by mass of platinum metal relative to the entire composition) was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0135] [Comparative Example 3] Mixture 6 was fed at 170°C into a twin-screw hot melter for cylindrical pails (Nordson VersaPail melter, labeled "1" in Figure 1) at a rate of 9.70 kg / hr. Next, a mixture consisting of component (c'') 0.150 kg / hr, 2-hydroxy-2-methylpropiophenone (in an amount equivalent to 1000 ppm by mass relative to the entire composition) was fed through pump 3-a shown in Figure 1. The set temperature of the feeding section was 150°C. Next, a mixture consisting of component (b) 0.15 kg / hr, 2,6-di-tert-butyl-4-methylphenol (in an amount equivalent to 100 ppm by mass relative to the entire composition) was fed through pump 3-b in Figure 1 (the temperature set at the input section was 80°C), and degassing, melting, and kneading were performed with a vacuum of -0.08 MPa inside the extruder. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0136] [Comparative Example 4] Mixture 7 was fed at 170°C into a twin-screw extruder (Figure 1, "2") from a hot melter for cylindrical pails (Nordson VersaPail melter, "1" in Figure 1) at a rate of 9.74 kg / hr. next, (OMe)3SiO(Me2SiO) 800 Si(OMe)3 A mixture consisting of 0.15 kg / hr of trimethoxysiloxy group-bound dimethylpolysiloxane at both ends of the molecular chain, 0.110 kg / hr of isobutyltrimethoxysilane, and tetra-tertiary butyltitanium (in an amount equivalent to 800 ppm by mass as titanium metal relative to the total composition) was fed through pump 3-b in Figure 1 (the temperature of the input section was set to 80°C), and degassed melt-mixing was performed in the extruder under a vacuum of -0.08 MPa. The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened substance at this temperature. A nozzle with a diameter of 2.5 cm and a length of 13 cm was attached to the outlet of the twin-screw extruder, and the obtained mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, Nordson).

[0137] [Table 2] (*) Ultraviolet light with a wavelength of 365 nm, irradiation dose of 10 J / cm² 2 The irradiation was applied in such a manner that it resulted in the following:

[0138] [Summary] The curable silicone compositions of Examples 1 to 6 according to the present invention utilize a specific solid organopolysiloxane resin and a linear organopolysiloxane, and employ a photoactive hydrosilylation reaction catalyst (Examples 1 to 4) or hydrosilylation catalyst-containing polycarbonate resin fine particles (Examples 5 and 6). By controlling the melt viscosity characteristics, excellent hot-dispensability is achieved without compromising storage stability during dispensing, and good curability is triggered by UV irradiation or high-temperature exposure. Furthermore, the resulting cured silicone products have low surface tackiness and are relatively hard, making them suitable for applications such as protecting semiconductor devices.

[0139] On the other hand, Comparative Example 1 was a curable silicone composition using a photoactive hydrosilylation catalyst, but its melt viscosity was too high, making dispensing impossible at temperatures around 100°C. While the curable silicone composition of Comparative Example 2 achieved excellent dispensability, it was found to be extremely difficult to ensure storage stability during dispensing because it used a conventional hydrosilylation catalyst. Meanwhile, Comparative Examples 3 and 4 were curable silicone compositions using different curing systems than those in the examples. Comparative Example 3, which was UV curable, had difficulty forming a hard cured product, and Comparative Example 4, which was room temperature humidity curing, required a long time to cure.

[0140] [Reference examples 1~4] The curable silicone compositions of Examples 5 and 6 each contain (f) carbon black as a black pigment and (f') titanium dioxide as a white pigment, respectively, and yield black and white cured products. They also contain a catalyst (d2) that is activated as a hydrosilylation reaction catalyst upon exposure to high temperatures, and are therefore usable in the following dispensing and molding methods.

[0141] [Example 1 (Hot Dispensing Method)] A 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 Engineering Co., Ltd.) attached to a desktop coating robot (SHOTmini200Sx, manufactured by Musashi Engineering Co., Ltd.). The temperature of the temperature control unit was set to 100°C, and the cartridge was heated. After the cartridge was sufficiently heated, it was dispensed onto a glass plate at a pressure of 0.5 MPa using a digital dispenser (ML-606GX, manufactured by Musashi Engineering Co., Ltd.). The composition maintained its shape without dripping. The resulting laminate was then exposed to 160°C for 1 hour to obtain a cured product. The obtained cured product adhered firmly to the glass substrate.

[0142] [Reference Example 2 (Hot Dispensing Method)] In the same manner as in Reference Example 1, a second glass plate was placed on top of the curable silicone composition (Example 6) dispensed from a digital dispenser onto a glass plate and manually pressed apart. The resulting laminate was then exposed to 160°C for 1 hour to obtain a cured product. The resulting cured product adhered firmly to the two glass substrates.

[0143] [Reference Example 3 (Transfer Molding Method)] A cartridge filled with the curable silicone composition obtained in Example 5 was placed in a temperature control unit (THERMO MASTER TCU-02, manufactured by Musashi Engineering Co., Ltd.) attached to a desktop coating robot (SHOTmini200Sx, manufactured by Musashi Engineering Co., Ltd.). The temperature of the temperature control unit was set to 100°C, and the cartridge was heated. After the cartridge was sufficiently heated, the composition was applied to a transfer molding machine at a pressure of 0.5 MPa using a digital dispenser (ML-606GX, manufactured by Musashi Engineering Co., Ltd.). A tetrafluoroethylene resin release film was placed between the mold and the machine, and the mixture was molded onto a 10cm x 10cm aluminum substrate at a temperature of 160°C for 10 minutes, resulting in a clean molded body.

[0144] [Reference Example 4 (Compression Molding Method)] In the same manner as in Reference Example 3, the composition was applied from a digital dispenser into a compression molding machine, and a tetrafluoroethylene resin release film was placed between the machine and the mold. The mixture was then molded onto a 10cm x 10cm aluminum substrate at a temperature of 160°C for 10 minutes, resulting in a clean molded body.

[0145] [Reference Example 5 (Hot Dispensing + Slot Die Method)] A slot die with a heatable outlet gap of 100 μm was attached to the tip of the digital dispenser of Reference Example 1, and the curable silicone composition obtained in Preparation Example 1 was dispensed and applied to a glass plate with the die temperature set to 100°C. This composition was then irradiated with ultraviolet light at a wavelength of 365 nm at a dose of 10 J / cm². 2 The material was irradiated in such a manner and then exposed to 100°C for 1 hour to obtain a cured product. The resulting cured product adhered firmly to the glass substrate, and its film thickness was 100 μm, the same as when it was applied. [Explanation of symbols]

[0146] 1: Hot melter 2: Extruder 3-a: Pump 3-b: Pump 3-c: Vacuum pump 4: Discharge port (Optional: A nozzle for cartridge filling may be attached)

Claims

1. (A) 100 parts by mass of an organopolysiloxane resin that is solid at 25°C and contains the components (A1) and (A2) listed below in a mass ratio of 20:80 to 90:10, with each component not having hot-melt properties on its own. (A1) Having a hardening-reactive functional group containing a carbon-carbon double bond within the molecule, and SiO ４／２ An organopolysiloxane resin containing at least 20 mol% or more of the siloxane units represented by the formula, (A2) It does not have a hardening-reactive functional group containing a carbon-carbon double bond within the molecule, and SiO ４／２ An organopolysiloxane resin containing at least 20 mol% or more of the siloxane units represented by the formula, (B) 10 to 100 parts by mass of a linear organopolysiloxane that is liquid at 25°C and has a curing-reactive functional group containing at least two carbon-carbon double bonds within the molecule. (C) An organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, in an amount such that the number of hydrogen atoms bonded to silicon atoms per alkenyl group bonded to silicon atoms in the entire composition is 0.5 to 20.

0. (D) A catalyst for hydrosilylation reactions that is inert at room temperature but exhibits activity in the composition upon external energy stimulation, (D1) A catalyst for hydrosilylation reactions that exhibits activity in the composition upon irradiation with high-energy rays, and (D2) Thermoplastic resin fine particles containing a catalyst for hydrosilylation reaction, using a thermoplastic resin having a glass transition temperature in the range of 130 to 200°C and containing polycarbonate resin in at least a portion thereof. One or more catalysts for hydrosilylation reactions selected from the following: Catalytic amount A curable silicone composition comprising the above, having hot-melt properties as a whole, and having a melt viscosity at 100°C (measured by a flow tester: outlet nozzle diameter 1 mm, pressure 2.5 MPa) of 50 Pa·s or less.

2. Furthermore, the curable silicone composition according to claim 1, further comprising (E) a curing retarder for hydrosilylation reactions having a boiling point of 200°C or higher at atmospheric pressure, in an amount of 1 to 5000 ppm relative to the total mass of the composition.

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

4. The above (A1) component is (A1-1) given by the following average unit formula: (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ SiO ３／２ ) ｃ (SiO ４／２ ) ｄ (R ２ O １／２）ｅ (In the formula, each R １ R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, provided that all R in one molecule １ Of these, 1 to 12 mol% are alkenyl groups; each R ２ a, b, c, d, and e are numbers satisfying the following conditions: 0.10 ≤ a ≤ 0.60, 0 ≤ b ≤ 0.70, 0 ≤ c ≤ 0.80, 0.2 ≤ d ≤ 0.65, 0 ≤ e ≤ 0.05, where c + d > 0.20 and a + b + c + d = 1. It is an organopolysiloxane resin that is represented as such and does not possess hot-melt properties on its own, The above (A2) component is (A2-1) the following average unit formula: (R ３ ３ SiO １／２ ) ｆ (R ３ ２ SiO ２／２ ) ｇ (R ３ SiO ３／２ ) ｈ (SiO ４／２ ) ｉ (R ２ O １／２）ｊ (In the formula, each R ３ R is a monovalent hydrocarbon group that independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond; ２ (where 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) It is an organopolysiloxane resin that is represented as such and does not possess hot-melt properties on its own, The above component (B) has the following structural formula: R ４ ３ SiO(SiR ４ ２ O) ｋ SiR ４ ３ (In the formula, each R ４ R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, provided that R in one molecule ４ (At least two of them are alkenyl groups, and k is a number between 20 and 5,000.) A curable silicone composition according to any one of claims 1 to 3, wherein the linear diorganopolysiloxane is represented by .

5. A hot-melt adhesive or hot-melt sealant comprising the curable silicone composition according to claims 1 to 4.

6. A cartridge containing a curable silicone composition, wherein the curable silicone composition according to claims 1 to 4 is filled into a dispensing cartridge, pail, or drum.

7. A cured product obtained by curing the curable silicone composition according to claims 1 to 4.

8. An electronic component, semiconductor device, or optoelectronic device having the cured product described in claim 7.

9. A laminate comprising a base material and an uncured portion or layer on part or all of the surface of the base material, comprising the curable silicone composition of claims 1 to 4.

10. A laminate comprising two or more substrates, wherein at least part or all of the surfaces of the two substrates are joined together via the cured product described in claim 7.

11. The laminate according to claim 10, wherein the laminate is one or more selected from electronic components, semiconductor devices, or optoelectronic devices.

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