Curable silicone composition, cured body therefrom, and manufacturing process for said composition

Abstract

[Problem] This invention provides a curable polysiloxane composition, etc., which has good hot melt properties and excellent melting characteristics, thus exhibiting excellent workability and curing characteristics during sealing, and the cured product has excellent mechanical strength and bonding strength to the substrate, making it suitable for use as a sealant for semiconductor devices. [Solution] A curable polysiloxane composition and its use, characterized in that it contains (A) a hot meltable MDT-type organic polysiloxane resin having a specific siloxane unit ratio, (B) an organic hydrosiloxane compound, (C) a hydrosilicification catalyst, and (D) a functional inorganic filler comprising 400 to 3000 parts by mass relative to 100 parts by mass of components (A) to (C), and is solid at 25°C and hot meltable at temperatures below 200°C.

Description

[Technical Field]

[0001] This invention relates to a curable polysiloxane composition that has good thermal fusibility and forms a cured material with excellent mechanical strength and bonding strength to a substrate. Furthermore, this invention also relates to a cured material composed of the polysiloxane composition, a method for molding the cured material, and a semiconductor device having the cured material. [Previous Technology]

[0002] Because curable polysiloxane compositions can form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency after curing, they can be applied in many industrial fields. Compared with other organic materials, the cured products of this type of curable polysiloxane composition are generally less prone to discoloration, and their physical properties decrease less, making them suitable for use as sealants in optical materials and semiconductor devices. On the other hand, in recent years, considering factors such as operability, thermosetting curable polysiloxane compositions have been widely used as sealants in optical materials and semiconductor devices.

[0003] Epoxy sealants are commonly used in the semiconductor device industry. It is known that epoxy materials have poorer heat resistance compared to polysiloxane materials. On the other hand, the mechanical strength of cured polysiloxane materials is sometimes inferior to that of epoxy materials.

[0004] In recent years, with the trend of miniaturization and high output of semiconductor devices, the applications of polysiloxane sealants with excellent heat resistance have expanded. In Patent Documents 1-3, the applicant proposed a heat-melt curable polysiloxane composition for molding, which is mainly composed of resin-like polysiloxane and can be used for the aforementioned purposes. Similarly, Patent Document 4 discloses a heat-melt curable composition that contains a mixture of organic framework and polysiloxane components, and Patent Documents 5 and 6 disclose a white curable composition using resin-like polysiloxane with a specific structure.

[0005] However, when using such polysiloxane-based curable compositions as sealants, the mechanical strength of the cured product is inferior compared to that of epoxy sealants. Therefore, there is a need for heat-melt curable polysiloxane compositions that offer superior mechanical strength in addition to workability and heat resistance. (Preferred Art Documents, Patent Documents)

[0006] Patent Document 1: International Publication No. 2018 / 030288; Patent Document 2: International Publication No. 2018 / 235491; Patent Document 3: Japanese Patent Application Publication No. 2001-19933; Patent Document 4: International Publication No. 2013 / 051600; Patent Document 5: Japanese Patent Application Publication No. 2015-74751; Patent Document 6: Japanese Patent Application Publication No. 2013-221075. [Summary of the Invention]

[0007] The problem that the invention aims to solve

[0008] The object of the present invention is to provide a curable polysiloxane composition that has good thermal fusibility and excellent melting and curing characteristics, thus exhibiting excellent workability during sealing. Simultaneously, the cured material possesses excellent mechanical strength and bonding strength to the substrate, making it suitable for use as a sealant in semiconductor devices. Furthermore, the present invention provides a cured material formed by curing the curable polysiloxane composition, a component for a semiconductor device comprising the cured material, a semiconductor device having the cured material, and a method for molding the cured material. Technical Means for Solving the Problem

[0009] The inventors have conducted research and found that the above-mentioned problems can be solved by the following hot-melt curable polysiloxane composition, which uses a hot-melt organic polysiloxane resin containing specific siloxane units as the main agent and has a high content of functional inorganic fillers.

[0010] More specifically, the above-mentioned problem can be solved by the following curable polysiloxane composition, characterized by containing the following (A) to (D): (A)(R13SiO)1 / 2)a(R22SiO2 / 2)b(R2SiO3 / 2)c(SiO4 / 2)d(R3O1 / 2)e (In the formula, each R1 is an independent monovalent hydrocarbon group with 1 to 10 carbon atoms, wherein at least two of all R1 in a molecule are alkenyl groups; each R2 is an independent monovalent hydrocarbon group without alkenyl groups and with 1 to 10 carbon atoms; each R3 is a hydrogen atom or an alkyl group with 1 to 10 carbon atoms; a, b, c, d and e are numbers that satisfy the following relationships: 0.10≤a≤0.40, 0.05≤b≤0.50, 0.30≤c≤0.90, 0≤d≤0.20, 0≤e≤0.05, where a+b+c+d=1) The hot-melt organopolysiloxane resin, (B) an organohydrosiloxane compound having at least two silicon-bonded hydrogen atoms in one molecule, (C) a hydrosilicification catalyst in an amount sufficient to carry out the hydrosilicification of the aforementioned reactive polysiloxane composition, and (D) a functional inorganic filler in a quantity of 400 to 3000 parts by mass relative to 100 parts by mass of components (A) to (C); is solid at 25°C and hot-melt at temperatures below 200°C.

[0011] The composition may further contain an organosiloxane compound comprising a specific siloxane unit and containing more than 10% by mass of an alkenyl group, or may contain any other arbitrary components. In addition, the composition may be in any form, such as granules, pellets, or flakes.

[0012] Furthermore, the above-mentioned problems can be solved by the cured product of the above-mentioned curable polysiloxane composition, its use as a component for semiconductor devices, and the molding method of the cured product. Effects of the Invention

[0013] The curable polysiloxane composition of the present invention has the following advantages: it has good hot melt properties and excellent melting characteristics, thus exhibiting excellent gap filling properties during melting and excellent workability during sealing, and excellent curing characteristics, making it easy to apply in molding processes. Furthermore, the cured product of the composition of the present invention has high hardness at room temperature to high temperature, a low coefficient of linear expansion, and excellent mechanical strength represented by high flexural strength, thus exhibiting strength and toughness, and excellent bonding strength to the substrate, making it suitable for use as a sealant for semiconductor devices. In particular, the curable polysiloxane composition of the present invention, possessing these characteristics, is preferably applied to semiconductor devices in which semiconductor elements are integrally sealed by bottom filling and injection molding.

[0014] Furthermore, this curable polysiloxane composition has the advantage of being able to be produced using only a simple mixing process, enabling highly efficient manufacturing. Moreover, the cured material of the present invention can be used as a component of a semiconductor device, and by using the molding method of the present invention, it has the advantage of being able to efficiently manufacture such cured materials for corresponding applications.

Implementation Method

[0016] [Cureable Polysiloxane Composition] The curable polysiloxane composition of the present invention is characterized by containing the following (A) to (D): (A) (R13SiO1 / 2)a(R22SiO2 / 2)b(R2SiO3 / 2)c(SiO4 / 2)d(R3O1 / 2)e (In the formula, each R1 is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms, wherein at least two of all R1 in a molecule are alkenyl groups; each R2 is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms without alkenyl groups; each R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d, and e are numbers satisfying the following relationships: 0.10≤a≤0.40, 0.05≤b≤0.50, 0.30≤c≤0.90, 0≤d≤0.20, 0≤e≤0.05, where a+b+c+d=1) represents a hot-melt organopolysiloxane resin; (B) an organohydrosiloxane compound having at least two silicon-bonded hydrogen atoms in a molecule; (C) a hydrosilicifying catalyst in an amount sufficient to carry out the hydrosilicification of the aforementioned reactive polysiloxane composition; (D) The present invention comprises 400 to 3000 parts by mass of a functional inorganic filler relative to 100 parts by mass of components (A) to (C); and is solid at 25°C and has thermal fusibility at temperatures below 200°C, and may contain other arbitrary components. The components and arbitrary components of the composition are described below. Furthermore, unless otherwise defined in this invention, "average particle size" refers to the primary average particle size.

[0017] Unless otherwise specified in this invention, "having hot melt properties" means having a softening point of 50°C or higher, a melt viscosity (preferably less than 1000 Pa·s) at 180°C, and the property of flowing. On the other hand, when the softening point is 200°C or higher, it is above the general operating temperature for molding applications, etc., and is therefore defined as "not having hot melt properties".

[0018] [(A) Component] Component (A) is one of the main components of this composition and is represented by the average unit formula: (R13SiO1 / 2)a(R22SiO2 / 2)b(R2SiO3 / 2)c(SiO4 / 2)d(R3O1 / 2)e. It is an organopolysiloxane that is solid at room temperature and has the thermal melting property of softening with increasing temperature. Here, component (A) is an MDT-type hot-melt organic polysiloxane resin component, one of its characteristics being the ratio of the siloxane unit represented by R13SiO1 / 2 (hereinafter, sometimes referred to as "M unit"), the siloxane unit represented by R22SiO2 / 2 (hereinafter, sometimes referred to as "D unit"), and the siloxane unit represented by R13SiO1 / 2 (hereinafter, sometimes referred to as "T unit"), i.e., the values ​​of a, b, and c are within a specific range, and the molecule has at least two alkenyl groups bonded to the M unit.

[0019] In the formula, each R1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, wherein at least two of all R1 in a molecule are alkenyl groups. R1 is preferably selected from alkyl groups such as methyl, aryl groups such as phenyl, aralkyl groups such as benzyl, and alkenyl groups such as vinyl, which may be arbitrarily substituted with halogen atoms such as fluorine. Industrially, it is preferably selected from methyl, phenyl, and alkenyl groups described below. Each R2 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms without an alkenyl group, for example, alkyl groups such as methyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. Industrially, it is preferably methyl or phenyl. Furthermore, from the viewpoint of imparting better hot-melt properties to this component, at least a portion of R2 is preferably aryl, and more preferably phenyl. Each R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, methyl, ethyl, or propyl.

[0020] From the viewpoint of the curability of this composition, it is preferable that at least two of R1 in component (A) are alkenyl groups, and that R1 contains alkenyl groups in a range of 10 to 20 mol% relative to all silicon atoms bonded with monovalent hydrocarbon groups within the molecule (i.e., the sum of R1 and R2). This is because if the content of alkenyl groups in component (A) is within the aforementioned range, the strength of the cured material can be sufficiently improved, resulting in a strong and tough cured material without brittleness. Examples of alkenyl groups in component (A) include vinyl, allyl, butenyl, pentenyl, and hexenyl.

[0021] (A) The component is an MDT-type hot-melt organosiloxane resin component containing M units, D units, and T units within a specific range. Specifically, in the formula, a represents the ratio of siloxane units represented by the general formula: R13SiO1 / 2, and satisfies 0.10≦a≦0.40, preferably 0.10≦a≦0.30. The reason is that when a is below the upper limit of the above range, the obtained cured material has good hardness at room temperature, and when it is above the lower limit of the lower range, good hot-melt properties can be obtained. In addition, in the formula, b represents the ratio of siloxane units represented by the general formula: R22SiO2 / 2, and satisfies 0.05≦b≦0.50, more preferably 0.05≦b≦0.40. The reason is that when b is below the upper limit of the above range, the hardness of the obtained hardened material is sufficiently high, and when it is above the lower limit, the strength of the obtained hardened material is improved. Furthermore, c is the number representing the ratio of siloxane units in the general formula: R2SiO3 / 2, and it is a number satisfying 0.30≦c≦0.90, preferably 0.35≦c≦0.85. The reason is that when c is above the lower limit of the above range, the obtained hardened material has good hardness at room temperature; on the other hand, when c is below the upper limit of the above range, the obtained hardened material has good mechanical strength. Furthermore, d is the number representing the ratio of siloxane units in the general formula: SiO4 / 2, and it is a number satisfying 0≦d≦0.20, preferably 0≦b≦0.10. The reason is that when d is below the upper limit of the above range, the obtained hardened material has good mechanical strength. Furthermore, e represents the ratio of units represented by the general formula R₂O₁ / ₂, and is a number that satisfies 0 ≤ e ≤ 0.05. This is because when e is below the upper limit of the aforementioned range, the resulting hardened material exhibits good hardness at room temperature. Additionally, the sum of a, b, c, and d in the formula is 1.

[0022] (A) The component itself exhibits heat-melting properties, preferably being non-flowable at 25°C, and having a melt viscosity at 150°C of 8000 Pa·s or less, more preferably 5000 Pa·s or less, and even more preferably in the range of 10~3000 Pa·s. Non-flowability means not flowing under no-load conditions, for example, indicating a state below the softening point determined by the ring and ball method of hot melt adhesives as specified in JIS K 6863-1994 "Test Method for Softening Point of Hot Melt Adhesives". That is, in order to be non-flowable at 25°C, the softening point must be higher than 25°C.

[0023] In addition, as described above, component (A) is a solid at room temperature. Therefore, from the viewpoint of operability when mixed with other components, it is preferable to use it as a resin in the form of microparticles or as a liquid mixture dissolved in other components required in this composition.

[0024] When component (A) is used in the form of microparticles, the particle size is not limited, but the average primary particle size is preferably in the range of 1~5000 µm, 1~500 µm, 1~100 µm, 1~20 µm, or 1~10 µm. This average primary particle size can be obtained by observation, for example, using an optical microscope or SEM. The shape of the microparticle-like component (A) is not limited, and examples include spherical, spindle-shaped, plate-shaped, needle-shaped, and irregular shapes. From the viewpoint of uniform melting, spherical or perfectly spherical shapes are preferred. In particular, by making component (A) into perfectly spherical microparticles, the process of producing the composition described below by powder mixing and melt kneading can be carried out efficiently.

[0025] When microparticles of component (A), there is no limitation on the manufacturing method, and well-known methods can be used. In addition, to obtain component (A) in microparticle form, it is possible and more preferably to microparticle the silicon hydrocracking catalyst described later as component (C) together with component (A).

[0026] As a method for microparticle-forming component (A), specific examples include pulverizing component (A) which is fixed at room temperature using a pulverizer, and directly microparticle-forming it in the presence of a solvent. The pulverizer is not limited; examples include roller mills, ball mills, jet mills, turbine mills, and planetary mills. Furthermore, the aforementioned component (A) can be directly microparticle-forming in the presence of a solvent, for example, by spraying using a spray dryer or by forming microparticles using a twin-shaft mixer and belt dryer. When microparticle-forming component (A), it is preferable to microparticle the orthospherical hot-melt organopolysiloxane resin obtained by spraying using a spray dryer.

[0027] By using a spray dryer or similar equipment, it is possible to manufacture component (A) which has a spherical shape and an average primary particle size of 1 to 500 µm. Furthermore, the heating and drying temperatures of the spray dryer must be appropriately set based on the heat resistance of the organopolysiloxane resin microparticles. Additionally, to prevent secondary agglomeration of the organopolysiloxane resin microparticles, it is preferable to control the temperature of the organopolysiloxane resin microparticles below their glass transition temperature. The organopolysiloxane resin microparticles thus obtained can be recovered using a hydrocyclone, bag filter, or similar equipment.

[0028] To obtain a uniform composition (A), solvents may be used in the above process within a range that does not impair the hardening reaction. Solvents are not limited, but examples include aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-heptane; aromatic hydrocarbons such as toluene, xylene, and mesitylene; ethers such as tetrahydrofuran and dipropyl ether; silicates 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.

[0029] Component (A) can be used in a solution that is soluble in component (B) described later. Component (B) is a polysiloxane compound and is liquid at room temperature, therefore exhibiting a certain degree of mutual solubility with component (A). By adding 10 to 50 parts by mass of component (B) relative to 100 parts by mass of component (A), component (A) can be dissolved. By liquefying component (A), the composition described later can be produced efficiently through powder mixing and melt kneading.

[0030] [(B) Component] Component (B) is the crosslinking agent of this composition, which is an organohydrogen polysiloxane compound having at least two silicon-bonded hydrogen atoms in one molecule. Its structure is not particularly limited and can be linear, branched, cyclic or resinous. From the viewpoint of obtaining excellent curing properties of the composition, it is preferred to be an organohydrogen polysiloxane with a hydrogen diorganosiloxy unit (MH unit, where R is an independent monovalent organic group) represented by HR2SiO1 / 2 at the end.

[0031] (B) Preferably, the component is an organopolysiloxane having two or more silicon atoms bonded to hydrogen atoms per molecule, and 20-70 moles of all organic groups bonded to silicon atoms being phenyl. (B) The silicon atoms in the component have two or more hydrogen atoms bonded to hydrogen atoms per molecule, thus ensuring sufficient cross-linking for curing and resulting in a hardened product with good hardness. Furthermore, this is because when the phenyl content is above the lower limit of the aforementioned range, the resulting cured product exhibits good mechanical strength at high temperatures; conversely, when it is below the upper limit of the aforementioned range, the resulting cured product exhibits good mechanical strength.

[0032] In addition, as an organic group bonded to silicon atoms in component (B), examples of alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, and xylyl; and aralkyl groups such as benzyl and phenethyl, which are monovalent hydrocarbon groups without aliphatic unsaturated bonds, are preferred to be phenyl or alkyl groups with 1 to 6 carbon atoms.

[0033] As such component (B), the following two examples are possible: (B-1) a linear organopolysiloxane represented by the general formula: HR42SiO(R42SiO)nSiR42H, and (B-2) a branched organopolysiloxane represented by the average unit formula: (R4SiO3 / 2)p(R42SiO2 / 2)q(HR42SiO1 / 2)r(SiO4 / 2)s(XO1 / 2)t. It is preferred to use a combination of these two components (B).

[0034] In the formula, R4 is the same or different phenyl or alkyl with 1 to 6 carbon atoms. Examples of alkyl groups for R4 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, cyclopentyl, and cyclohexyl. In addition, the content of phenyl in all R4 is in the range of 30 to 70 mol%.

[0035] Furthermore, in the formula, n is an integer in the range of 5 to 1,000. In addition, in the formula, p is a positive number, q is 0 or a positive number, r is a positive number, s is 0 or a positive number, t is 0 or a positive number, and q / p is a number in the range of 0 to 10, r / p is a number in the range of 0.1 to 5, s / (p+q+r+s) is a number in the range of 0 to 0.3, and t / (p+q+r+s) is a number in the range of 0 to 0.4.

[0036] In this (B) component, from the viewpoint of easily controlling the curing speed of the composition and the crosslinking density of the obtained cured product, it is preferable to use it in combination with components (B-1) and (B-2). As a preferred ratio of the two components, relative to each alkenyl group of the composition, it is in the range of (B-1):(B-2) = 0.05~0.6:0.4~0.95, more preferably 0.05~0.5:0.5~0.95, and even more preferably 0.05~0.4:0.5~0.95.

[0037] [(C) Component] Component (C) is a catalyst for initiating the hydrosilicification reaction of the composition. Examples of catalysts include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Considering the viewpoint of significantly promoting the curing of the composition, platinum-based catalysts are preferred. Examples of such platinum-based catalysts include platinum micropowder, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, platinum-alkenyl silicate complexes, platinum-olefin complexes, platinum-carbonyl complexes, and catalysts that disperse or encapsulate these platinum-based catalysts using thermoplastic resins such as silicone resin, polycarbonate resin, and acrylic resin. Platinum-alkenyl silicate complexes are particularly preferred. Examples of alkenyl siloxanes include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenyl siloxanes in which one methyl portion of the methyl group is replaced by ethyl, phenyl, or the like, and alkenyl siloxanes in which the vinyl group of the methyl group is replaced by allyl, hexenyl, or the like. In particular, considering the good stability of the platinum-alkenyl siloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred. Furthermore, non-platinum metal catalysts such as iron, ruthenium, and iron / cobalt can also be used as catalysts to promote the hydrosilylation reaction.

[0038] Furthermore, from the viewpoint of improving the stability, operability, and shelf life of the composition during production, component (C) is preferably a thermoplastic resin microparticle containing a platinum catalyst. This can be either microparticles in which the platinum catalyst is dissolved or dispersed in the thermoplastic resin, or microcapsule microparticles in which the platinum catalyst serves as the core within the shell of the thermoplastic resin. Examples of platinum catalysts include platinum black, platinum-supported carbon micropowder, platinum-supported silicon dioxide micropowder, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complexes, and platinum alkenyl silicate complexes. The thermoplastic resin is not particularly limited as long as it is substantially impermeable to the platinum catalyst at least during the production and storage of the composition, and substantially insoluble in the organopolysiloxane of the main component of the composition. The softening point or glass transition point of the thermoplastic resin is preferably 80°C or higher, more preferably 120°C or higher. Specifically, polysiloxane resin, epoxy resin, acrylic resin, and methylcellulose polycarbonate resin are preferably used. The softening point, the temperature at which the resin begins to flow due to its own weight or surface tension, can be determined by observing the crushed particles under a microscope while heating at a constant rate. The glass transition point can be determined using DSC (Differential Scanning Calorimeter). In this invention, both the softening point and the glass transition point are preferably 120°C or higher. This is because if the softening point or glass transition point of the thermoplastic resin is less than 120°C, there is a concern that platinum components may begin to dissolve during the process of uniformly mixing the components described later. Furthermore, the average particle size of the thermoplastic microparticles containing the platinum catalyst 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. The reason is that it is difficult to prepare thermoplastic resin microparticles containing platinum catalysts with an average particle size smaller than the lower limit of the above range. On the other hand, the reason is that if the upper limit of the above range is exceeded, the dispersibility in the curing polysiloxane resin composition will decrease.

[0039] There is no limitation on the method for preparing such thermoplastic resin microparticles containing platinum catalysts. Examples include previously known chemical methods such as interfacial polymerization or in-situ polymerization, and physical / mechanical methods such as coagulation or liquid drying. In particular, liquid drying and gas-phase drying are preferred because microcapsule microparticles with narrow particle size distributions can be obtained relatively easily. Microparticles obtained by these methods can also be used directly, but in order to obtain curable polysiloxane compositions with excellent storage stability, it is preferable to remove the platinum catalyst adhering to their surface by washing them with a suitable cleaning solvent. Here, a suitable cleaning solvent refers to one that has the property of not dissolving the thermoplastic resin but dissolving the platinum catalyst. Examples of such cleaning solvents include alcohols such as methanol and ethanol, and low molecular weight organic polysiloxanes such as hexamethyldisiloxane. The ratio of the catalyst to the thermoplastic resin in the hydrosiliconization reaction varies considerably depending on the manufacturing method of the granules, and therefore cannot be specifically limited. However, it is preferable that the content of the platinum catalyst relative to the thermoplastic resin is 0.01% by mass or more. This is because if the content of the platinum catalyst is less than 0.01% by mass, the physical properties of the cured product will be impaired if the thermoplastic resin microparticles containing the platinum catalyst are not present in large quantities in this composition.

[0040] The amount of catalyst added for the silicon hydrocracking reaction is the amount of catalyst, preferably the amount of metal atoms in the range of 0.01 to 500 ppm, 0.01 to 100 ppm or 0.01 to 50 ppm relative to the entire composition.

[0041] [(D) Component] Component (D) is a functional inorganic filler that provides a curable polysiloxane composition that, upon curing, forms a cured product with excellent hardness and toughness from room temperature to high temperature. In this invention, from the viewpoint of achieving high mechanical strength (especially low average coefficient of linear expansion, flexural strength, etc.) in the obtained cured product, the content of component (C) is preferably in the range of 400 to 3000 parts by mass relative to 100 parts by mass of components (A) to (C), and more preferably in the range of 500 to 3000 parts by mass or 800 to 3000 parts by mass. Furthermore, considering the viewpoint of achieving a low average coefficient of linear expansion in the cured product, the content of component (D) is preferably 50% by volume or more of the total composition, more preferably 60% by volume or more, more preferably 70% by volume or more, and particularly preferably in the range of 80 to 95% by volume.

[0042] To achieve the above-mentioned mixing amount and to obtain a hardened product with a low average coefficient of linear expansion, component (D) is preferably treated with a specific surface treatment agent, particularly a surface treatment agent with a content of 0.1 to 2.0% by mass, 0.1 to 1.0% by mass, and 0.2 to 0.8% by mass relative to the total mass of component (D). Treating component (D) with the above-mentioned amount of surface treatment agent has the advantage of being able to stably mix component (D) in the composition at a high volume percentage. Furthermore, the surface treatment method is arbitrary, and desired methods such as uniform mixing using mechanical force (dry mixing) or wet mixing using solvents can be employed.

[0043] Examples of such surface treatment agents include methylhydropolysiloxanes, silicone resins, metal soaps, silane coupling agents, perfluoroalkyl silanes, and perfluoroalkyl phosphate salts, etc., and fluorinated compounds, with polysiloxane-based surface treatment agents being particularly preferred. Furthermore, when silane-based surface treatment agents such as methyltrimethoxysilane or phenyltrimethoxysilane are selected as the surface treatment agent for component (D), in addition to potentially impairing the overall hot melt properties of the composition, it may also be impossible to stably mix component (D) to the stated volume percentage. Moreover, when alkyltrialkoxysilanes having long-chain alkyl groups such as octyl are selected as surface treatment agents, there is a tendency to maintain the hot melt properties of the composition and the mixing stability of component (D), but the strength of the hardened product obtained by hardening the composition of the present invention may deteriorate, leading to cracking and poor molding problems.

[0044] Here, examples of surface treatment agents, i.e., organosilicone compounds, include low molecular weight organosilicone compounds such as silanes, silazanes, siloxanes, or similar compounds, as well as organosilicone polymers or oligomers such as polysiloxanes, polycarbosiloxanes, or similar compounds. A preferred example of a silane is a so-called silane coupling agent. Representative examples of such silane coupling agents include alkyltrialkoxysilanes (methyltrimethoxysilane, vinyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, or similar compounds), and trialkoxysilanes containing organic functional groups (glycidoxypropyltrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, methoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, or similar compounds). Examples of preferred siloxanes and polysiloxanes include hexamethyldisiloxane, 1,3-dihexyl-tetramethyldisiloxane, single-terminated (trialkoxysilyl) polydimethylsiloxane, single-terminated (trialkoxysilyl) dimethylvinyl single-terminated (trialkoxysilyl) polydimethylsiloxane, single-terminated (trialkoxysilyl) organofunctional single-terminated (trialkoxysilyl) doubly terminated (trialkoxysilyl) polydimethylsiloxane, organofunctional doubly terminated (organofunctional) polydimethylsiloxane, or similar compounds. When using siloxanes, the number of siloxane bonds, n, is preferably in the range of 2 to 150. Examples of preferred silazanes include hexamethyldisilazane, 1,3-dihexyl-tetramethyldisilazane, or similar compounds. A preferred polycarbosiloxane may be a polymer with Si-CC-Si bonds in its main chain.

[0045] Preferred polysiloxane surface treatment agents include, for example, polysiloxane surface treatment agents having at least one polysiloxane structure and a hydrolyzable silyl group within the molecule. Preferably, polysiloxane surface treatment agents having at least one polysiloxane structure and a hydrolyzable silyl group within the molecule are used, for example, organopolysiloxanes with a straight-chain alkoxysilane terminus represented by structural formula (1): R'n(RO)3-nSiO-(R'2SiO)m-SiR'n(RO)3-n or structural formula (2): R'3SiO-(R'2SiO)m-SiR'n(RO)3-n. In the formula, R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (= methyl, ethyl, or propyl), and R' is individually an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen-substituted aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and examples of the same groups as above can be given. n is a number in the range of 0 to 2, m is a number in the range of 2 to 200, and m can also be a number in the range of 2 to 150.

[0046] This (D) component is preferably at least one inorganic filler that does not have a softening point between room temperature and 200°C. It can also be a component that improves the workability of the composition and gives the hardened form of the composition mechanical and other properties. Examples of inorganic fillers as (D) components include reinforcing fillers, white pigments, thermally conductive fillers, electrically conductive fillers, phosphors, and mixtures of at least two of these. To achieve a high volume percentage of filler, it is preferable to contain a reinforcing filler with an average particle size of 10.0 µm or more. In addition, examples of organic fillers that can be used in conjunction with (D) components include polysiloxane resin fillers, fluoropolymer fillers, and polybutadiene resin fillers. Furthermore, the shape of these fillers is not particularly limited and can be spherical, spindle-shaped, flat, needle-shaped, plate-shaped, or amorphous.

[0047] (D) Preferably, at least 50% of all components (D) are inorganic fillers with an average particle size of 10.0 µm or more. Especially considering the small rate of change in rigidity and storage modulus at room temperature to high temperature, spherical inorganic fillers with an average particle size of 10.0 µm or more are preferred. Compared to components (A) to (C), this type of inorganic filler can be formulated or filled in larger quantities, providing tangible benefits such as improved mechanical strength of the hardened material and reduced average coefficient of linear expansion. On the other hand, to impart or improve the light reflection characteristics, electrical conductivity, thermal conductivity, fluorescence characteristics, and stress relief characteristics of the composition of the present invention, inorganic or organic fillers with an average particle size of 5 µm or less can be formulated.

[0048] When this composition is used as a sealant, protective agent, adhesive, light-reflecting material, etc., from the viewpoint of giving the hardened material mechanical strength and improving its protective or adhesive properties, it is preferable to formulate a reinforcing filler as component (E). Examples of such reinforcing fillers include: smoked silica, precipitated silica, fused silica, calcined silica, smoked titanium dioxide, quartz, calcium carbonate, diatomaceous earth, alumina, aluminum hydroxide, zinc oxide, zinc carbonate, glass beads, glass powder, talc, clay and mica, kaolin, silicon carbide, silicon nitride, aluminum nitride, carbon black, graphite, titanium dioxide, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, cellulose, aromatic polyamide, etc. In addition, the surface treatment of these reinforcing fillers can also be performed using organoalkoxysilanes such as methyltrimethoxysilane; organohalosilanes such as trimethylchlorosilane; organosilazanes such as hexamethyldisilazane; and siloxane oligomers such as α,ω-silanol-terminated dimethylsiloxane oligomers, α,ω-silanol-terminated methylphenylsiloxane oligomers, and α,ω-silanol-terminated methylvinylsiloxane oligomers. In addition, as reinforcing fillers, fibrous inorganic fillers such as calcium metasilicate, potassium titanate, magnesium sulfate, sepiolite, hard calcium silicate, aluminum borate, rock wool, glass fiber, carbon fiber, asbestos fiber, metal fiber, wollastonite, terephthalite, sepiolite, aluminum borate whiskers, potassium titanate fiber, calcium carbonate whiskers, titanium oxide whiskers, and ceramic fiber can also be used; fibrous fillers such as aromatic polyamide fiber, polyimide fiber, and poly(p-phenylenebenzobisazole) fiber can also be used. Alternatively, talc, kaolin clay, calcium carbonate, zinc oxide, calcium silicate hydrate, mica, glass flakes, glass powder, magnesium carbonate, silicon dioxide, titanium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, silicon nitride, and pulverized forms of the above fibrous fillers, as well as plate-shaped or granular fillers, may be used.

[0049] In particular, considering the viewpoint of imparting hardness to the hardened material at room temperature to high temperature, in this composition, 50% by mass or more of all (D) components are preferably spherical silicon dioxide or aluminum oxide (alumina) with an average particle size of 10.0 µm or more.

[0050] (D) The component may also contain polysiloxane microparticles, which can improve stress relief properties or be adjusted as desired. Examples of polysiloxane microparticles include non-reactive silicone resin microparticles and polysiloxane elastomer microparticles. Considering the viewpoint of improving softness or stress relief properties, polysiloxane elastomer microparticles are preferred.

[0051] Polysiloxane elastomer microparticles are cross-linked products of linear organosiloxanes mainly composed of diorganosiloxane units (D units). Polysiloxane elastomer microparticles can be prepared by cross-linking reactions of organosiloxanes, such as hydrosilicification or condensation reactions of silanol groups. Specifically, they can be appropriately obtained by cross-linking organohydrogen polysiloxanes with silanized hydrogen atoms on the side chains or at the ends with organosiloxanes with unsaturated hydrocarbon groups such as alkenyl groups on the side chains or at the ends, catalyzed by hydrosilicification. Polysiloxane elastomer microparticles can take various shapes, such as spherical, flat, and irregular shapes. From the viewpoint of dispersibility, spherical shapes are preferred, and even more preferably, perfectly spherical shapes. Commercially available products of this type of polysiloxane elastomer microparticle include, for example, Dow Corning Toray's "Trefil E series" and "EP Powder series," and Shin-Etsu Chemical Co., Ltd.'s "KMP series." Furthermore, polysiloxane elastomer microparticles can also undergo surface treatment. Additionally, acrylonitrile-butadiene rubber, isoprene, styrene-butadiene rubber, and ethylene-propylene rubber can be used as elastomer microparticles.

[0052] Furthermore, when this composition is used as a wavelength conversion material for LEDs, a phosphor can also be mixed as component (D) to convert the emission wavelength from the optical semiconductor element. There are no particular limitations on the phosphor used; examples include yellow, red, green, and blue phosphors composed of oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, and oxysulfide phosphors, which are widely used in light-emitting diodes (LEDs). Examples of oxide phosphors include YAG-type green to yellow phosphors containing cerium ions (yttrium, aluminum, garnet); TAG-type yellow phosphors containing cerium ions (tungsten, aluminum, garnet); and silicate-type green to yellow phosphors containing cerium and europium ions. Examples of oxynitride phosphors include SiAlON-type red to green phosphors containing europium ions (silicon, aluminum, oxygen, nitrogen). Examples of nitride-based fluoresces include red-emitting fluoresces of calcium, strontium, aluminum, silicon, and nitrogen (CASN type). Examples of sulfide-based fluoresces include green-emitting fluoresces of ZnS type containing copper and aluminum ions. Examples of oxide-based fluoresces include red-emitting fluoresces of Y₂O₂S type containing europium ions. Two or more of these fluoresces can also be combined in this composition.

[0053] Furthermore, in order to give the hardened material thermal or electrical conductivity, the composition may also contain a thermally conductive or electrically conductive filler. Examples of such thermally conductive or electrically conductive fillers include metal powders such as gold, silver, nickel, copper, and aluminum; metal powders such as gold, silver, nickel, copper, tin, lead, zinc, bismuth, and antimony deposited or electroplated on the surface of powders such as ceramics, glass, quartz, and organic resins; metal compounds such as alumina, magnesium oxide, aluminum nitride, boron nitride, and zinc oxide; graphite; and mixtures of two or more of these. When the composition is to have electrical insulation properties, metal oxide powders or metal nitride powders are preferred, especially alumina powder, zinc oxide powder, or aluminum nitride powder.

[0054] In addition, to give the hardened material color, this composition may also contain a coloring agent. Examples of such coloring agents include black titanium dioxide, asphalt (the residue from the distillation of tar obtained by the dry distillation of organic substances such as petroleum, coal, and wood), carbon black, acetylene black, and iron oxide. Acetylene black is preferred when reducing the content of metallic impurities. In addition, it may also contain black dyes such as anthraquinone dyes (sometimes referred to as "anthraquinone"), azo dyes, diazo dyes, and chromium zirconia dyes. When used in combination with yellow dyes such as methylene dyes, diazo dyes, azocobalt zirconia dyes, and azochromium zirconia dyes, the color can be close to that of a black pigment.

[0055] Furthermore, this composition may contain any thermally expandable filler. By formulating a thermally expandable filler, the volume expansion rate of the composition of the present invention can be improved, and the uneven distribution of the composition can be reduced. The aforementioned thermally expandable filler is preferably a core-shell structure, and the shell of the core-shell structure contains a volatile expanding agent. Here, the volatile expanding agent refers to a substance that generates gas at a temperature below the softening point of the shell. The thermally expandable filler has a structure in which a volatile expanding agent is contained inside a shell with gas barrier properties as a core agent. As the aforementioned volatile expanding agent becomes gaseous due to heat, the aforementioned shell can soften and expand. Such a component is exemplified by, for example, Japanese Patent Application Publication No. 2020-084094, and can be obtained from products such as FN-100SSD and FN-80GSD manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.

[0056] When the hardened product obtained by hardening this composition is used in magnetic components such as powder magnetic cores, coils, and electromagnetic wave shielding materials, it may also contain magnetic particles as component (C). These magnetic particles contain one or more elements selected from the group consisting of Fe, Cr, Co, Ni, Ag, and Mn. In particular, as soft magnetic particles, they may contain magnetic particles including iron (Fe), Fe-Si alloys, Fe-Al alloys, Fe-Ni alloys, Fe-Co alloys, Fe-Si-Al alloys, Fe-Si-Cr alloys, Fe-Cr alloys, carbonyl iron, stainless steel, etc. Considering availability, they may contain magnetic particles containing carbonyl iron. These magnetic particles may also be surface-treated with silane compounds, titanate compounds, aluminate compounds, or their partial hydrolysates, similar to the inorganic fillers described above, which can prevent the deactivation of the hardening catalyst and crosslinking agent and improve storage stability. Furthermore, these magnetic particles can have a surface coating layer containing a silicone polymer by means of, for example, the method described in Japanese Patent Application Publication No. 2021-036013.

[0057] [(E) Components] In addition, this composition may contain an organosiloxane compound containing an alkenyl group of 10% by mass or more in one molecule as component (E), represented by (R13SiO1 / 2)a'(R22SiO2 / 2)b'(R2SiO3 / 2)c'(SiO4 / 2)d'(R3O1 / 2)e' (wherein, each R1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, at least 2 of all R1 in one molecule are alkenyl groups, each R2 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms without alkenyl groups; each R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

[0058] This component (E) is an organosiloxane compound containing a certain amount or more of alkenyl groups within its molecule, which functions as an adjuster for crosslinking density. Specifically, by using it in combination with components (A) to (C) above, the crosslinking density of the cured product of this composition can be increased, its mechanical strength can be improved, and the melt viscosity of the obtained thermoplastic curable polysiloxane composition can be reduced, thereby improving workability and gap filling properties.

[0059] In the formula, each R1, R2, and R3 is an independent basis identical to the one described above. Examples of similar bases can be given. a', b', c', d', and e' are numbers that satisfy the following relations: 0.40≦a'≦0.80, 0≦b'≦0.90, 0≦c'≦0.60, 0≦d'≦0.50, 0≦e'≦0.05, where a'+b'+c'+d'=1.

[0060] Considering the viewpoint of improving the mechanical strength of the hardened product obtained by curing the present composition, it is preferable that at least two of R1 in component (E) are alkenyl groups, and that the R1 in the molecule contains alkenyl groups in the range of 10% by mass or more, preferably 10 to 40% by mass. This is because when the content of alkenyl groups in component (E) is within the aforementioned range, the strength of the hardened product can be sufficiently improved, resulting in a strong and tough hardened product without brittleness. Examples of alkenyl groups in component (E) include vinyl, allyl, butenyl, pentenyl, and hexenyl.

[0061] In the formula, a' is a number representing the ratio of siloxane units as expressed in the general formula: R13SiO1 / 2, and it is a number that satisfies 0.40≦a'≦0.90, preferably 0.50≦a'≦0.85. This is because when a' is below the upper limit of the above range, the strength of the obtained hardened material is good, and when a' is above the lower limit of the lower range, the effect of reducing the melt viscosity of the composition is sufficient. Furthermore, in the formula, b' is a number representing the ratio of siloxane units as expressed in the general formula: R22SiO2 / 2, and it is a number that satisfies 0≦b'≦0.50. This is because when b' is below the upper limit of the above range, the effect of improving the strength of the obtained hardened material is sufficient. Furthermore, c' is a number that satisfies the ratio of siloxane units represented by the general formula: R2SiO3 / 2, and is a number that satisfies 0 ≤ c' ≤ 0.60. This is because when c' is below the upper limit of the above range, the mechanical strength of the obtained cured material is good. Additionally, d' is a number that represents the ratio of siloxane units represented by the general formula: SiO4 / 2, and is a number that satisfies 0 ≤ d' ≤ 0.50. This is because when d' is below the upper limit of the above range, the mechanical strength of the obtained cured material is good. Furthermore, e' is a number that represents the ratio of units represented by the general formula: R2O1 / 2, and is a number that satisfies 0 ≤ e' ≤ 0.05. This is because when e' is below the upper limit of the above range, the hardness of the obtained cured material at room temperature is good. Additionally, the sum of a', b', c', and d' in the formula is 1.

[0062] This component (E) has the above-mentioned structure and is therefore liquid at room temperature, and is particularly preferably viscous at 25°C with a viscosity of 10,000 mPa·s or less.

[0063] In addition, this composition may contain (F) a hardening delay agent, (G) a tackifier and (H) an organic wax as other arbitrary components, without prejudice to the purpose of the present invention.

[0064] [(F) component] (F) component is a hardening delay agent, especially when the composition is hardened by the hydrosilicification reaction, it can effectively suppress side reactions and further improve the storage stability of the composition of the present invention and the usable time when heated and melted.

[0065] There are no particular limitations on the structure and type of the curing delay agent that can be used. It can be selected from known inhibitors of silane reaction, such as alkynols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; alkenyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; low molecular weight siloxanes containing alkenyl groups such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; and alkynoxysilanes such as methyl-tris(1,1-dimethyl-2-propynoxy)silane and vinyl-tris(1,1-dimethylpropynoxy)silane.

[0066] (F) It is particularly preferable to use a compound with a boiling point of 200°C or higher at atmospheric pressure. From the viewpoint of homogenization, the composition of the present invention can be manufactured through processes such as melt mixing of the composition accompanied by heating. If a compound with a lower boiling point is used as a curing retardant, some or all of the curing retardant may volatilize during the melt mixing process, failing to achieve the target curing retardation effect for the final curable polysiloxane composition. Furthermore, methyl-tris(1,1-dimethyl-2-propynoxy)silane has a boiling point of 245°C at atmospheric pressure, and can be cited as an example of a preferred component (F).

[0067] (F) The amount of component used is arbitrary, but it is preferably in the range of 1 to 10,000 ppm in terms of mass relative to the whole composition.

[0068] [(G) component] The (G) component is a thickener, and an example is an organosilicone compound having at least one alkoxy group bonded to a silicon atom in one molecule. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy, with methoxy being particularly preferred. In addition, examples of groups other than the alkoxy group in the organosilicone compound that are bonded to a silicon atom include halogen-substituted or unsubstituted monovalent hydrocarbon groups such as alkyl, alkenyl, aryl, aralkyl, and haloalkyl; glycidoxyalkyl groups such as 3-glycidoxypropyl and 4-glycidoxybutyl; epoxycyclohexylalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl and 3-(3,4-epoxycyclohexyl)propyl; epoxyalkyl groups such as 3,4-epoxybutyl and 7,8-epoxyoctyl; monovalent organic groups containing an acrylic group such as 3-methacryloxypropyl; and hydrogen atoms. The organosilicone compound preferably has a group that can react with the alkenyl or silicon-bonded hydrogen atom in the composition; specifically, it preferably has a silicon-bonded hydrogen atom or an alkenyl group. Furthermore, considering good adhesion to various substrates, the organosilicone compound preferably has at least one monovalent organic group containing an epoxy group per molecule. Examples of such organosilane compounds include organosilanes, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of the organosiloxane oligomer or alkyl silicate include linear, partially branched linear, branched, cyclic, and network structures, with linear, branched, and network structures being particularly preferred. Examples of organosilicone compounds include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; siloxane compounds in which one molecule has at least one silicon atom bonded to an alkenyl group or a silicon atom bonded to a hydrogen atom and a silicon atom bonded to an alkoxy group; mixtures of silane compounds or siloxane compounds having at least one silicon atom bonded to an alkoxy group and siloxane compounds in which one molecule has at least one silicon atom bonded to a hydroxyl group and a silicon atom bonded to an alkenyl group; and organoalkoxysilanes containing amino groups and those containing... A reaction mixture of an epoxy-containing organic alkoxysilane, an organic compound having at least two alkoxysilyl groups in one molecule and containing bonds other than silicon-oxygen bonds between these silyl groups, represented by the general formula: RanSi(ORb)4-n (where Ra is a monovalent epoxy-containing organic group, Rb is an alkyl group with 1 to 6 carbon atoms or a hydrogen atom, and n is a number in the range of 1 to 3), a reaction mixture of a vinyl-containing silicate oligomer (including those with chain or cyclic structures) and an epoxy-containing trialkoxysilane, polymethyl silicate, polyethyl silicate, and epoxy-containing polyethyl silicate. The tackifier is preferably a low-viscosity liquid, the viscosity of which is not limited, but is preferably in the range of 1 to 500 mPa·s at 25°C.In addition, the content of the tackifier is not limited, but it is preferably in the range of 0.01 to 10 parts by mass relative to the total 100 parts by mass of the composition.

[0069] In this invention, a preferred tackifier is, for example, a reaction mixture of an organoalkoxysilane containing an amino group and an organoalkoxysilane containing an epoxy group. This component improves the initial adhesion to various substrates in contact with the curing polysiloxane composition during curing, and particularly improves low-temperature adhesion to uncleaned adherends. Such a reaction mixture is disclosed in Japanese Patent Publication No. 52-8854 or Japanese Patent Application Publication No. 10-195085.

[0070] Examples of alkoxysilanes containing an organic group containing an amino group that constitute this component include: aminomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)aminomethyltributoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and 3-anilinepropyltriethoxysilane.

[0071] In addition, examples of organoalkoxysilanes containing epoxy groups include: 3-glycidoxyprolyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane.

[0072] The ratio of the alkoxysilanes having an amino group to the alkoxysilanes having an epoxy group, in molar ratio, is preferably in the range of (1:1.5) to (1:5), and more preferably in the range of (1:2) to (1:4). This component can be readily synthesized by mixing the alkoxysilanes having an amino group and the alkoxysilanes having an epoxy group as described above, and reacting them at room temperature or under heating.

[0073] In particular, the curable thermoplastic polysiloxane composition of the present invention preferably contains a general formula generated by cyclization, particularly by alcohol exchange reaction, when an alkoxysilane having an organic group containing an amino group reacts with an alkoxysilane having an organic group containing an epoxy group, as described in Japanese Patent Application Publication No. 10-195085: [Chemical Formula 1] {wherein, R1 is alkyl, alkenyl or alkoxy, R2 is the same or different selected from the general formula: [Chemical Formula 2] (wherein, R4 is an alkyl or alkoxyalkyl, R5 is a monovalent hydroxyl, R6 is an alkyl, R7 is an alkyl, R8 is an alkyl, alkenyl or acetyl, a is 0, 1 or 2), and R3 is the same or different hydrogen atom or alkyl} representing a carbasilatrane derivative. Examples of such carbocyclic rodenticide silicon derivatives include those represented by the following structures, which contain silicon atoms bonded to alkoxy groups or silicon atoms bonded to alkenyl groups in a single molecule. [Chemical Formula 3] (where Rc is a group selected from methoxy, ethoxy, vinyl, allyl, and hexenyl groups.)

[0074] Furthermore, in this invention, the rodenticide silica derivative represented by the following structural formula can also be used as a thickener. [Chemical Formula 4] In the formula, R1 is the same or different hydrogen atom or alkyl group, and R1 is preferably a hydrogen atom or methyl group. In addition, R2 in the above formula is the same or different group selected from the group consisting of hydrogen atom, alkyl group and alkoxysilyl group represented by the general formula: -R4-Si(OR5)xR6(3-x), wherein at least one R2 is the alkoxysilyl group. Examples of alkyl groups of R2 include methyl group. In addition, in the alkoxysilyl group of R2, R4 is a divalent organic group, and examples include alkyl or alkoxyalkyl, preferably vinyl, propenyl, butenyl, methyleneoxypropenyl, and methyleneoxypentenyl. In addition, R5 is an alkyl group with 1 to 10 carbon atoms, preferably methyl or ethyl. Furthermore, R6 in the formula is a substituted or unsubstituted monovalent hydrocarbon group, preferably methyl. Additionally, x in the formula is 1, 2, or 3, preferably 3.

[0075] Examples of alkoxysilyl groups as the organic groups containing this type of R2 include: -(CH2)2Si(OCH3)2(CH2)2Si(OCH3)2CH3 -(CH2)3Si(OC2H5)2(CH2)3Si(OC2H5)(CH3)2 -CH2O(CH2)3Si(OCH3)3 -CH2O(CH2)3Si(OC2H5)3 -CH2O(CH2)3Si(OCH3)2CH3 -CH2O(CH2)3Si(OC2H5)2CH3 -CH2OCH2Si(OCH3)2CH2OCH2Si(OCH3)(CH3)2

[0076] In the above formula, R3 is at least one group selected from the group consisting of substituted or unsubstituted monovalent hydrocarbon groups, alkoxy groups having 1 to 10 carbon atoms, glycidoxyalkyl groups, epoxyalkylalkyl groups, and aceoxyalkyl groups; examples of monovalent hydrocarbon groups of R3 include alkyl groups such as methyl; examples of alkoxy groups of R3 include methoxy, ethoxy, and propoxy; examples of glycidoxyalkyl groups of R3 include 3-glycidoxypropyl; examples of epoxyalkylalkyl groups of R3 include 4-epoxyalkylbutyl and 8-epoxyalkyloctyl; examples of aceoxyalkyl groups of R3 include ethoxypropyl and 3-methpropenylaceoxypropyl. R3 is preferably alkyl, alkenyl, or alkoxy, and more preferably alkyl or alkenyl, especially preferably a group selected from methyl, vinyl, allyl, and hexenyl groups.

[0077] There is no particular limitation on the amount of component (G). However, considering the viewpoint of improving adhesion to difficult-to-bond substrates, it is preferably in the range of 0.1 to 1.0% by mass of the total composition, and more preferably in the range of 0.2 to 1.0% by mass. Furthermore, relative to a total of 100 parts by mass of components (A) and (B), the amount of component (G) can be in the range of 5 to 50 parts by mass, or in the range of 5 to 40 parts by mass.

[0078] [(H) Component] Component (H) is a thermoplastic microparticle other than component (A), specifically an organic wax with a melting point in the range of 30~160°C. Examples of this (H) component include one or more of various thermoplastic synthetic resins, waxes, and fatty acid metal salts. This wax component can form a melt with low kinematic viscosity and excellent fluidity at high temperatures (150°C). Furthermore, by using it together with components (A) to (C), the wax component within the melt formed by this composition can rapidly expand throughout the entire composition at high temperatures, thus achieving the following effects: reducing the viscosity of the substrate surface and the composition as a whole after use, rapidly reducing surface friction of the substrate and the molten composition, and significantly improving the overall fluidity of the composition. Therefore, only a very small amount needs to be added relative to the total amount of other components to significantly improve the viscosity and fluidity of the molten composition.

[0079] The wax component only needs to meet the above-mentioned conditions of dropping point and kinematic viscosity at melting point to be petroleum-based waxes such as paraffin wax, natural waxes such as carnauba wax, synthetic waxes such as lignite ester wax, etc. However, from the perspective of the technical effect of the present invention, it is preferable to be a hot-melt component composed of fatty acid metal salts or fatty acid esters of erythritol derivatives, especially metal salts of higher fatty acids such as stearic acid, palmitic acid, oleic acid, isononanoic acid, neopentyl tert-stearate, dinepentyl tert-stearate, glyceryl tri-18-hydroxystearate, and neopentyl tert-stearate. Here, there is no particular limitation on the types of the above-mentioned fatty acid metal salts, but preferred examples include alkali metal salts such as lithium, sodium, and potassium; alkaline earth metal salts such as magnesium, calcium, and barium; or zinc salts.

[0080] As a wax component, it is preferably a fatty acid metal salt or erythritol derivative with a free fatty acid content of 5.0% or less, preferably 4.0% or less, or 0.05 to 3.5%. For example, at least one stearate metal salt can be used as such a component. Specifically, it is best to use a hot-melt component with a melting point of less than 150°C, selected from calcium stearate (melting point 150°C), zinc stearate (melting point 120°C), magnesium stearate (melting point 130°C), neopentyl tert-stearate (melting point 60-70°C), neopentyl tert-stearate (melting point 55-61°C), and neopentyl tert-stearate (melting point 62-67°C).

[0081] When the total composition is 100 parts by weight, the amount of wax component used is in the range of 0.01 to 5.0 parts by weight, or 0.01 to 3.5 parts by weight or 0.01 to 3.0 parts by weight. When the amount of wax component used exceeds the upper limit, the adhesion and mechanical strength of the cured product obtained by the particulate curable polysiloxane composition of the present invention may sometimes be insufficient. In addition, when the amount used is less than the lower limit, sufficient fluidity may not be achieved when heated and melted.

[0082] Furthermore, without prejudice to the purpose of this invention, this composition may also contain, as other arbitrary components, heat-resistant agents such as iron oxide (red lead), cerium oxide, cerium dimethylsilyl alcohol, cerium salts of fatty acids, cerium hydroxide, and zirconium compounds; as well as dyes, pigments other than white, flame retardants, heat insulation agents such as aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphonium nitride, ion traps / pH adjusters such as magnesia pyroxene, bismuth oxide, and yttrium oxide, flame retardants such as aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphonium nitride, hindered phenolic compounds, etc. The following substances are considered as potential sources of flame retardants: hindered amine compounds, sulfide compounds, and other antioxidants; pure iron, silicon steel, iron-cobalt alloys, iron-nickel alloys, iron-chromium alloys, iron-aluminum alloys, carbonyl iron, stainless steel, or composite materials containing one or more of these substances; soft magnetic particles; inorganic flame retardants (such as hydrated metal compounds like aluminum hydroxide); halogen flame retardants; phosphorus flame retardants; organometallic salt flame retardants; polysiloxane oil; polysiloxane rubber; polyisoprene; 1,2-polybutadiene; 1,4-polybutadiene; styrene-butadiene rubber; and acrylonitrile-butadiene rubber. Carboxyl-terminated butadiene acrylonitrile rubber, polychloroprene, poly(oxypropylene), poly(oxytetramethylene) glycol, polyolefin glycol, poly-ε-caprolactone and other thermoplastic elastomers, polysulfide rubber, fluororubber and other low-stress agents, barium titanate (BaTiO3), strontium titanate (SrTiO3), lead zirconate titanate (Pb(Zr,Ti)O3, also known as PZT), aluminum oxide (Al2O3, also known as aluminum oxide), zirconium oxide (ZrO2, also known as zirconium dioxide), magnesium oxide (MgO, also known as magnesium monoxide), silicon oxide (SiO2) Other names include: silicon dioxide, titanium dioxide (TiO2), aluminum nitride (AlN), silicon nitride (Si3N4), silicon carbide (SiC), barium calcium zirconate titanate (BCTZ), polyvinylidene fluoride and other dielectric ceramics; copper chloride, cuprous iodide, copper acetate, cerium stearate and other metal salt stabilizers; hindered amines, hindered phenols, sulfur-containing compounds, acrylates, phosphorus organic compounds and other antioxidants and heat stabilizers; benzophenones, salicylates, benzotriazoles and other ultraviolet absorbers, weathering agents, light stabilizers, etc.

[0083] [Use of this composition] This composition can be produced in any of the following forms: granules, pellets, balls, or flakes, through its manufacturing process. Here, the granules or pellets can be further processed into ingots using known methods to produce pellets or ingots for use.

[0084] Here, "pellet" and "ingot" are common or general terms for granular ingots formed from resin compositions. The shape of the pellets / ingots is not limited, and they are usually spherical, ellipsoidal, or cylindrical. In addition, the size of the pellets is not limited, for example, having an average particle size or equivalent spherical diameter of 500 µm or more, or having an average particle size or equivalent spherical diameter of 1 mm or more.

[0085] [Method for Manufacturing a Curable Polysiloxane Composition] This composition can be manufactured into a granular composition by mixing components (A) to (D) and any other components at a temperature below 100°C. The powder mixer used in this manufacturing method is not limited, and examples include single-shaft or bi-shaft continuous mixers, twin-drum mixers, Ross mixers, Hobart mixers, alginate impression powder mixers, planetary mixers, kneading mixers, laboratory mixers, small grinders, and Henschel mixers, with laboratory mixers, small grinders, and Henschel mixers being preferred. The curable polysiloxane composition can be manufactured into powder using such mixers, and by pressing the aforementioned granular composition using a pressing machine or similar device, a curable ingot composition for transfer molding can be produced.

[0086] Especially when this composition is intended to be used for compression molding, it is preferable to use a single-shaft or dual-shaft continuous mixer, twin-drum mixer, Ross mixer, kneading mixer, etc., at a temperature of 150°C or below to melt and knead the mixture to form a homogenized granular or sheet-like form before use.

[0087] The reason is that there is less material movement in compression molding, therefore, unlike transfer molding, a completely homogenized composition is required. For example, sheets composed of curable polysiloxane compositions with an average thickness of 100~1000 µm have thermosetting properties and are heat-curable at high temperatures, thus offering excellent workability and melting characteristics, especially advantageous for compression molding or vacuum lamination. Furthermore, particles composed of curable polysiloxane compositions with a particle size of 0.1~10 mm have thermosetting properties and are heat-curable at high temperatures, making them particularly suitable for compression molding of large-area sealing or bonding applications. Such sheet-like or granular compositions can be produced by: melting and mixing the curable granular composition obtained by the aforementioned method using a continuous mixer, or by separately feeding the constituent components of this composition to a continuous mixer for melt mixing, followed by sheeting or granulation using the method described later.

[0088] [Method for Manufacturing Curable Polysiloxane Sheets] The curable polysiloxane sheets of the present invention are characterized in that they contain components (A) to (D) as essential components and other components as optional components, and the manufacturing method comprises the following processes 1 to 3. Process 1: A process of heating, melting and mixing the constituent components of the curable polysiloxane composition. Process 2: A process of obtaining a heated and melted mixture in a film-to-film lamination process 1 having at least one peelable surface. Process 3: A process of forming a curable polysiloxane sheet with a specific film thickness from a laminate obtained in a roller stretching process 2. Here, "having heat-melting properties" means having a softening point in the range of 50°C to 200°C, and having the property of softening or flowing by heating.

[0089] [Process 1] The above-mentioned process 1 is a process of heating, melting and mixing the constituent components of the hardening polysiloxane composition of the present invention. The mixture with heat-melting properties is heated and mixed at a temperature above its softening point, preferably 50°C to 150°C, more preferably 50°C to 120°C, so that the composition is melted or softened as a whole, thereby enabling the components (A) to (D) and any other components to be uniformly dispersed as a whole.

[0090] The mixing device in process 1 is not limited and can be a batch heating mixing device such as a kneader, Bamboo mixer, Henschel mixer, planetary mixer, 2-roll mill, 3-roll mill, Ross mixer, or laboratory mixing extruder with heating / cooling functions, or a continuous heating mixing device such as a single-screw extruder or twin-screw extruder with heating / cooling functions. There is no particular limitation, and the appropriate device can be selected based on the efficiency of processing time and the ability to control shear heat. Considering the processing time, a continuous heating mixing device such as a single-screw extruder or twin-screw extruder, or a batch mixer such as a laboratory mixing extruder, can be used. However, considering the production efficiency of curable polysiloxane sheets, a continuous heating mixing device such as a single-screw extruder or twin-screw extruder is preferred.

[0091] When the mixture is pressurized into a sheet in process 3 via process 2, a uniform thin-layer sheet can be formed in one press, which has the practical benefit of avoiding poor molding and cracking of the sheet itself. If the temperature is below the lower limit, the softening is insufficient, and even with mechanical force, it is difficult to obtain a molten or softened mixture in which all components are uniformly dispersed. If such a mixture is pressurized into a sheet in process 4 via process 3, a uniform thin-layer sheet cannot be formed, which may lead to sheet breakage and cracking. Conversely, if the temperature exceeds the upper limit, the hardener will react during mixing, resulting in significant overall thickening or hardening, loss of heat meltability, and possible formation of hardened material, which is undesirable. Therefore, component (C) can use a microparticle-like platinum-containing hydrochemical catalyst that disperses or encapsulates a thermoplastic resin with a softening point above the mixing temperature.

[0092] As a method for feeding the constituent components of the present invention into the aforementioned mixing apparatus, each component may be supplied to the mixing apparatus separately, or all constituent components may be mixed in powder form to form a granular hardened polysiloxane composition before being fed into the mixing apparatus.

[0093] [Process 2] Process 2 is a process for obtaining a heated and melted mixture from a film-to-film lamination process 1, which has at least one peelable surface. It is a preparatory process for pressure molding performed in process 3. By forming a laminate containing the mixture obtained in process 1 between the films, a sheet-like molded product can be obtained by pressing it from the film using a roller stretching method. After molding, only the film can be removed from the sheet-like molded product using the peelable surface.

[0094] Depending on the intended use of the obtained curable polysiloxane sheet, both films preferably have a release surface, and it is particularly preferable that the mixture obtained in process 1 is deposited between the release surfaces of each film in process 2. By adopting this deposition form, after pressure molding in process 3 and subsequent arbitrary cutting, a laminated sheet in which a thin layer of curable polysiloxane sheet is sandwiched between release films and can be peeled off from both sides can be obtained. When using it, there is no need to worry about the formed curable polysiloxane sheet breaking; both films can be peeled off, exposing only the curable polysiloxane sheet.

[0095] There are no particular limitations on the film substrate used in process 2. Examples include paperboard, corrugated paper, clay-coated paper, polyolefin laminated paper, especially polyethylene laminated paper, synthetic resin sheets / boards, natural fiber cloth, synthetic fiber cloth, artificial leather cloth, and metal foil. Synthetic resin films / boards are particularly preferred. Examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and nylon. Especially when heat resistance is required, films of heat-resistant synthetic resins such as polyimide, polyetherketone ether, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide-imide, and polyether ether are preferred. On the other hand, for applications requiring legibility, such as display devices, transparent substrates are preferred, specifically transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN.

[0096] There is no particular limitation on the film thickness, which is usually around 5~300 µm.

[0097] The film has at least one release layer, preferably in contact with the mixture obtained in process 1. Thereby, after processes 2 and 3, the pressure-formed thermosetting polysiloxane sheet can be easily peeled off from the film. The release layer is also referred to as a release liner, spacer, release layer, or release coating, and is preferably a release layer with release coating properties such as a polysiloxane release agent, a fluorinated release agent, an alkyd release agent, or a fluorinated polysiloxane release agent. It can also be a substrate surface physically formed with micro-protrusions, or it can be the substrate itself that does not easily adhere to the thermosetting polysiloxane sheet involved in this invention.

[0098] In process 2, the mixture obtained in process 1 is laminated between two films. This process is not particularly limited; the mixture obtained in process 1 can be discharged or coated onto the release layer of one film for supply, and the release layer of another film can be bonded onto the mixture to form a laminate. Meanwhile, in the continuous manufacturing process of curable polysiloxane sheets, each film is transported to the mixture supply position in process 1 via a rotary roller, and the lamination operation between the films is performed.

[0099] The supply amount of the mixture obtained in process 1 to the inter-film layer in process 2 can be designed according to the manufacturing speed and scale. For example, the mixture obtained in process 2 can be supplied to the inter-film layer at a rate of 1 to 10 kg / hour, but it is not limited to this. However, in process 2, the amount of the mixture obtained in process 1 of the inter-film layer lamination process needs to be determined based on the average thickness of the curable polysiloxane sheet designed in process 3, and needs to be the thickness that can be rolled in process 3.

[0100] When the mixture obtained in process 1 has a low viscosity and is fluid when heated to melt, it is preferable to use a mold in process 2 to form the heated and melted mixture obtained in process 1 into a thin film and discharge it, depositing it between the films. Here, the purpose of using a mold is to temporarily shape the mixture. There are no particular restrictions on the type of mold or the thickness of the temporary shaping. It is permissible and preferable to use a T-shaped mold to temporarily shape the mixture into a roughly sheet-like form with a thickness in the range of 100~2000 µm (=2 mm).

[0101] When the mixture obtained in process 1 has a low viscosity upon heating and is fluid, it is preferable that, after the aforementioned temporary molding, a process including overall cooling or temperature regulation of the laminate obtained in process 2 is used as the preceding process or process 3. This is because cooling the heated melt and solidifying it allows for effective pressure molding in process 3. There are no particular limitations on this cooling process; the mixture supplied or laminated onto the film can be cooled to a range of -50°C to room temperature using cooling rollers or similar methods. Details regarding temperature regulation will be explained in process 3.

[0102] On the other hand, when the mixture obtained in process 1 has a high melting viscosity and is not fluid, it can be supplied and deposited on the film without temporary molding of the semi-solid mixture in process 2.

[0103] [Process 3] Process 3 is a process of stretching the laminate obtained by process 2 between rollers to form a curable polysiloxane sheet with a specific film thickness. It is a process of pressing and stretching the mixture obtained by process 1 on the film to form a uniform curable polysiloxane sheet.

[0104] Regarding the rolling process in process 3, the laminate obtained in process 2 can be rolled using known rolling methods such as roller rolling. In particular, roller rolling has the advantage of allowing the design of a curable polysiloxane sheet of desired thickness by adjusting the gap between the rollers. For example, by adjusting the gap between the rollers to a fixed value within an average thickness range of 10 to 2000 µm and performing rolling, a curable polysiloxane sheet with excellent flatness and minimal surface and internal defects can be obtained. More specifically, during roller rolling, it is particularly preferable to adjust the gap between the rollers within a range of 1.5 to 4.0 times the average thickness of the target organopolysiloxane cured film.

[0105] By performing stretching in process 3, a substantially flat, curable polysiloxane sheet with a thickness of 10 to 2000 µm can be obtained. By performing roller stretching in process 2 on the mixture after heating and melting in process 1 in the form of laminations between release films, a releaseable laminate containing a heat-fusible curable polysiloxane sheet with low defects and excellent workability for peeling can be obtained.

[0106] [Temperature Control in Process 3] In Process 3, when stretching the laminate obtained in Process 2 between rollers, preferably the rollers have a temperature control function, so that the temperature of the laminate as a whole is controlled during roller rolling, and heating or cooling is performed as needed. This temperature control provides the practical benefit of ensuring stable gaps between rollers and improving the flatness and uniformity (film thickness uniformity) of the obtained thermosetting polysiloxane sheet. The specific range of temperature control can be appropriately designed according to the heat resistance of the film, the thickness (design thickness) of the thermosetting polysiloxane sheet, its reactivity, etc., and is generally in the range of 5~150°C.

[0107] [Cutting Process] Through process 3, a releaseable laminate containing a thermosetting curable polysiloxane sheet between releaseable films can be obtained. A process for cutting the laminate containing the curable polysiloxane sheet can also be included. Furthermore, the curable polysiloxane sheet can also be wound using a winding device. Thus, a releaseable laminate containing a thermosetting curable polysiloxane sheet of desired size can be obtained.

[0108] [Laminated Body] The laminated system obtained by the above process has the following structure: a laminate composed of components (A) to (D) of the present invention and any other components, substantially flat, with a thickness of 10 to 2000 µm, and having heat-fusible properties, laminated between films having at least one release surface. Furthermore, all films may have, and preferably have, a release surface.

[0109] [Cureable Polysiloxane Sheet] The curable polysiloxane sheet obtained by the manufacturing method of the present invention has heat-melting properties and exhibits adhesiveness / bonding properties when heated and melted. Therefore, it has excellent formability, gap filling properties, and adhesion, and can be used as a wafer mounting film, film adhesive, and film sealant. In addition, it is also suitable as a curable polysiloxane sheet for compression molding, pressure molding, and vacuum lamination.

[0110] Specifically, the curable polysiloxane sheet obtained by the manufacturing method of the present invention can be peeled off from the release film and then placed on a desired location such as a semiconductor to form a thin film adhesive layer on the adherend that fills gaps and irregularities, temporarily fixing, arranging, and bonding the adherends. The curable polysiloxane sheet is then heated to 150°C or higher, and the hardened product of the curable polysiloxane sheet adheres to the adherends. Furthermore, the release film can be heated to form a hardened product on the curable polysiloxane sheet, and then peeled off. The timing of peeling can be selected according to the purpose and method of use of the curable polysiloxane sheet.

[0111] This curable polysiloxane sheet is thermoplastic. Heating the sheet before final curing softens it or allows it to flow. For example, even if the surface of the adhered object has unevenness, it can fill the unevenness or gaps, ensuring a gap-free bond and forming an adhesive surface. As a heating mechanism for this curable polysiloxane sheet, various thermostatic baths, hot plates, electromagnetic heating devices, heating rollers, etc., can be used. For more efficient bonding and heating, electric heating presses, film laminators, coating machines, etc., are preferred.

[0112] [Manufacturing Method of Granular Curable Polysiloxane Composition] This composition is a granular form containing at least the above-mentioned components (A) to (C), exceeding the degree of homogenization achieved by mechanical mixing alone. This granular composition is preferably obtained by melt-mixing the entire composition while heating. More specifically, it is preferable to melt-mix components (A) to (C) and any other components at a temperature range of 50°C to 150°C, more preferably 50°C to 120°C, using a single-shaft or dual-shaft continuous mixer, twin-drum mixer, Ross mixer, kneader mixer, etc., and then shape it into granules for use. Specific production methods are illustrated below.

[0113] The manufacturing method of the granular curable polysiloxane composition of the present invention includes the following process: a curable polysiloxane composition containing the above-mentioned components (A) to (C) and other arbitrary components, wherein the content of component (C) is in the range of 400 to 3000 parts by mass relative to the total of 100 parts by mass of components (A) and (B), is melt-blended at a temperature range of 50°C to 150°C, more preferably 50 to 120°C, and then molded into granules with an average particle size in the range of 0.1 to 10.0 mm. There are no particular limitations as long as the composition is melt-blended and molded into granules, for example, the following processes 1 to 3 are included. Process 1: A process of heating and melting the components of the curable polysiloxane composition at a temperature range of 50°C to 150°C, more preferably 50°C to 120°C, and then mixing them. Process 2: A process of discharging and cooling the mixture obtained in Process 1 after heating and melting. Process 3: A process of cutting or breaking down the mixture obtained in Process 2 to form granular curable polysiloxane composition.

[0114] [Process 1] The above-mentioned process 1 is a process of heating and melting the constituent components of the curable polysiloxane composition of the present invention in a temperature range of 50°C to 150°C and mixing them. The mixture with heat-melting properties is heated and mixed in a temperature range above its softening point, preferably 50°C to 120°C, so that the composition is melted or softened as a whole, thereby enabling the components (A) to (C) and any other components to be uniformly dispersed as a whole.

[0115] The mixing device in process 1 is not limited and can be a batch heating mixing device such as a kneader, Bamboo mixer, Henschel mixer, planetary mixer, 2-roll mill, 3-roll mill, Ross mixer, or laboratory mixing extruder with heating / cooling functions, or a continuous heating mixing device such as a single-screw extruder or twin-screw extruder with heating / cooling functions. There is no particular limitation, and the appropriate device can be selected based on the efficiency of processing time and the ability to control shear heat. Considering the processing time, a continuous heating mixing device such as a single-screw extruder or twin-screw extruder, or a batch mixer such as a laboratory mixing extruder, can be used. However, considering the production efficiency of granular hardening polysiloxane composition, a continuous heating mixing device such as a single-screw extruder or twin-screw extruder is preferred.

[0116] The mixture becomes granular in process 3 after process 2. However, if the temperature is below the aforementioned lower limit, the softening is insufficient, and even with mechanical force, it is difficult to obtain a molten or softened mixture in which all components are uniformly dispersed. Such a mixture has poor uniformity of components, and when the obtained granular hardening polysiloxane composition is used in the molding process, a uniform hardened product cannot be obtained. Conversely, if the temperature exceeds the aforementioned upper limit, the hardener will react during mixing, resulting in significant overall thickening or hardening, loss of heat meltability, and possible formation of a hardened product, which is undesirable. Therefore, component (C) is preferably a microparticle-shaped platinum-containing hydrosiliconization catalyst dispersed or encapsulated with a thermoplastic resin whose softening point is above the mixing temperature.

[0117] As a method for feeding the constituent components of the present invention into the aforementioned mixing apparatus, each component may be supplied to the mixing apparatus separately, or all constituent components may be mixed into powder by mechanical force or the like to form a granular hardened polysiloxane composition and then fed into the mixing apparatus.

[0118] [Process 2] Process 2 is the process of discharging the mixture after melting and mixing in Process 1 from the mixer. The mixture can be discharged in any shape, but in order to cut and break the mixture into granules in Process 3, it is preferable to be in a shape that is easy to cut and break. For example, rods (strips) with a diameter of about 0.5 to 5.0 mm or sheets with a thickness of about 0.5 to 5.0 mm can be used. In order to granulate in Process 3, the mixture is preferably a non-adhesive solid, so the discharged mixture needs to be cooled naturally or rapidly to bring its temperature down to near room temperature. As a method of rapid cooling, examples include using a cooler or water cooling.

[0119] [Process 3] Process 3 is a process of cutting or breaking the mixture discharged in Process 2 to granulate it. When the mixture has a hardness that can be broken by shear stress alone at room temperature, it can be granulated by breaking it with two rollers or the like. Here, the size and shape of the particles obtained by this Process 3 can be adjusted to some extent by controlling the size of the mixture discharged in Process 2 and the gap between the rollers. In this invention, the average particle size of the granular molded product needs to be in the range of 0.1 to 10.0 mm. Alternatively, when it is not possible to break the mixture with rollers or the like, particles can be obtained by discharging the mixture in the form of rods in Process 2, cooling it, and then cutting it into a specified size with a rotary cutter or the like.

[0120] The granular hardened polysiloxane composition obtained by the manufacturing method of the present invention has a highly homogeneous composition, making it difficult for non-uniformity or physical movement of the composition to occur during compression molding, pressure molding, lamination, and other molding processes. Therefore, it has the advantage of being easy to mold the composition uniformly as a whole, and can be better applied even in molding processes that do not generate shear pressure. In addition, even if the granular composition is molded a second time, the above advantages are not lost. Therefore, the granular hardened polysiloxane composition can also be used as a transfer molding ingot or pellet by compression or ingot molding using an ingot maker or the like.

[0121] [Curved Material] The above-mentioned curable polysiloxane composition has excellent heat-fusibility, excellent fluidity, workability, and curability when melted (hot-melted), and high hardness at room temperature to high temperature after curing. It also has excellent mechanical strength represented by a low coefficient of linear expansion and high flexural strength, thus exhibiting strength and toughness, and excellent bonding strength to the substrate. Therefore, it forms a cured material suitable for semiconductor components, etc. Considering the molding method described later, this composition is preferably cured by heat curing in the range of 80°C to 200°C. In addition, in this invention, the physical properties of the cured material, such as the coefficient of linear expansion, flexural strength, and hardness, can be easily designed to the following preferred ranges based on the types of components (A), (E), and the amount of component (D).

[0122] [Coefficient of Linear Expansion of the Cured Material] The average coefficient of linear expansion of the cured material obtained by curing the above-mentioned components is 30 ppm / ℃ or less, preferably 20 ppm / ℃ or less, and more preferably 15 ppm / ℃ or less, within the range of 25℃ to 200℃. If it is within this range, the difference between its average coefficient of linear expansion and that of the substrate used is lower, which can reduce the residual stress in the obtained integral molded product and improve the reliability of the equipment.

[0123] [Flexural strength of the hardened material] Furthermore, it is applicable to sealing materials for semiconductors that require high hardness and high strength. Therefore, the flexural strength of the hardened material determined according to the method specified in JIS K 6911-1995 "General Test Methods for Thermosetting Plastics" is preferably 15 MPa or more or 20 MPa or more.

[0124] [Hardness of the hardened material] In order to be suitable for protective components such as semiconductors, the hardness of the hardened material obtained after hardening this composition at 25°C is preferably 20 or higher using a D-type hardness tester. Furthermore, the hardness of this D-type hardness tester can be obtained using a D-type hardness tester based on JIS K 6253-1997 "Test method for hardness of vulcanized rubber and thermoplastic rubber".

[0125] [Method for molding the cured material] This composition can be cured by a method consisting of at least the following processes (I) to (III). (I) A process of heating the composition to above 100°C to melt it; (II) A process of injecting the curable polysiloxane composition obtained by said process (I) into a mold, or a process of distributing the curable polysiloxane composition obtained by said process (I) into a mold by means of clamping; and (III) A process of curing the curable polysiloxane composition injected in said process (II).

[0126] This composition is applicable to molding methods that include injection molding of semiconductor elements in a single process and underfilling (so-called mold underfilling method). Furthermore, by virtue of the above characteristics, this composition is applicable to molding methods that include injection molding of a cover process (so-called wafer molding) in which the surface of a semiconductor substrate (including a wafer substrate) on which one or more semiconductor elements are mounted is covered, and the gaps between the semiconductor elements are filled by using the hardened material.

[0127] In the above process, a transfer molding machine, a compression molding machine, an injection molding machine, an auxiliary pressure head molding machine, a sliding molding machine, a double pressure head molding machine, a low-pressure sealing molding machine, or a vacuum laminator can be used. In particular, the composition of the present invention is suitable for obtaining hardened materials by transfer molding and compression molding.

[0128] Finally, in process (III), the curable polysiloxane composition injected (applicable) in process (II) is cured. Furthermore, when an organic peroxide is used as component (C), the heating temperature is preferably 150°C or higher or 170°C or higher.

[0129] In order to be suitable for protective components such as semiconductors, the hardened material obtained after curing this composition preferably has a D-type hardness of 20 or higher at 25°C. Furthermore, the D-type hardness can be obtained using a D-type hardness tester based on JIS K 6253-1997 "Test Method for Hardness of Vulcanized Rubber and Thermoplastic Rubber".

[0130] [Applications of the Composition] Due to its heat-melting properties and excellent flowability, workability, and hardening properties when melted (heat-melted), this composition is suitable for use as a sealant or underfill for semiconductors; sealant or underfill for power semiconductors such as SiC and GaN; sealant or light-reflecting material for optoelectronic semiconductors such as light-emitting diodes, photodiodes, phototransistors, and laser diodes; and adhesives, potting compounds, protective agents, and coating agents for electrical or electronic applications. Furthermore, due to its heat-melting properties, this composition is also suitable for materials used in transfer molding, compression molding, or injection molding. It is particularly suitable as a sealant for semiconductors using mold underfilling or wafer forming methods during molding. Moreover, when this composition is formed into sheets, it can be used as a hardening film adhesive or a stress-relief layer between two substrates with different coefficients of linear expansion.

[0131] As described above, this composition is suitable for use as a sealant for semiconductors, etc. It can replace some or all of the conventionally known sealants in the process of sealing semiconductors by molding methods such as injection molding, underfilling, mold underfilling and wafer forming, etc., using conventionally known sealants (including non-polysiloxane hot melt sealants such as epoxy sealants). It can be used to manufacture semiconductor packages, power semiconductor modules, MEMS (microelectromechanical systems), micro-sensors (fingerprint sensors) and other small integrated devices, magnetic components such as coils containing magnetic particles, flexible substrates (stretchable wiring boards) used in wearable devices, electrical wiring boards, optical waveguides connected by connectors and other semiconductor / optical components. For example, the curable polysiloxane composition of this invention can replace Japanese Patent Application Publication Nos. 2021-097123, 2021-024945, 2020-132771, 2020-132750, 2020-125399, 2020-123670, 2020-084094, 2020-088055, 2019-006905, 2018-188494, 2017-179185, 2020-023643, 2020-063459, 2020-090634, etc. Use in whole or in part the sealants (especially sealants containing polysiloxane elastomers, pastes containing functional fillers, and hot-melt sealants) described in 2020-088055, 2020-107767, 2021-080411, 2021-036013, 2020-152844, 2020-158684, 2021-019031, 2021-059741, 2020-057775, 2021-015985, 2015-114390, and 2016-177106. Alternatively, and preferably as needed, the present invention can be applied to the technical elements used in the sealant composition, and the composition, properties of the hardened material, and melting characteristics of the composition of the present invention can be adjusted.

[0132] [Uses of the hardened material] The uses of the hardened material of the present invention are not particularly limited. The composition of the present invention has excellent heat-melting properties and excellent formability, and the hardened material has excellent adhesion properties, high modulus and low coefficient of linear expansion. Therefore, the hardened material formed by hardening the composition can be used as a component for semiconductor devices, and can be used as a sealing material for semiconductor elements or IC chips, or as a light-reflecting material for optoelectronic semiconductor devices.

[0133] There are no particular limitations on the semiconductor device having a component made of the hardened material of the present invention, but power semiconductor devices, optical semiconductor devices, and semiconductor devices mounted on flexible semiconductor devices that are stretchable or deformable are particularly preferred. [Example]

[0134] The following examples and comparative examples illustrate in detail the thermosetting curable polysiloxane composition of the present invention and its manufacturing method. Furthermore, in the formula, Me, Ph, and Vi represent methyl, phenyl, and vinyl, respectively. In addition, the softening point and melt viscosity of the curable polysiloxane compositions of each example and comparative example were determined using the following method. Furthermore, the curable polysiloxane composition was heated at 180°C for 2 hours to prepare a cured product, and the adhesion to various substrates was determined using the following method. The results are recorded in Table 1.

[0135] [Softening Point of Curable Polysiloxane Composition] A curable polysiloxane composition was molded into a cylindrical pellet with a diameter of φ14 mm × 22 mm. The pellet was placed on a hot plate set at 25°C to 100°C, and a 100-gram load was applied from above and held down for 10 seconds. After the load was removed, the deformation of the pellet was measured. The temperature at which the deformation in the height direction was 1 mm or more was defined as the softening point.

[0136] [Melt Viscosity] The melt viscosity of the curable polysiloxane composition at 180°C was measured using a high-performance flow meter CFT-500EX (manufactured by Shimadzu Corporation) under a pressure of 100 kgf and with a nozzle of 1.0 mm diameter. [Curing Characteristics] The curing characteristics were measured using a Curelastometer (registered trademark) (PREMIERMDR, manufactured by Alpha Technologies) at a molding temperature (160°C) for 600 seconds, following the method specified in JIS K 6300-2:2001 "Uncured rubber - Physical properties - Part 2: Method for calculating curing characteristics using a vibration vulcanization tester". Furthermore, approximately 5 g of the curable hot melt polysiloxane composition was measured, clamped in a 50 µm thick PET film, and placed on the lower mold. The measurement started when the upper mold was closed. Furthermore, using a rubber R-type mold, measurements were performed with an amplitude angle of 0.53°, a vibration frequency of 100 times / minute, and a maximum torque range of 230 kgf·cm. The measurement results were recorded in seconds as the time (ts⁻¹) required for the torque value to exceed 1 dNm. [Storage Stability] The curing polysiloxane composition was aged in a 40°C oven for 1 week, and the curing characteristics were measured according to the above method, with the ts⁻¹ value recorded.

[0137] [Flexural Strength of the Cured Material] A curable polysiloxane composition was heated at 180°C for 2 hours to produce a cured material. The flexural strength of the cured material was determined by the method specified in JIS K 6911-1995 "General Test Methods for Thermosetting Plastics".

[0138] [Wafer Shear Strength] Approximately 500 mg of a curable polysiloxane composition was applied at four locations on various substrates measuring 25 mm × 75 mm. Next, a 1 mm thick 10 mm square glass wafer was coated onto the composition. The wafer was then heated at 180°C for 2 hours under hot-pressing conditions using a 1 kg plate to harden it. After cooling to room temperature, the shear strength of the wafer was measured using a shear strength testing device (Bond Tester SS-100KP manufactured by Nishishin Shoji Co., Ltd.). [Linear Expansion Coefficient Curve of the Cured Material] The curable polysiloxane composition was hardened using the above method to produce a cured material. The linear expansion coefficient of the cured material was measured using a Vacuum Rikko Co., Ltd. TM9200 within a temperature range of 20°C to 200°C.

[0139] Hereinafter, an organopolysiloxane resin containing a hydrosiliconization catalyst was prepared using the method shown in Reference Example 1, and the organopolysiloxane resin microparticles were adjusted using the methods shown in Reference Examples 2 and 3. The presence or absence of hot melt properties was evaluated by the presence or absence of a softening point. In addition, the 1,1,3,3-tetramethyl-1,3-divinyldisiloxane used as the hydrosiliconization catalyst in the platinum complex in the Reference Examples is described as "1,3-divinyltetramethyldisiloxane".

[0140] [Reference Examples 1-6] In a 1L flask, 550g of each resinous organopolysiloxane (a white solid at 25°C) represented by the average unit formula in Table 1 below was dissolved in 450g of toluene to prepare a toluene solution of resinous organopolysiloxanes (1)-(6). The softening points of the above-mentioned resinous organopolysiloxanes are also shown in Table 1.

Table 1

[0141] [Reference Example 7] 270.5 g of a 55% by mass toluene solution of a resinous organopolysiloxane, which is a white solid at 25°C and expressed by the average unit formula: (Me2ViSiO1 / 2)0.20(PhSiO3 / 2)0.80, was added to a 1 L flask. The viscosity was 5, expressed by the formula: HMe2SiO(Ph2SiO)SiMe2H. 21.3 g of diphenylsiloxane (silicon-bonded hydrogen content = 0.6 wt%) with both ends of the molecular chain capped with dimethylhydrosiloxy groups (the amount of silicon-bonded hydrogen atoms in this component is 0.5 mol relative to the vinyl 1 mol in the resinous organosiloxane) and 0.034 g of a 1,3-divinyltetramethyldisiloxane solution of platinum (platinum metal content = about 4000 ppm) (the amount of platinum metal in mass units is 10 ppm relative to this liquid mixture), and stirred uniformly at room temperature. Then, the temperature inside the flask was raised to 100°C in an oil bath, and the mixture was stirred under reflux in toluene for 2 hours to prepare a toluene solution of an organosiloxane crosslinker (1) consisting of a resinous organosiloxane from the aforementioned resinous organopolysiloxane and a chain organosiloxane from the aforementioned diphenylsiloxane, and having vinyl groups that did not participate in the above reaction. Furthermore, when the organosiloxane crosslinker (2) was analyzed by FT-IR, no peaks of silicon atom bonded to hydrogen atoms were found. In addition, the softening point of the organosiloxane crosslinker (1) was 75°C.

[0142] [Reference Example 8] 270.5 g of a 55% by mass toluene solution of a resinous organopolysiloxane that is white at 25°C and is expressed by the average unit formula: (ViMe2SiO1 / 2)0.23(Ph2SiO2 / 2)0.07(PhMeSiO2 / 2)0.04(MeSiO3 / 2)0.35(PhSiO3 / 2)0.31 and 0.034 g of a 1,3-divinyltetramethyldisiloxane complex of platinum (platinum metal content = approximately 4000 ppm) were added to a 1 L flask and stirred uniformly at room temperature (25°C) to prepare a toluene solution of a resinous organopolysiloxane (7) containing 10 ppm platinum metal by mass. In addition, the softening point of the resinous organic polysiloxane (7) is 100°C.

[0143] [Reference Examples 9-16: Preparation of Hot-Melt Polysiloxane Microparticles (1)-(8)] Toluene was removed from the toluene solutions of resinous organosiloxanes (1)-(7) prepared in Reference Examples 1-6 and 8 as described in Table 2, and the toluene solution of organosiloxane crosslinked product (1) prepared in Reference Example 7, by spray drying at 40°C, and microparticles were formed to produce spherical hot-melt polysiloxane microparticles (1)-(8). The average particle size of each microparticle observed by optical microscopy is shown in Table 2.

Table 2

[0144] [Reference Example 17: Preparation of Resin-like Organic Polysiloxane Solution (1)] To 55.8 g of (A2) hot-melt polysiloxane microparticles (2), add 2.9 g of (C1) a diphenylsiloxane with a viscosity of 5 mPa·s and whose molecular chain is capped with dimethylhydrosiloxy groups (silicon atom bonded hydrogen atom content = 0.6 wt%), expressed as HMe2SiO(Ph2SiO)SiMe2H; and 22.3 g of (C2) a branched organic polysiloxane with more than 2 silicon atom bonded hydrogen atoms and a viscosity of 25 mPa·s, expressed as (PhSiO3 / 2)0.4(HMe2SiO1 / 2)0.6 (silicon atom bonded hydrogen atom content = 0.65 wt%). g, and stir at 60°C for 30 minutes to prepare a transparent resinous organic polysiloxane solution 1.

[0145] [Examples 1-14, Comparative Examples 1-7] The following ingredients were used in the examples and comparative examples of this case. (D) Inorganic fillers (D1) Fused silica with an average particle size of 14.5 µm (Nippon Steel Materials Micron S6105P) (D2) Fused silica with an average particle size of 0.7 µm (Nippon Steel Materials Micron SPH507M) (D3) Fused silica with an average particle size of 17.0 µm (Nippon Steel Materials Micron S6050P) (D4) Carbon black with an average particle size of 35 nm (DENKA BLACK pressed products) (ds) Inorganic filler treatment agent (ds-1) Dimethyl polysiloxane represented by Me2ViSiO(Me2SiO)29Si(OMe)3 (viscosity 23 mPa·s) (ds-1) Me3SiO(Me2SiO)110Si(OMe)3 represents dimethyl polysiloxane (H) wax (H) calcium stearate (Kawamura Chemicals) (A) Hot-melt polysiloxane components (A1)~(A8): Hot-melt polysiloxane microparticles (1)~(8) prepared in Examples 9~16 (A9) Resinous organopolysiloxane solution 1 of Example 17 (a mixture of components (A2), (C1), and (C2)) (E) Organosiloxane compound (E1) Formula: (ViMe2SiO1 / 2)0.75(PhSiO3 / 2)0.25, with a viscosity of 5 mPa·s and branched organopolysiloxane containing vinyl groups at the molecular ends (vinyl content = 23% by mass) (E2) Formula: (ViMe2SiO)2SiPh2, with a viscosity of 8 A linear organopolysiloxane with a viscosity of 300 mPa·s and vinyl groups at the molecular ends (vinyl content = 16% by mass) (E3) Formula: (Me2ViSiO1 / 2)0.55(Me3SiO1 / 2)0.05(SiO4 / 2)0.40 A branched organopolysiloxane with a viscosity of 19% by mass and vinyl groups at the molecular ends (E'1) Formula: ViMe2SiO(MePhSiO)17.5SiViMe2 A linear organopolysiloxane with a viscosity of 1.5% by mass and vinyl groups at the molecular ends (E'2) Formula: ViMe2SiO(MePhSiO)92SiViMe2 A linear organopolysiloxane with a viscosity of 0.5% by mass and vinyl groups at the molecular ends (E'2) Formula: ViMe2SiO(MePhSiO)92SiViMe2 A linear organopolysiloxane with a viscosity of 0.5% by mass and vinyl groups at the molecular ends (E'2)(B) SiH siloxane (B1) Formula: HMe2SiO(Ph2SiO)SiMe2H, a diphenyl siloxane with a viscosity of 5 mPa·s and whose molecular chain is capped with dimethylhydrosiloxy groups at both ends (content of silicon-bonded hydrogen atoms = 0.6% by mass). (B2) A branched organic polysiloxane with more than 2 silicon-bonded hydrogen atoms in a molecule and a viscosity of 25 mPa·s, represented by the average unit formula: (PhSiO3 / 2)0.4(HMe2SiO1 / 2)0.6 (content of silicon-bonded hydrogen atoms = 0.65% by mass). (C) Hydrogenation reaction catalyst; (C1) Containing 4000 g of platinum. Thermoplastic polycarbonate resin of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex with Pt (0 valence) in ppm (softening point of thermoplastic resin = 150 °C) (F) Inhibitor (F1) Methyltris-1,1-dimethyl-2-propynyloxysilane (boiling point = 245 °C (1013.25 hPa), in an amount of 300 ppm by mass relative to this composition) (F2) 1-ethynyl-1-cyclohexanol (in an amount of 300 ppm by mass relative to this composition) (G) Tackifier (G1) Bis(trimethoxysilylpropoxymethyl)vinyl rodenticide silicon (G2) Bis(trimethoxysilylpropoxymethyl)allyl rodenticide silicon (G2) Formula: (Me2ViSiO1 / 2)0.2(MeEpSiO2 / 2)0.25(PhSiO3 / 2)0.55(HO1 / 2)0.005 The formula represents an epoxy-containing polysiloxane.

[0146] Examples 1-7, 9-14, and Comparative Examples 1-7 were prepared as uniform and granular white or black curable polysiloxane compositions in the order shown below. On the other hand, Example 8 was prepared as a uniform and granular curable polysiloxane composition by feeding all components into a small pulverizer in the following order. The composition and proportions of each component are shown in the table. Furthermore, the softening viscosity, melt viscosity, TS-1, flexural strength, coefficient of linear expansion, and wafer shear strength of each component are shown in the table.

[0147] <Examples 1-7, 9-14, Comparative Examples 1-7> The treatment agents of (D) inorganic filler, (H) wax and (ds) inorganic filler were collectively added to a small pulverizer and stirred at 100°C for 1 minute. After surface treatment of (D) inorganic filler, the temperature of the pulverizer was restored to 25°C. Then, (A) hot-melt polysiloxane component, and any (E) organic polysiloxane compound, (B) SiH siloxane {relative to 1.0 moles of vinyl in this composition, the amount of silicon atoms bonded to hydrogen atoms in the above (B) component is the amount of moles of the SiH / Vi ratio shown in the table}, (F) inhibitor, (G) binder, and (C) silanization reaction catalyst were added to the small pulverizer and stirred at room temperature (25°C) for 1 minute to prepare a uniform and granular white or black curable polysiloxane composition.

[0148] <Example 8> (A) a hot-melt polysiloxane component, (E) an organopolysiloxane compound, (B) SiH siloxane {relative to 1.0 moles of vinyl in this composition, the amount of silicon atoms bonded to hydrogen atoms in component (B) is the amount of moles of the SiH / Vi ratio shown in the table}, (F) an inhibitor, (G) a binder, (C) a silanization reaction catalyst, (D) an inorganic filler, and (H) a wax were put into a small pulverizer and stirred at room temperature (25°C) for 1 minute to prepare a uniform and granular white curable polysiloxane composition.

[0149]

Table 3

[0151] [Summary] It can be seen that the curable polysiloxane compositions of Examples 1 to 14 of the present invention have good hot melt properties, and the coefficient of linear expansion of the cured product is low. In practical applications, they exhibit sufficient mechanical strength such as bending strength and wafer shear strength. In particular, in Examples 4 to 7 and 9 to 14, by adding component (E) to the composition, a low melt viscosity of the composition can be achieved without reducing the strength of the cured product.

[0152] Furthermore, according to the results of Example 8, the inorganic filler as component (D) is preferably treated with a specific treatment agent. Additionally, according to the results of Examples 9 and 10, component (F) as any component is preferably a specific compound, and component (C) is also preferably treated with a specific catalyst. Furthermore, according to the results of Example 11, it is confirmed that the combination of specific crosslinking agents is more effective for component (B), and according to the results of Example 12, it is confirmed that using a specific carbocyclic rodenticide silica compound as component (G) can further improve adhesion.

[0153] On the other hand, in Comparative Examples 1 to 7, which do not meet the main compositional conditions of the present invention, the mechanical strength of the obtained hardened product cannot be sufficiently improved when the (A) component with a specific structure is not used. According to the results of Comparative Examples 4 and 5, it is important to add the (R2SiO2 / 2) unit to the structure of the main agent. Even when a compound containing this unit is added as another component, no significant increase in strength is observed. Furthermore, in Comparative Example 6, although a compound with one (R2SiO2 / 2) unit added to the main agent was used, no significant increase in strength was observed in this example. This indicates that the (R2SiO2 / 2) unit added to the main agent needs to use a chain-like siloxane structure composed of D units having continuous units of this unit. On the other hand, according to Comparative Example 7, when a compound having continuous (R2SiO2 / 2) units is used simultaneously with component (E) which has the effect of increasing crosslinking density, the obtained composition loses its heat-melting properties.

[0154] <Manufacturing Example 1> The granular curable polysiloxane composition prepared in Example 1 above was heated to 80°C and simultaneously melt-blended using a twin-screw extruder. The resulting semi-solid softened material was supplied at a rate of 5 kg / hour to a release film (manufactured by TAKARA Corporation, Biwaraina), and laminated between two release films. The laminate was then stretched between rollers to form a 500 µm thick thermoplastic curable polysiloxane sheet laminated between the two release films. The entire laminate was then cooled using a cooling roller set to -15°C. By separating the release films from the laminate, a flat and homogeneous thermoplastic curable polysiloxane sheet was obtained.

[0155] <Manufacturing Example 2> The granular curable polysiloxane composition prepared in Example 1 above was heated to 80°C and simultaneously melt-mixed using a twin-screw extruder. It was then shaped into a generally sheet-like form using a T-die (opening size: 800 µm × 100 mm, heated to 80°C) and supplied to a release film (manufactured by TAKARA Co., Ltd., Biwaraina) at a rate of 5 kg / hour. After cooling by a cooling roller set to -15°C, the entire assembly was deposited between two release films. Subsequently, the stack was stretched between the rollers to form a 500 µm thick thermoplastic curable polysiloxane sheet deposited between the two release films. Within this stack, by separating the release films, a flat and homogeneous thermoplastic curable polysiloxane sheet was obtained. [Simplified Explanation of the Diagram]

[0015] None

Claims

1. A curable polysiloxane composition comprising the following (A) to (E): (A) (R13SiO)1 / 2)a(R22SiO2 / 2)b(R2SiO3 / 2)c(SiO4 / 2)d(R3O1 / 2)e (wherein, each R1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, wherein at least two of all R1 in a molecule are alkenyl groups, each R2 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms without alkenyl groups; each R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d and e are numbers satisfying the following relationships: 0.10≤a≤0.40, 0.05≤b≤0.50, 0.30≤c≤0.90, 0≤d≤0.20, 0≤e≤0.05, wherein a+b+c+d=1) (A) The hot-melt organosiloxane resin represented; (B) An organohydrosiloxane compound having at least two silicon-bonded hydrogen atoms in one molecule; (C) A hydrosilicifying catalyst in an amount sufficient to carry out the hydrosilicification of the aforementioned reactive polysiloxane composition; (D) A functional inorganic filler in an amount of 400 to 3000 parts by mass relative to 100 parts by mass of components (A) to (C); (E) (R13SiO1 / 2)a'(R22SiO2 / 2)b'(R2SiO3 / 2)c'(SiO4 / 2)d'(R3O1 / 2)e' (In the formula, each R1 is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms, wherein at least two of all R1 in a molecule are alkenyl groups; each R2 is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms without alkenyl groups; each R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a', b', c', d' and e' are numbers that satisfy the following relationships: 0.40≤a'≤0.80, 0≤b'≤0.90, 0≤c'≤0.60, 0≤d'≤0.50, 0≤e'≤0.05, where a'+b'+c'+d'=1) represents an organosiloxane compound containing more than 10% by mass of alkenyl groups in one molecule; and is solid at 25°C and has thermal fusibility at temperatures below 200°C.

2. The curable polysiloxane composition of claim 1, further comprising, based on the total mass of the composition, 1 to 5000 ppm of a curing retarder for hydrosiliconization reaction with a boiling point above 200°C at atmospheric pressure as component (F).

3. The curable polysiloxane composition of claim 1 or 2 further contains one or more tackifiers selected from rodenticide silicon derivatives and carbocyclic rodenticide silicon derivatives as component (G).

4. The curable polysiloxane composition of claim 1 or 2 further contains an organic wax with a melting point in the range of 30 to 160°C as component (H).

5. The curable polysiloxane composition as claimed in claim 1 or 2, wherein component (C) comprises a combination of two compounds: a linear organopolysiloxane represented by the general formula HR42SiO(R42SiO)nSiR42H, and a branched organopolysiloxane represented by the average unit formula (R4SiO3 / 2)p(R42SiO2 / 2)q(HR42SiO1 / 2)r(SiO4 / 2)s(XO1 / 2)t (where R4 is the same or different phenyl groups or alkyl groups with 1 to 6 carbon atoms, and the phenyl content in all R4 groups is in the range of 30 to 70 mol%). n is an integer in the range of 1 to 50, p is a positive number, q is 0 or a positive number, r is a positive number, s is 0 or a positive number, t is 0 or a positive number, and q / p is in the range of 0 to 10, r / p is in the range of 0.1 to 5, s / (p+q+r+s) is in the range of 0 to 0.3, and t / (p+q+r+s) is in the range of 0 to 0.4). For each alkenyl group in the composition as a whole, the ratio is (C-1):(C-2) = 0.05 to 0.6:0.4 to 0.

95.

6. The curable polysiloxane composition as claimed in claim 1 or 2, wherein component (C) contains thermoplastic resin microparticles containing a platinum catalyst with a glass transition temperature of 80°C or higher (the amount of platinum metal in the microparticles is 0.1 to 2,000 ppm by mass relative to the composition).

7. The curable polysiloxane composition of claim 1 or 2, wherein component (D) is formed by treatment with a polysiloxane surface treatment agent having at least one polysiloxane structure and a hydrolyzable silyl group within the molecule.

8. The curable polysiloxane composition of claim 1 or 2, wherein the curable material can be formed by curing in the range of 25°C to 200°C with an average linear expansion coefficient of less than 30 ppm / °C.

9. The curable polysiloxane composition as claimed in item 1 or 2, wherein curing produces a cured material with a flexural strength of 15 MPa or higher as determined by the method specified in JIS K 6911-1995 "General Test Methods for Thermosetting Plastics".

10. The curable polysiloxane composition of claim 1 or 2, wherein component (D) is a reinforcing filler, pigment, thermally conductive filler, electrically conductive filler, phosphor, or a mixture of at least two of these.

11. The curable polysiloxane composition of claim 1 or 2 is in any form, such as granules, pellets, or flakes.

12. A curing compound formed by curing a curable polysiloxane composition as claimed in any one of claims 1 to 11.

13. A component for a semiconductor device having a hardened material as claimed in claim 12.

14. A semiconductor device having a hardened material as claimed in claim 12.

15. A method for molding a hardened material, comprising at least the following processes (I) to (III): (I) a process of heating a hardened polysiloxane composition as claimed in any one of claims 1 to 11 to melt it to 100°C or above; (II) a process of dispersing the hardened polysiloxane composition obtained in the aforementioned process (I) into a mold by injecting the softened hardened polysiloxane composition in the aforementioned process (I) into a mold or by locking the mold; and (III) a process of hardening the hardened polysiloxane composition injected in the aforementioned process (II).

16. The method for forming a hardened material as claimed in claim 15, comprising performing a semiconductor device injection molding and underfilling cover process in one step by hardening a hardened material formed by hardening a hardened polysiloxane composition as claimed in any one of claims 1 to 11.

17. A method for forming a hardened material as claimed in claim 15, comprising a covering process in which a hardened material formed by curing a hardened polysiloxane composition as claimed in any one of claims 1 to 11 is used to cover the surface of a semiconductor substrate on which one or more semiconductor elements are mounted, and the hardened material is used to fill the gaps between the semiconductor elements, in a manner that is performed by injection molding.