Curable silicone composition and its cured product

Abstract

[Problem] To provide: a curable silicone composition that can be handled as a liquid at room temperature and that provides a cured product that exhibits excellent adhesive characteristics and mechanical characteristics and a relatively high hardness; and uses of the curable silicone composition. [Solution] A curable silicone composition that is characterized by containing prescribed mass% ranges of (A1) an organopolysiloxane resin that has a curing-reactive functional group that contains a carbon-carbon double bond, (A2) an organopolysiloxane resin that does not contain a curing-reactive functional group that contains a carbon-carbon double bond, and (B) a straight-chain organopolysiloxane that is liquid at 25°C and has a curing-reactive functional group that contains a carbon-carbon double bond, and also contains (C) a curing agent, wherein the viscosity of the composition as a whole is not more than 50 Pa·s and the amount of the curing-reactive functional group in 100 g of the composition is at least 1.5 mol%; the cured product from the curable silicone composition; and use of the curable silicone composition in, for example, semiconductor applications.

Description

[Technical Field]

[0001] The present invention relates to a curable silicone composition that can be handled as a liquid at room temperature and forms a cured product with excellent adhesive strength and mechanical strength upon curing, and to the cured product thereof. Furthermore, the present invention relates to applications of the composition or cured product (in particular, semiconductor components such as semiconductor device components and optoelectronic device components, and semiconductor devices having the cured product, etc.). [Background technology]

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

[0003] For example, Patent Documents 1 and 2 propose curable silicone compositions that form relatively high-hardness silicone elastomers, comprising a linear polyorganosiloxane containing alkenyl groups, a resinous polyorganosiloxane containing alkenyl groups, a polyorganosiloxane containing silicon atom-bonded hydrogen groups, and a curing catalyst. However, these silicone compositions exhibit good adhesion to common substrates such as aluminum, but have the problem of exhibiting almost no adhesion to difficult-to-adhere substrates such as polyphenylsulfone resins.

[0004] On the other hand, Patent Document 3 proposes a silicone pressure-sensitive adhesive comprising a linear polyorganosiloxane containing alkenyl groups, a resinous polyorganosiloxane not containing alkenyl groups, a polyorganosiloxane containing silicon atom-bonded hydrogen groups, and a curing catalyst. While these silicone compositions exhibit excellent adhesion to various substrates, the resulting cured products are known to be very soft.

[0005] Furthermore, Patent Document 4 proposes an invention to reduce the viscosity of a paste-like curable silicone composition consisting of a linear polyorganosiloxane containing alkenyl groups, a polyorganosiloxane containing silicon atom-bonded hydrogen groups, an inorganic filler, and a curing catalyst, by adding a small amount of resinous polyorganosiloxane that does not contain alkenyl groups. However, the amount of dendritic polyorganosiloxane that does not contain alkenyl groups added is too small, and a curable silicone composition exhibiting excellent adhesion like that described in Patent Document 3 has not been obtained.

[0006] Next, Patent Document 5 discloses a hot-melt, curable silicone sheet comprising a linear polyorganosiloxane containing alkenyl groups, a resinous polyorganosiloxane not containing alkenyl groups, a resinous polyorganosiloxane containing alkenyl groups, a polyorganosiloxane containing silicon atom-bonded hydrogen groups, and a curing catalyst. This composition is expected to form a cured product with a certain degree of hardness and excellent adhesive properties. However, due to their properties, these compositions are solid at room temperature and cannot be handled as a liquid, posing a problem as they cannot be used in applications requiring a liquid form. As described above, no silicone composition is known that can be handled as a liquid at room temperature and possesses both excellent adhesive properties like those of a silicone pressure-sensitive adhesive and hardness in the elastomer range. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2012-12433 [Patent Document 2] Japanese Patent Publication No. 2012-12434 [Patent Document 3] Japanese Patent Application Publication No. 7-197008 [Patent Document 4] Japanese Patent Application Publication No. 7-179764 [Patent Document 5] Special Publication No. 2017-512224 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention was made to solve the above problems, and the object of the present invention is to provide a curable silicone composition that can be handled as a liquid at room temperature, whose cured product has excellent adhesive properties and mechanical properties, and exhibits relatively high hardness, and its applications. [Means for solving the problem]

[0009] As a result of diligent research, the present inventors have found that the above problems can be solved by a curable silicone composition characterized by containing an organopolysiloxane resin having a curing-reactive functional group containing a carbon-carbon double bond, an organopolysiloxane resin without the same curing-reactive functional group, and a linear organopolysiloxane that is liquid at 25°C and has the same curing-reactive functional group in a specific mass% range, and also containing a curing agent, having a total viscosity of 50 Pa·s or less, and the amount of curing-reactive functional group in 100 g of the composition being 1.5 mol% or more, and by using the cured product thereof and its use in semiconductor applications, etc., and have completed the present invention.

[0010] From the standpoint of the technical effects of the present invention, it is particularly preferable that the organopolysiloxane resin having a curing-reactive functional group containing a carbon-carbon double bond has a weight-average molecular weight of a certain amount or less, has an alkenyl group content of a certain amount or more within the molecule, and the composition ratio of siloxane units constituting the organopolysiloxane resin is within a certain range. Furthermore, it is preferable that the composition is hydrosilylated reaction curable. Moreover, the cured product obtained by curing the composition according to the present invention can be suitably used as a semiconductor component. [Effects of the Invention]

[0011] The curable silicone composition of the present invention is liquid at room temperature and can be applied to processes that can only be applied to liquid compositions, such as dispensing. On the other hand, the resulting cured product exhibits good adhesion to various substrates, particularly so-called difficult-to-bond substrates such as polyphenylene sulfone resins, making it applicable to substrates, processes, and applications that were difficult to apply to with conventional, general-purpose silicone elastomer forming compositions. In addition, the cured product obtained by curing this composition exhibits sufficient mechanical strength and elastomer hardness, so it can be used not only as an adhesive to bond two substrates but also as a sealant or protective material to protect substrates. Furthermore, the curable silicone composition of the present invention can optionally be modified to include various inorganic fillers and functional fillers while maintaining the above-mentioned advantageous properties, thereby imparting special functions such as thermal conductivity and light reflectivity to the resulting cured product. For this reason, the cured product is extremely useful as a semiconductor component. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail below.

[0013] [Curing silicone composition] A curable silicone composition according to the present invention, (A1) Having a hardening-reactive functional group containing a carbon-carbon double bond within the molecule, and RSiO 3 / 2 (R is a monovalent organic group, hydroxyl group, or alkoxy group) or SiO 4 / 2 An organopolysiloxane resin containing at least 20 mol% or more of the siloxane units represented by the formula, (A2) The molecule does not have a hardening-reactive functional group containing a carbon-carbon double bond, and SiO 4 / 2 An organopolysiloxane resin containing at least 20 mol% or more of the siloxane units represented by the formula, (B) A linear organopolysiloxane having a curing-reactive functional group containing at least two carbon-carbon double bonds within the molecule, which is liquid at 25°C. (C) One or more curing agents necessary to cure this composition The composition is characterized by containing at least one of the following, having a total viscosity of 50 Pa·s or less, and having a curing-reactive functional group content of 1.5 mol% or more per 100 g of the composition. The composition may optionally contain one or more fillers selected from reinforcing fillers, white pigments, thermally conductive fillers, conductive fillers, or organic fillers to impart further functionality to the cured product. Other additives may also be included, as long as they do not impair the technical effects of the present invention.

[0014] [Organopolysiloxane resin having curing-reactive functional groups (A1)] The above component (A1) is one of the main components of this composition, and has a curing-reactive functional group containing a carbon-carbon double bond in its molecule, and is a branched unit RSiO 3 / 2 or SiO 4 / 2 This organopolysiloxane resin contains at least 20 mol% or more of the siloxane units represented by the formula, of the total siloxane units. Here, R is a monovalent organic group, a hydroxyl group, or an alkoxy group, and is preferably selected from a curing reactive group having a carbon-carbon double bond, a monovalent hydrocarbon group having 1 to 10 carbon atoms without a carbon-carbon double bond, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, as described later.

[0015] The curing reactive group having a carbon-carbon double bond may be a functional group having a carbon-carbon double bond, such as a (meth)acryloxy group, but it is particularly preferable that it is a hydrosilylation reactive functional group. Such a functional group can form a cured product when component (C), described later, is an organohydrogenpolysiloxane and a curing agent that is a hydrosilylation reaction catalyst. Examples of such curing reactive groups include alkenyl groups having 2 to 10 carbon atoms, and it is particularly preferable that they be vinyl groups or 1-hexenyl groups.

[0016] Preferably, in the (A1) component, the proportion of alkenyl groups in the organic groups bonded to all silicon atoms is in the range of 1 to 50 mol%, preferably 2 to 45 mol%, more preferably 2 to 35 mol%. By setting the amount of alkenyl groups in the (A1) component within the above range, even when the amount of the (A1) component used is small in the raw material ratio of the present composition, a relatively high hardness can be imparted to the resulting cured product.

[0017] (A1) component may contain other functional groups having no carbon-carbon double bond. In particular, it preferably contains a functional group selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms having no carbon-carbon double bond, especially alkyl groups having 1 to 10 carbon atoms such as methyl group. On the other hand, when it is desired to obtain a transparent composition, in the (A1) component, the proportion of aryl groups such as phenyl groups in the organic groups bonded to all silicon bonds is in the range of 0 to 5 mol%, more preferably in the range of 0 to 2 mol%, and most preferably contains no aryl group (= 0 mol%).

[0018] Preferably, in the (A1) component, the functional group bonded to the silicon atom is a group selected from alkenyl groups such as methyl group and vinyl group, and 50 mol to 99 mol% of the organic groups bonded to all silicon atoms are preferably methyl groups, more preferably 55 to 98 mol% are methyl groups, 65 to 98 mol% are methyl groups, and the other organic groups bonded to silicon atoms are alkenyl groups such as vinyl group is particularly preferred. In such a range, the mutual solubility of the (A1) component with other components is increased, and the coloring resistance and the like of the resulting cured product at high temperatures are improved. Incidentally, the (A1) component may contain a small amount of hydroxyl groups or alkoxy groups.

[0019] (A1) component is a branched unit RSiO 3 / 2 or SiO 4 / 2 contains at least 20 mol% or more of the siloxane unit represented by in all siloxane units, and the branched unit RSiO 3 / 2 or SiO 4 / 2The unit is preferably present in an amount of at least 40 mol%, more preferably 50 mol%, and particularly preferably in an amount between 50 and 90 mol% of the total siloxane units. R is preferably a monovalent organic group, and particularly preferably a methyl group from the viewpoint of compatibility with other components.

[0020] Preferably, component (A1) is (A1-1) The following is the average unit formula: (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2)e (In the formula, each R 1 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, provided that the total R in one molecule 1 1 to 50 mole% of the group is an alkenyl group; each R 2 a is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; a, b, c, d, and e are numbers satisfying the following: 0.10 ≤ a ≤ 0.90, 0 ≤ b ≤ 0.70, 0 ≤ c ≤ 0.80, 0 ≤ d ≤ 0.65, 0 ≤ e ≤ 0.05, where c + d > 0.20 and a + b + c + d = 1. This is an organopolysiloxane resin represented by [formula].

[0021] In the above average unit formula, each R 1 The group is a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms such as a methyl group, particularly preferably a methyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group. Furthermore, the total R in one molecule 1 2 to 45 mol% of the total R in one molecule is an alkenyl group, preferably 2 to 45 mol% of the total R 12 to 35 mol% of the component is an alkenyl group, particularly preferably a vinyl group and / or a 1-hexenyl group. If the alkenyl group content is below the lower limit of the above range, the mechanical strength (hardness, etc.) of the resulting cured product may be insufficient. On the other hand, if the alkenyl group content is below the upper limit of the above range, a composition containing this component can form a cured product with excellent mechanical strength. Note that each R 1 It is preferable that R is a functional group selected from the alkyl and alkenyl groups, and from the viewpoint of the technical effects of the present invention, 1 It is preferable that the compound substantially does not contain aryl groups such as phenyl groups.

[0022] In the above formula, R 2 R is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms. 2 Base R including 2 O 1 / 2 This corresponds to a hydroxyl group or alkoxy group possessed by the organopolysiloxane resin of component (A1).

[0023] In the above formula, a is the general formula: R 1 3SiO 1 / 2 This number represents the proportion of siloxane units. 'a' satisfies 0.1 ≤ a ≤ 0.90, preferably 0.15 ≤ a ≤ 0.85. If 'a' is within the above range, a composition containing this component can form a cured product with excellent mechanical strength.

[0024] In the above formula, b is the general formula: R 1 2SiO 2 / 2 This number represents the proportion of siloxane units. b satisfies 0 ≤ b ≤ 0.70, preferably 0 ≤ b ≤ 0.60. If b is below the upper limit of the above range, a composition containing this component can be obtained in which the viscosity does not become excessively high.

[0025] In the above formula, c is the general formula: R 3 SiO 3 / 2This number represents the proportion of siloxane units. c satisfies the condition 0 ≤ c ≤ 0.80, preferably 0 ≤ c ≤ 0.75. If c is below the upper limit of the above range, the viscosity of the composition containing this component will not become too high, and a composition with excellent mechanical strength of the resulting cured product can be obtained. In the present invention, c may be 0, and it is preferable that c is 0.

[0026] In the above formula, d is the formula SiO 4 / 2 This number represents the proportion of siloxane units, and it is necessary that 0.00 ≤ d ≤ 0.65, preferably 0.15 ≤ d ≤ 0.65, and particularly preferably 0.20 ≤ d ≤ 0.65. If d is within the above numerical range, the viscosity of the composition containing this component will not become too high, and a composition with excellent mechanical strength of the resulting cured product can be obtained.

[0027] In the present invention, c or d in the above formula may be 0, but it is necessary that c+d > 0.20. If the value of c+d is 0.20 or less, the hardness of the resulting cured product cannot be increased, and the technical effects of the present invention may not be fully achieved.

[0028] In the above formula, e is the general formula: R 2 O 1 / 2 This number represents the proportion of units, and these units refer to hydroxyl groups or alkoxy groups bonded to silicon atoms that may be contained in the organopolysiloxane resin. e satisfies 0 ≤ e ≤ 0.05, preferably 0 ≤ e ≤ 0.03. In the above formula, the sum of a, b, c, and d, which are the sums of each siloxane unit, is equal to 1.

[0029] Component (A1) is an organopolysiloxane resin having the above-described characteristics. It may be liquid or solid at room temperature, but its weight-average molecular weight (Mw), measured by gel permeation chromatography (GPC) using toluene as a solvent, is preferably 15,000 or less, more preferably 10,000 or less, and particularly preferably in the range of 100 to 10,000. Using a relatively low molecular weight component (A1) can lower the overall viscosity of the composition.

[0030] The amount of component (A1) added must be in the range of 1 to 50% by mass relative to the total amount (100% by mass) of components (A1), (A2), and (B). Preferably, it is in the range of 1 to 45% by mass, and more preferably, 1 to 40% by mass. By setting the amount of component (A1) added within this range, it is possible to balance the adhesive properties, mechanical strength, and hardness of the cured product obtained from the composition of the present invention. In particular, when the molecular weight and alkenyl group content of component (A1) are within the above preferred range, the overall viscosity of the composition and the amount of component (A1) added can be suppressed, and the amount of component (A2) added can be relatively increased, thereby further improving the adhesiveness and mechanical strength, represented by the hardness, of the cured product.

[0031] [Organopolysiloxane resin without curing-reactive functional groups (A2)] Component (A2) is one of the main components of this composition, and does not have a curing-reactive functional group containing a carbon-carbon double bond, and is SiO 4 / 2 This organopolysiloxane resin contains at least 20 mol% or more of the siloxane units represented by the formula, of the total siloxane units. By using component (A2) in combination with components (A1) and (B) within a predetermined quantitative range, a low viscosity can be achieved for the curable silicone composition as a whole, and excellent adhesive properties and mechanical strength can be realized in the cured product obtained by curing the curable silicone composition. Furthermore, by using it in combination with component (A1), which has a curing-reactive functional group, the hardness of the cured curable silicone composition can be adjusted.

[0032] Component (A2) preferably does not contain any curing-reactive functional groups containing carbon-carbon double bonds, such as alkenyl groups, within its molecule, but rather contains monovalent hydrocarbon groups having 1 to 10 carbon atoms that do not have carbon-carbon double bonds, particularly alkyl groups having 1 to 10 carbon atoms such as methyl groups, and functional groups selected from aryl groups. On the other hand, component (A2) preferably has a proportion of aryl groups such as phenyl groups in the total silicon-bonded organic groups that is in the range of 0 to 5 mol%, more preferably in the range of 0 to 2 mol%, and most preferably contains no aryl groups at all (= 0 mol%). If the content of aryl groups in component (A2) exceeds the above upper limit, component (A2) becomes hot-melt, making it difficult to obtain the desired liquid composition, and the SiO in the molecule 4 / 2 The reinforcing effect of the cured product derived from the siloxane units represented by may decrease, and the color resistance of the cured product at high temperatures may deteriorate.

[0033] Preferably, 70 to 100 mol% of the organic groups bonded to the silicon atoms in component (A2) are methyl groups, more preferably 80 to 100 mol%, and particularly preferably 88 to 100 mol% are methyl groups. Within this range, component (A2) is SiO 4 / 2 This component can be particularly excellent in reinforcing cured products containing siloxane units represented by [the formula shown]. The organopolysiloxane resin of component (A2) may also contain small amounts of hydroxyl groups or alkoxy groups.

[0034] Component (A2) is an organopolysiloxane resin, and contains branched siloxane units called SiO2 within its molecule. 4 / 2 The material is characterized by containing at least 20 mol% or more of siloxane units represented by SiO2. Preferably, the organopolysiloxane of component (A2) is SiO2. 4 / 2 The unit is at least 40 mol% of the total siloxane units, and is preferably 50 mol% or more, and particularly preferably in the range of 50 to 65 mol%.

[0035] Preferably, component (A2) is (A2-1) the following average unit formula: (R3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2)j (In the formula, each R 3 R is a monovalent hydrocarbon group that independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond; 2 The organopolysiloxane resin is represented as follows: (where is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; f, g, h, i, and j are numbers satisfying the following: 0.35 ≤ f ≤ 0.55, 0 ≤ g ≤ 0.20, 0 ≤ h ≤ 0.20, 0.30 ≤ i ≤ 0.65, 0 ≤ j ≤ 0.05, and f + g + h + i = 1).

[0036] In the above average unit formula, R 2 R is a group similar to those described above, preferably a hydrogen atom or a methyl group. 3 R is a monovalent hydrocarbon group that independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond, such as an alkyl group like methyl. Here, the total R in one molecule 3 It is particularly preferable, from the standpoint of industrial production and the technical effects of the invention, that 70 mol% or more, more preferably 88 mol% or more, be alkyl groups having 1 to 10 carbon atoms, such as methyl groups, especially methyl groups. On the other hand, R 3 It is preferable that the compound substantially does not contain aryl groups such as phenyl groups.

[0037] In the above formula, f is the general formula: R 3 3SiO 1 / 2 This number represents the proportion of siloxane units. f satisfies 0.35 ≤ f ≤ 0.55, preferably 0.40 ≤ f ≤ 0.50. If f is within the above range, the cured product made from the curable silicone composition containing this component can be given excellent adhesive properties and mechanical strength.

[0038] In the above formula, g is the general formula: R1 2SiO 2 / 2 This number represents the proportion of siloxane units. g satisfies 0 ≤ g ≤ 0.20, preferably 0 ≤ g ≤ 0.10. If g is below the upper limit of the range, the viscosity of the curable silicone composition containing this component will not become too high. In the present invention, g may be 0, and it is preferable that g is 0.

[0039] In the above formula, h is the general formula: R 1 SiO 3 / 2 This number represents the proportion of siloxane units. h satisfies 0 ≤ h ≤ 0.20, preferably 0 ≤ h ≤ 0.10. If h is below the upper limit of the range, the viscosity of the curable silicone composition containing this component will not become too high, and the resulting cured product can be given excellent mechanical strength. In the present invention, h may be 0, and it is preferable that h is 0.

[0040] In the above formula, i is SiO 4 / 2 i is a number that indicates the proportion of siloxane units, and is preferably 0.30 ≤ i ≤ 0.65, and particularly preferably 0.50 ≤ i ≤ 0.65. When i is within this numerical range, the cured product obtained by curing a curable silicone composition containing this component can be given excellent adhesion and mechanical strength.

[0041] In the above formula, j is the general formula: R 2 O 1 / 2 This number represents the proportion of units, where each unit refers to a hydroxyl group or alkoxy group bonded to a silicon atom that may be contained in the organopolysiloxane resin. j satisfies 0 ≤ j ≤ 0.05, preferably 0 ≤ j ≤ 0.03. In the above formula, the sum of the individual siloxane units, f, g, h, and i, is equal to 1.

[0042] Component (A2) is an organopolysiloxane resin having the above-described characteristics, and may be liquid or solid at room temperature. However, from the viewpoint of imparting excellent adhesive properties and mechanical strength to the cured product made from this composition, it is preferable that its weight-average molecular weight (Mw), as measured by GPC using toluene as a solvent, be 15,000 or more, and particularly preferable that it be in the range of 15,000 to 100,000.

[0043] The amount of component (A2) added is in the range of 20 to 70% by mass, preferably 25 to 60% by mass, relative to the total amount (100% by mass) of components (A1), (A2), and (B).

[0044] Furthermore, in order to balance the overall properties of the composition of the present invention, it is preferable to design the composition such that a relatively high molecular weight component (A2) is added in large quantities relative to the total amount of components (A1), (A2), and (B) to impart excellent adhesive properties and mechanical strength to the resulting cured product, while a small amount of component (A1), which has a relatively low molecular weight and contains a large amount of curing reactive groups, is added to lower the viscosity of the overall composition and increase the hardness of the resulting cured product.

[0045] [(B) Component] Component (B) is one of the main components of this curable silicone composition, and is a liquid linear organopolysiloxane at 25°C, having a curing-reactive functional group containing at least two carbon-carbon double bonds in its molecule. Such a curing-reactive linear organopolysiloxane can impart mechanical strength to the resulting cured product when used in combination with the organopolysiloxane resin which is component (A1) or component (A2) described above.

[0046] Component (B) must have a curing-reactive functional group having a carbon-carbon double bond within its molecule. Such a curing-reactive functional group has hydrosilylation reactivity and forms a cured product through crosslinking reactions with other components. Such a curing-reactive functional group is preferably an alkenyl group similar to that of component (A1), particularly a vinyl group or a hexenyl group.

[0047] Component (B) is a liquid linear organopolysiloxane at 25°C (room temperature) and plays an important role in reducing the viscosity of the composition of the present invention. The chemical structure of the organopolysiloxane of component (B) is preferably, (B1) The following structural formula: R 4 3SiO(SiR 4 20) k SiR 4 3 (In the formula, each R 4 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, however, R in one molecule 4 A linear diorganopolysiloxane is represented by (at least two of which are alkenyl groups, and k is a number between 20 and 1,000). Preferably, a linear diorganopolysiloxane having one alkenyl group, particularly a vinyl group, at each end of the molecular chain is preferred.

[0048] In the above formula, each R 4 R is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group such as methyl, particularly preferably a methyl group; an alkenyl group such as vinyl, particularly preferably a vinyl group and / or a hexenyl group; an aryl group such as phenyl; or an aralkyl group such as benzyl. Furthermore, R in one molecule 4 At least two of them are alkenyl groups, preferably vinyl groups. Also, each R 4 It is preferable that the functional group is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, such as methyl groups, and alkenyl groups, such as vinyl groups and hexenyl groups, and all R 4 Of these, at least two per molecule are alkenyl groups, and the remaining R 4 It is preferable that R is a methyl group. Furthermore, from the viewpoint of the technical effects of the invention, 4It is preferable that it substantially does not contain aryl groups such as phenyl groups. If it contains a large amount of aryl groups such as phenyl groups, the color resistance of the cured product obtained from the curable silicone composition at high temperatures may deteriorate. Particularly preferable is having one alkenyl group such as a vinyl group at each end of the molecular chain, and other R 4 It is preferable that the group is a methyl group.

[0049] In the above formula, k is a number between 20 and 1,000, preferably between 30 and 800, and particularly preferably between 30 and 500. If k is above the lower limit of the above range, sufficient mechanical properties can be imparted to the resulting cured product. On the other hand, if k is below the upper limit of the above range, the increase in viscosity of the curable silicone composition as a whole can be suppressed.

[0050] Here, the amount of component (B) added is in the range of 15 to 70% by mass, preferably 20 to 65% by mass, and more preferably 20 to 60% by mass, relative to the total amount (100% by mass) of components (A1), (A2), and (B). By setting the amount of component (B) added within this range, it is possible to balance the viscosity of the composition of the present invention with the mechanical strength and hardness of the resulting cured product.

[0051] [(C) component] Component (C) is a curing agent for curing components (A1) and (B) described above, and specifically, it is one or more curing agents selected from (c1) or (c2) below. Two or more of these curing agents may be used in combination, for example, a curing system containing both component (c1) and component (c2) may be used. (c1) Organic peroxide (c2) Organohydrogenpolysiloxanes and hydrosilylation reaction catalysts having at least two silicon-bonded hydrogen atoms in the molecule

[0052] (c1) The organic peroxide is a component that cures the above-mentioned components (A) and (B) by heating, and examples thereof include alkyl peroxides, diacyl peroxides, ester peroxides, and carbonate peroxides. Incidentally, the component (c1) can also react with some of the component (A2). Further, the organic peroxide preferably has a temperature at which its half-life is 10 hours of 90 °C or higher, or 95 °C or higher. Examples of such organic peroxides include dicumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,3-bis(tert-butylperoxyisopropyl)benzene, di-(2-t-butylperoxyisopropyl)benzene, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-trioxonan.

[0053] (c1) The content of the organic peroxide is not limited, but it is preferably within the range of 0.05 to 10 parts by mass, or within the range of 0.10 to 5.0 parts by mass, based on the sum (100 parts by mass) of the components (A1), (A2) and (B).

[0054] (c2) An organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst are components that cure the composition by an addition reaction (hydrosilylation reaction) of the carbon-carbon double bond in the components (A1) and (B) with the organohydrogenpolysiloxane as a crosslinking agent in the presence of the hydrosilylation reaction catalyst.

[0055] The structure of the organohydrogenpolysiloxane as a crosslinking agent is not particularly limited and may be linear, branched, cyclic or resinous. That is, the component (c2) has a hydrogenorganosiloxy unit (D 1 / 2 unit, R is independently a monovalent organic group) represented by as a main constituent unit, and a hydrogen dioorganosiloxy unit (M H unit) represented by at its terminal 1 / 2 H ​The unit, R may independently be a monovalent organic group), and may be an organohydrogenpolysiloxane. In particular, in the case of applications other than the molding process described later, the present curable silicone composition is the above-mentioned D H Even if it is a chain organohydrogenpolysiloxane composed of units such as, practically sufficient curing is possible.

[0056] On the other hand, when the present curable silicone composition is used in a molding process, since the content of the curing-reactive functional group containing a carbon-carbon double bond in the present composition is small, from the viewpoints of the curing rate, its moldability and curability, the organohydrogenpolysiloxane is RSiO 3 / 2 A monoorganosiloxy unit (T unit, R is a monovalent organic group or a silicon atom-bonded hydrogen atom) represented by, or a siloxy unit (Q unit) represented by SiO 4 / 2 It contains a branched unit, and at least two HR2SiO in the molecule 1 / 2 A hydrogen dioorganosiloxy unit (M H Unit, R is independently a monovalent organic group), and an organohydrogenpolysiloxane resin having an M H Unit at the molecular end is preferred.

[0057] A particularly suitable organohydrogenpolysiloxane is the following average unit formula: (R 5 3SiO 1 / 2 ) l (R 6 )]]2SiO 2 / 2 ) m (R 6 SiO 3 / 2 ) n (SiO 4 / 2 ) p (R 2 O 1 / 2 ) q It is an organohydrogenpolysiloxane resin represented by.

[0058] In the formula, each R 5R is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms and not having an aliphatic unsaturated carbon bond, or hydrogen atom, provided that there are at least two R in one molecule. 5 R is a hydrogen atom. 5 The monovalent hydrocarbon group is, for example, an alkyl group such as methyl; an aryl group such as phenyl; an aralkyl group such as benzyl; or other halogenated alkyl groups. From an industrial standpoint, a methyl group or a phenyl group is preferred.

[0059] In the formula, R 6 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated carbon bond, and examples of groups similar to the monovalent hydrocarbon group described above are given. On the other hand, R 2 R is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms, and R is in component (A1) or component (A2) above. 2 Similar groups are given as examples.

[0060] In the formula, l, m, n, and p are numbers satisfying the following: 0.1 ≤ l ≤ 0.80, 0 ≤ m ≤ 0.5, 0 ≤ n ≤ 0.8, 0 ≤ p ≤ 0.6, 0 ≤ q ≤ 0.05, where n + p > 0.1 and l + m + n + p = 1. Here, when this composition is used in the molding process, the organohydrogenpolysiloxane resin which is part of component (d2) is specifically M H MT resin, M H MTT H Resin, M H MTQ resin, M H MQ resin, M H MTT H Q, M H Q resin is preferred.

[0061] Particularly preferred is the organohydrogenpolysiloxane, which is part of component (c2). (H(CH3)2SiO 1 / 2 ) l1 (SiO 4 / 2 ) p1 M HThe resin is Q. Here, l1 + p1 = 1, and it is preferable that 0.1 ≤ l1 ≤ 0.80 and 0.20 ≤ p1 ≤ 0.90.

[0062] Similarly, the organohydrogenpolysiloxane, which is part of component (c2), may include linear diorganopolyloxanes, organohydrogenpolysiloxanes, or diorganopolysiloxane-organohydrogensiloxane copolymers, in which the molecular chain ends are sealed by silicon-bonded hydrogen atoms or trimethylsiloxy groups. The degree of siloxane polymerization of these linear organohydrogenpolysiloxanes is not particularly limited but is in the range of 2 to 200, and preferably in the range of 5 to 100.

[0063] The amount of organohydrogenpolysiloxane, which is part of component (c2), is sufficient to cure the curable silicone composition of the present invention, and is such that the molar ratio of silicon atom-bonded hydrogen atoms in the organohydrogenpolysiloxane to curing-reactive functional groups containing carbon-carbon double bonds in components (A1) and (B) (e.g., alkenyl groups such as vinyl groups) is 0.9 or more, and is preferably in the range of 0.9 to 2.0.

[0064] (c2) Examples of catalysts for the hydrosilylation reaction, which are part of component (c2), include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the curing of the composition. Examples of platinum-based catalysts include platinum fine powder, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, platinum-alkenylsiloxane complexes, platinum-olefin complexes, platinum-carbonyl complexes, and catalysts in which these platinum-based catalysts are dispersed or encapsulated in thermoplastic resins such as silicone resin, polycarbonate resin, or acrylic resin, with platinum-alkenylsiloxane complexes being particularly preferred. In particular, a platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is preferred, and it is preferable to add the complex in the form of an alkenylsiloxane solution. In addition, from the viewpoint of improving handling workability and the pot life of the composition, particulate platinum-containing hydrosilylation reaction catalyst dispersed or encapsulated in a thermoplastic resin may be used. Furthermore, non-platinum metal catalysts such as iron, ruthenium, or iron / cobalt may be used as catalysts to promote the hydrosilylation reaction.

[0065] On the other hand, the hydrosilylation catalyst, which is part of component (c2), may be a hydrosilylation catalyst (component (c2-1)) that does not show activity without irradiation with high-energy rays but shows activity in the composition upon irradiation with high-energy rays. Component (c2-1) is a so-called high-energy ray activated catalyst or photoactivated catalyst and is well known in the art. By using component (c2-1), the entire composition can be cured even at low temperatures triggered by irradiation with high-energy rays, has excellent storage stability, and is easy to control the reaction, thus achieving excellent handling properties.

[0066] High-energy rays include ultraviolet rays, gamma rays, X-rays, alpha rays, and electron beams. In particular, ultraviolet rays, X-rays, and electron beams irradiated from commercially available electron beam irradiation devices are preferred. Among these, ultraviolet rays are preferred from the viewpoint of catalyst activation efficiency, and ultraviolet rays in the wavelength range of 280 to 380 nm are preferred from the viewpoint of industrial use. The irradiation dose varies depending on the type of high-energy ray activated catalyst, but in the case of ultraviolet rays, the cumulative irradiation dose at a wavelength of 365 nm is 100 mJ / cm². 2 ~100J / cm 2 It is preferable that it be within the range.

[0067] (c2-1)Specific examples of components include (methylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)trimethylplatinum(IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)dimethylethylplatinum(IV), (cyclopentadienyl)dimethylacetylplatinum(IV), (trimethylsilylcyclopentadienyl)trimethylplatinum(IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum(IV), (dimethylphenylsilylcyclopentadienyl)trimethylcyclopentadienylplatinum(IV), trimethyl(acetylacetonate)platinum(IV), trimethyl(3,5- Examples include heptanedione)platinum(IV), trimethyl(methylacetoacetate)platinum(IV), bis(2,4-pentanedionato)platinum(II), bis(2,4-hexanedionato)platinum(II), bis(2,4-heptanedionato)platinum(II), bis(3,5-heptanedionato)platinum(II), bis(1-phenyl-1,3-butanedionato)platinum(II), bis(1,3-diphenyl-1,3-propanedionato)platinum(II), and bis(hexafluoroacetylacetonato)platinum(II). Among these, (methylcyclopentadienyl)trimethylplatinum(IV) and bis(2,4-pentanedionato)platinum(II) are preferred in terms of versatility and availability.

[0068] The amount of the hydrosilylation catalyst, which is part of these (c2) components, added is preferably such that the amount of metal atoms is in the range of 0.01 to 500 ppm, 0.01 to 100 ppm, or 0.01 to 50 ppm relative to the total composition by mass.

[0069] Particularly preferred component (c2) is one which comprises at least an organohydrogenpolysiloxane resin represented by the average unit formula and a hydrosilylation reaction catalyst.

[0070] [(D) component] If functionality is to be imparted to the cured product obtained from the curable silicone composition of the present invention, in addition to the above components (A1) to (C), the composition may further contain (D) a functional filler.

[0071] (D) The functional filler is a component that imparts mechanical properties and other properties to the cured product, and examples include inorganic fillers, organic fillers, and mixtures thereof. Examples of inorganic fillers include reinforcing fillers, white pigments, thermally conductive fillers, conductive fillers, phosphors, and mixtures of at least two of these, and examples of organic fillers include silicone resin-based fillers, fluororesin-based fillers, and polybutadiene resin-based fillers. The shape of these fillers is not particularly limited and may be spherical, spindle-shaped, flattened, needle-shaped, irregular, etc.

[0072] When this composition is used in applications such as sealants, protective agents, and adhesives, a reinforcing filler may be included in at least a portion of component (D) from the viewpoint of improving the mechanical strength, protective properties, and adhesive properties of the cured product.

[0073] Reinforcing fillers improve the mechanical strength of the cured product, enhance its protective and adhesive properties, and may also be added as binder fillers to maintain the solid particulate state of the curable silicone composition before curing. Examples of such reinforcing fillers include fumed silica, precipitated silica, fused silica, calcined silica, fumed titanium dioxide, quartz, calcium carbonate, diatomaceous earth, aluminum oxide, aluminum hydroxide, zinc oxide, and zinc carbonate. These reinforcing fillers may also be surface-treated with organoalkoxysilanes such as methyltrimethoxysilane; organohalosilanes such as trimethylchlorosilane; organosilazanes such as hexamethyldisilazane; and siloxane oligomers such as α,ω-silanol group-sealed dimethylsiloxane oligomers, α,ω-silanol group-sealed methylphenylsiloxane oligomers, and α,ω-silanol group-sealed methylvinylsiloxane oligomers. The particle size of this reinforcing filler is not limited, but it is preferable that the median diameter measured by laser diffraction scattering particle size distribution measurement is in the range of 1 nm to 500 μm. Furthermore, fibrous fillers such as calcium metasilicate, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, rock wool, and glass fiber may be used as the reinforcing filler.

[0074] Furthermore, white pigments, thermally conductive fillers, conductive fillers, or phosphors may be added to the cured product obtained using this composition in order to impart other functions to the product. Additionally, organic fillers such as silicone microparticles may be added for purposes such as improving the stress relaxation properties of the cured product.

[0075] The white pigment is a component that imparts whiteness to the cured product and improves its light reflectivity. By incorporating this component, the cured product obtained by curing the composition can be used as a light-reflecting material for light-emitting / optical devices. Examples of this white pigment include metal oxides such as titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, and magnesium oxide; hollow fillers such as glass balloons and glass beads; and others such as barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, and antimony oxide. Titanium dioxide is preferred due to its high light reflectivity and opacity. Aluminum oxide, zinc oxide, and barium titanate are also preferred due to their high light reflectivity in the UV region. The average particle size and shape of this white pigment are not limited, but the average particle size is preferably in the range of 0.05 to 10.0 μm, or in the range of 0.1 to 5.0 μm. Furthermore, this white pigment may be surface-treated with a silane coupling agent, silica, aluminum oxide, etc.

[0076] Thermally conductive fillers or conductive fillers are added to the cured product for the purpose of imparting thermal conductivity / electrical conductivity. Specifically, examples include fine metal powders such as gold, silver, nickel, copper, and aluminum; fine powders of ceramics, glass, quartz, organic resins, etc., on which metals such as gold, silver, nickel, and copper are deposited or plated; metal compounds such as aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, and zinc oxide; graphite; and mixtures of two or more of these. When electrical insulation is required for the composition, metal oxide powders or metal nitride powders are preferred, and aluminum oxide powder, zinc oxide powder, or aluminum nitride powder are particularly preferred. These may be used in combination of type, particle size, particle shape, etc., depending on the requirements for thermal conductivity / electrical conductivity.

[0077] A phosphor is a component added to a cured material to convert the emission wavelength from a light source (optical semiconductor device) when the cured material is used as a wavelength conversion material. There are no particular restrictions on the phosphor, but examples include yellow, red, green, and blue emitting phosphors made of oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, oxysulfide-based phosphors, etc., which are widely used in light-emitting diodes (LEDs).

[0078] Silicone microparticles include non-reactive silicone resin microparticles and silicone elastomer microparticles, but from the viewpoint of improving the flexibility or stress relaxation properties of the cured product, silicone elastomer microparticles are preferably exemplified.

[0079] For the purpose of stably incorporating the above-mentioned functional fillers into this composition, the filler surface may be treated by using a specific surface treatment agent in an amount of 0.1 to 2.0% by mass, 0.1 to 1.0% by mass, or 0.2 to 0.8% by mass relative to the total mass of component (D). Examples of these surface treatment agents include, for example, methyl hydrogen polysiloxane, silicone resin, metal soap, silane coupling agent, perfluoroalkylsilane, and fluorine compounds such as perfluoroalkyl phosphate salts.

[0080] The content of component (D) is not limited, but it is preferable that it be in the range of 1 to 2000 parts by mass, 1 to 1500 parts by mass, or 1 to 1000 parts by mass relative to the sum of components (A1) to (C) above (100 parts by mass).

[0081] The curable silicone composition of the present invention may further contain a curing retarder in addition to the above components (A) to (D). The type of curing retarder is not particularly limited, but examples include alkyne alcohols such as 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexyne-3-ol, 2-phenyl-3-butyne-2-ol, and 1-ethynyl-1-cyclohexanol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; low molecular weight siloxanes containing alkenyl groups such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; and alkynyloxysilanes such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane. Of these, it is particularly preferable to use a compound with a boiling point of 200°C or higher at atmospheric pressure. The content of the curing retarder in the curable silicone composition is not particularly limited, but it is preferably in the range of 1 to 10,000 ppm by mass relative to the composition.

[0082] [Other additives] In addition to the components described above, the curable silicone composition of the present invention may also contain materials known in the art as additives that can be used in the silicone composition. Examples of additives that can be used include, but are not limited to, the following.

[0083] The composition of the present invention may contain an adhesion promoter, provided that it does not impair the objectives of the present invention. Such adhesion promoters are common to the components suitably exemplified by the applicant in the international patent application (PCT / JP2020 / 12027), and include silane compounds such as 3-glycidoxypropyltrimethoxysilane, organosiloxane oligomers, alkyl silicates, as well as reaction mixtures of amino group-containing organoalkoxysilanes and epoxy group-containing organoalkoxysilanes disclosed in Japanese Patent Publication No. 52-8854 and Japanese Patent Application Publication No. 10-195085. In particular, carbasilatran derivatives having a silicon atom-bonded alkoxy group or a silicon atom-bonded alkenyl group in one molecule, and silatran derivatives having an alkoxysilyl group-containing organic group can be suitably used.

[0084] Furthermore, the composition may also contain, as long as it does not impair the purpose of the present invention, other optional components such as heat-resistant agents including iron oxide (red iron oxide), cerium oxide, cerium dimethyl silanolate, cerium fatty acid salts, cerium hydroxide, and zirconium compounds; as well as dyes, pigments other than white, flame retardants, etc.

[0085] Since the curable silicone composition of the present invention is in liquid or paste form, it can be produced by kneading the aforementioned components (A) to (D) and any other component in a known manner. The mixing apparatus used for mixing or kneading is not limited, and examples include a single-screw or twin-screw continuous mixer, a double-roll mixer, a Ross mixer, a Hobart mixer, a dental mixer, a planetary mixer, a kneader mixer, a lab mill mixer, a small pulverizer, and a Henschel mixer, with a lab mill mixer and a Henschel mixer being preferred.

[0086] The curable silicone composition forms a cured product by one of the following methods: thermosetting, high-energy ray curing, or high-energy ray + thermosetting. Therefore, by applying the composition to the substrate to be cured using a dispenser or the like before the curing process, and then curing it, it is possible to form a cured product while simultaneously achieving adhesion to the substrate.

[0087] [Uses of the composition] The curable silicone composition of the present invention can be used in liquid form at room temperature, and the cured product obtained by curing this composition exhibits excellent color resistance at high temperatures, adhesion to various substrates, and mechanical strength. Therefore, it is useful for semiconductor components such as encapsulants and light reflectors for light-emitting / optical devices, and for optoelectronic semiconductors having the cured product. Furthermore, because the cured product has excellent mechanical properties, it is suitable as a encapsulant for semiconductors; a encapsulant for power semiconductors such as SiC and GaN; and as an adhesive, potting agent, protective agent, and coating agent for electrical and electronic applications. On the other hand, since the hardness of the cured product can be freely controlled by adjusting the composition, a composition that forms a relatively soft, rubber-elastic cured product can also be used as a stress buffer layer (adhesive layer) between two substrates with different coefficients of thermal expansion.

[0088] Furthermore, cured products made from the curable silicone composition of the present invention exhibit good adhesion to difficult-to-bond substrates such as polyphenylene sulfone resins, silicone resins, and fluororesins, and can therefore be used for sealing these substrates or as stress-relieving layers for bonding two different substrates. In other words, the curable silicone composition of the present invention may be a sealant intended for single-sided sealing, or a sealant intended for double-sided sealing involving adhesion between two substrates, and possesses desirable properties suitable for these applications.

[0089] [Curing conditions for the composition] As described above, the curable silicone composition of the present invention can be cured by heat curing, high-energy ray curing such as ultraviolet light, or a combination of these methods, depending on the selection of component (C). In the case of heat curing, curing can generally be rapidly advanced by exposure to a temperature of 100°C or higher, preferably 150°C or higher. In the case of high-energy ray curing, curing progresses after irradiation with the light, either by leaving it at room temperature or by heating. Therefore, applying the composition to the substrate before irradiation with high-energy rays makes it easier to ensure the stability of the liquid composition. After applying this composition to the substrate, curing can be rapidly advanced at a low temperature of 25°C or 100°C or lower by irradiation with high-energy rays.

[0090] [Viscosity of the composition] The composition of the present invention is characterized by being able to be handled as a liquid at 25°C, and therefore its viscosity must be 50 Pa·s or less at a shear rate of 10 (1 / s). Preferably, it is 30 Pa·s or less, more preferably 10 Pa·s or less, and a range of 0.01 to 10 Pa·s is particularly preferred. By keeping the viscosity of the composition below the above range, it becomes possible to accommodate processes that require low viscosity.

[0091] [Concentration of curing-reactive groups containing carbon-carbon double bonds in the composition] The composition of the present invention contains a curing-reactive group comprising carbon-carbon double bonds derived from component (A1), component (B), and other components. In order for the hardness of the resulting cured product to be in the elastomer range, the amount of the curing-reactive group must be 1.5 mol% / 100g of composition or more, and preferably 1.5 to 15.0 mol% / 100g of composition. In particular, when the composition of the present invention is cured by a hydrosilylation reaction, it is preferable that the content of the alkenyl group, which is the curing-reactive group, be 1.5 mol% or more per 100g of composition. By setting this range above the lower limit, the resulting cured product will have sufficient crosslinking density, making it possible to increase its hardness.

[0092] [Hardness of hardened material] The preferred hardness of the cured product obtained by curing the curable hot-melt silicone composition of the present invention is preferably 20 or higher on the Type A durometer hardness specified in JIS K 7215-1986 "Durometer Hardness Test Method for Plastics". More preferably, it is 30 or higher. This is because if the hardness is below the above lower limit, the cured product becomes too soft, resulting in stickiness and making it unsuitable for sealing substrates. On the other hand, if the application is not for sealing substrates but as an adhesive layer to bond two types of substrates, the Type A durometer hardness may be near the lower limit. This is because lower hardness results in superior stress relaxation properties.

[0093] [Uses of hardened material] The applications of the cured product obtained by curing the curable silicone composition of the present invention are not particularly limited. Since the composition of the present invention can be handled as a liquid at room temperature, it can be suitably used in processes where a liquid state is required. Furthermore, the resulting cured product exhibits good adhesion properties to various substrates, has excellent mechanical strength, has low surface tack, and possesses hardness in the elastomer range. For this reason, the cured product obtained by curing this composition can be suitably used as a component for semiconductor devices, and can be suitably used as a encapsulant for semiconductor elements and IC chips, and as an adhesive / bonding member for conductive devices.

[0094] The semiconductor device comprising a component made from a cured product obtained by curing the curable silicone composition of the present invention is not particularly limited, but in particular, the composition of the present invention can form a cured product that is optically transparent to light-reflective or light-shielding depending on the presence or absence of component (D), and can be used selectively depending on the application. For example, it is preferable to use it as a light-emitting semiconductor device such as a light-emitting semiconductor device, an optical component for a display, or a component for a solar panel, and especially as a sealing material, case material or adhesive component used in such devices. Furthermore, since the cured product of the present invention has excellent color resistance at high temperatures, it can be more preferably used as a sealing material, case material or adhesive component used in electronic materials where transparency and light resistance / heat resistance are important. [Examples]

[0095] The curable silicone composition and its manufacturing method of the present invention will be described in detail below with reference to examples and comparative examples. In the following description, Me, Vi, and Ph in the average unit formulas represent methyl group, vinyl group, and phenyl group, respectively. Furthermore, the hardness, tensile elongation, surface tack, and adhesion to polyphenylene sulfone resin of the curable silicone composition of each example and comparative example were measured by the following method. The results are shown in Table 1. The weight-average molecular weight (Mw) of the organopolysiloxane resins was determined using Waters gel permeation chromatography (GPC) with toluene as the transfer solvent, and the weight-average molecular weight (Mw) of the organopolysiloxane resins in each reference example was calculated on a standard polystyrene basis using toluene as the solvent.

[0096] [Hardness of hardened material] A curable silicone composition was heated at 150°C for 2 hours to cure it and form a cured product. The hardness of this cured product was measured using a Type A durometer specified in JIS K 7215-1986 "Test Method for Durometer Hardness of Plastics".

[0097] [Tensile elongation of the cured material] A curable silicone composition was heated at 150°C for 2 hours to produce a cured product. The tensile elongation of this cured product was measured according to the method specified in JIS K 6251-2010 "Vulcanized rubber and thermoplastic rubber - Method for determining tensile properties". [Surface tack] A curable silicone composition was heated at 150°C for 2 hours to produce a cured product. A PET film was placed on the resulting cured product, and a load of 50 g / cm² was applied from above for 10 seconds. When the PET film was removed from the cured product, a circle (○) was used if it peeled off smoothly without sticking, an X was used if it stuck strongly and was difficult to remove, and a triangle (△) was used if the result was between ○ and X. [Adhesion to polyphenylene sulfone resin] Approximately 100 mg of a curable silicone composition was applied to five locations on a 25 mm x 75 mm polyphenylene sulfone resin plate using a dispenser. A 1 mm thick, 6 mm square aluminum chip was placed over the composition and pressed down with a 1 kg plate. This was then heated at 150°C for 2 hours to form a cured product. After cooling to room temperature, a die shear test was performed using a shear strength measuring device (Bond Tester SS-100KP manufactured by Nishishin Shoji Co., Ltd.), and the failure mode was observed visually to determine whether it was cohesive failure or interfacial delamination.

[0098] The following compounds were used in the examples and comparative examples shown below.

[0099] • Components (a1-1): Average unit formula (Me2ViSiO 1 / 2 ) 0.08 (Me3SiO 1 / 2 ) 0.42 (SiO 4 / 2 ) 0.50 (HO 1 / 2 ) 0.01 This organopolysiloxane resin is represented by (vinyl group content = 3.1 mol%, weight-average molecular weight (Mw) measured by GPC using toluene as a solvent is 4,300). • Components (a1-2): Average unit formula (Me2ViSiO 1 / 2 ) 0.65 (SiO 4 / 2 ) 0.35 (HO 1 / 2 ) 0.01 This is an organopolysiloxane resin represented by (vinyl group content = 19 mol%, weight-average molecular weight (Mw) measured by GPC using toluene as a solvent is 1,100). • Components (a1-3): Average unit formula (Me2ViSiO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.39 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02 This organopolysiloxane resin is represented by (vinyl group content = 1.9 mol%, weight-average molecular weight (Mw) measured by GPC using toluene as a solvent is 18,000). • Components (a2-1): Average unit formula: (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02 This represents an organopolysiloxane resin (vinyl group content = 0 mol%, weight-average molecular weight (Mw) of 18,500 as measured by GPC using toluene as a solvent). • Components (a2-2): Average unit formula (Me2ViSiO 1 / 2 ) 0.08 (Me3SiO 1 / 2 ) 0.42 (SiO 4 / 2 ) 0.50 (HO 1 / 2 ) 0.01 This organopolysiloxane resin is represented by (vinyl group content = 3.1 mol%, weight-average molecular weight (Mw) measured by GPC using toluene as a solvent is 4,300). ·Component (b-1): ViMe2SiO (Me2SiO) 300 SiViMe2 Dimethylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends of the molecular chain (vinyl group content = 0.23 mol%) ·Component (b-2): ViMe2SiO (Me2SiO) 45 SiViMe2 Dimethylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends of the molecular chain (vinyl group content = 1.53 mol%) ·Component (b-3): ViMe2SiO (Me2SiO) 140 SiViMe2 Dimethylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends of the molecular chain (vinyl group content = 0.44 mol%) ·Component (b-4): ViMe2SiO (Me2SiO) 800 SiViMe2 Dimethylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends of the molecular chain (vinyl group content = 0.09 mol%) • Component (c1-1): Me3SiO(Me2SiO) 37 (MeHSiO) 37 SiMe3 Organohydrogenpolysiloxanes • Components (c1-2): HMe2SiO(Me2SiO)17 SiMe2H Organohydrogenpolysiloxanes • Components (c1-3): (HMe2SiO) 1 / 2 ) 0.67 (SiO 4 / 2 ) 0.33 Organohydrogenpolysiloxane represented by Organohydrogenpolysiloxane represented by • Components (c1-4): Me3SiO(MeHSiO) 55 SiMe3 Organohydrogenpolysiloxanes • Component (c2): Platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (amount such that the platinum metal content is 5.0 ppm by mass relative to this composition) • Ingredient (d): Titanium dioxide with an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry Co., Ltd.) • Component (e): 1-Ethinylcyclohexanol (an amount that results in a platinum metal content of 50 ppm by mass relative to this composition) ·Component (f): Me2ViSiO (Me2SiO) 29 Si(OMe)3 Dimethylpolysiloxane is a molecular chain fragment whose ends are sealed with dimethylvinylsiloxy groups, and whose other molecular chain fragment ends are sealed with trimethoxysiloxy groups.

[0100] [Example 1~ 4 Comparative example C5、C6、 1-6] Curable silicone compositions were prepared by mixing each component in the quantities listed in Tables 1 and 2. The viscosity at a shear rate of 10 (1 / s) at 25°C, the hardness of the cured product, the tensile elongation, the surface tack, and the adhesion to polyphenylene sulfone resin are shown in the tables. In Comparative Example 6, a hot-melt material was obtained when the composition was exposed to 150°C for 2 hours, but no cured product was obtained, so the physical properties of the cured product are given as "NA".

[0101] [Table 1]

[0102] [Table 2]

[0103] [Summary] Examples 1 to 10 of the present invention 4 The curable silicone composition was found to have a viscosity of 50 Pas or less at 25°C by combining a specific organopolysiloxane resin and a chain-like organopolysiloxane in a specific ratio. The cured product exhibited excellent adhesive properties and mechanical strength, and had low surface tack with a hardness in the elastomer region of shore A20 or higher.

[0104] On the other hand, the curable silicone compositions of Comparative Examples 1 to 4 had a low concentration of curing reactive groups in their compositions, resulting in cured products that were very soft and sticky on the surface, making them unsuitable for applications involving sealing substrates. Furthermore, while the curable silicone composition of Comparative Example 5 formed a relatively hard cured product with low surface tack, its adhesive properties were inferior compared to the compositions of the Examples. In addition, the curable silicone composition of Comparative Example 6 was not liquid at room temperature, and no cured product was obtained even when heat was applied.

Claims

1. (A1-1) The average unit formula is as follows: (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ SiO ３／２ ) ｃ (SiO ４／２ ) ｄ (R ２ O １／２）ｅ (In the formula, each R １ R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, provided that all R in one molecule １ Of these, 2 to 40 mol% are alkenyl groups; each R ２ a is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; a, b, c, d, and e are numbers satisfying the following: 0.10 ≤ a ≤ 0.90, b = c = 0, 0.20 < d ≤ 0.65, 0 ≤ e ≤ 0.05, where a + d = 1) The organopolysiloxane resin represented by the above, wherein the weight-average molecular weight (Mw) of component (A1-1), as measured by gel permeation chromatography (GPC) using toluene as a solvent, is 15,000 or less, and the amount is in the range of 1 to 50% by mass of the total amount of components (A1-1), (A2-1), and (B1). (A2-1) The average unit formula is as follows: (R ３ ３ SiO １／２ ) ｆ (R ３ ２ SiO ２／２ ) ｇ (R ３ SiO ３／２ ) ｈ (SiO ４／２ ) ｉ (R ２ O １／２）ｊ (In the formula, each R ３ R is a monovalent hydrocarbon group that independently has 1 to 10 carbon atoms and does not contain a carbon-carbon double bond; ２ (where is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; f, g, h, i, and j are numbers satisfying the following: 0.35 ≤ f ≤ 0.70, g = h = 0, 0.30 ≤ i ≤ 0.65, 0 ≤ j ≤ 0.05, and f + g + h + i = 1) An organopolysiloxane resin represented by, in an amount in the range of 20 to 70% by mass relative to the total amount of components (A1-1), (A2-1), and (B1), (B1) The following structural formula: R ４ ３ SiO(SiR ４ ２ O) ｋ SiR ４ ３ (In the formula, each R ４ R is a monovalent hydrocarbon group having 1 to 10 carbon atoms independently, provided that R in one molecule ４ (At least two of them are alkenyl groups, and k is a number between 5 and 1,000.) A linear diorganopolysiloxane represented by the formula, in an amount that is in the range of 15 to 70% by mass relative to the total amount of components (A1-1), (A2-1), and (B1). (C) An organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst, The organohydrogen polysiloxane is added in an amount that gives 0.9 to 2.0 moles of silicon-bonded hydrogen atoms per mole of the total amount of carbon-carbon double bonds in the composition. (e) Curing retarder A curable silicone composition characterized by containing at least one of the above, and the entire composition being liquid at 25°C.

2. Furthermore, the curable silicone composition according to claim 1 is characterized in that it contains (D) a functional filler in an amount of 1 to 2000 parts by mass when the total amount of components (A1) to (C) is 100 parts by mass.

3. A cured product obtained by curing the curable silicone composition according to any one of claims 1 to 2.

4. The cured product according to claim 3, characterized in that ShoreA hardness is 20 or higher.

5. A semiconductor component comprising the cured product described in claim 3 or claim 4.

6. A semiconductor device comprising the cured product according to claim 3 or claim 4.

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