Curable silicone composition and cured product thereof

Abstract

The present invention provides a curable silicone composition and its use, the curable silicone composition can be handled in a liquid form at room temperature, and its cured product has excellent adhesive properties and mechanical properties, and shows high hardness. A curable silicone composition, its cured product and its use for semiconductor applications, etc., the curable silicone composition is characterized in that it contains (A1) a polyorganosiloxane resin having a curing reactive functional group containing a carbon-carbon double bond, (A2) a polyorganosiloxane resin without a curing reactive functional group, and (B) a straight-chain polyorganosiloxane having a curing reactive functional group and being liquid at 25°C, in a specific mass % range, and contains (C) a curing agent, the viscosity of the entire composition is 50 Pa·s or less, and the amount of curing reactive functional groups in 100g of the composition is 1.5 mol% or more.

Description

Technical Field

[0001] The present invention relates to a curable silicone composition and a cured product thereof, wherein the curable silicone composition can be handled in a liquid state at room temperature and forms a cured product having excellent adhesive force and mechanical strength by curing. Furthermore, the present invention also relates to a use of the composition or the cured product (particularly, semiconductor components such as semiconductor device components and optical semiconductor device components, and semiconductor devices having the cured product, etc.). Background Art

[0002] Curable silicone compositions can be cured to form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water resistance, and transparency, and are therefore used in a wide range of industrial fields. Cured products of such curable silicone compositions are generally less likely to change color than other organic materials, and their physical properties deteriorate less over time, so they are also suitable as sealants for optical materials and semiconductor devices.

[0003] For example, Patent Documents 1 and 2 propose curable silicone compositions for forming silicone elastomers having relatively high hardness, wherein the silicone elastomers are composed of alkenyl-containing linear polyorganosiloxanes, alkenyl-containing resinous polyorganosiloxanes, silicon-atom-bonded hydrogen-containing polyorganosiloxanes, and curing catalysts. These silicone compositions have a problem in that they exhibit good adhesion to common substrates such as aluminum, but exhibit almost no adhesion to difficult-to-bond substrates such as polyphenylsulfone resins.

[0004] On the other hand, Patent Document 3 proposes a silicone pressure-sensitive adhesive, which is composed of a straight-chain polyorganosiloxane containing an alkenyl group, a resinous polyorganosiloxane not containing an alkenyl group, a polyorganosiloxane containing a silicon atom-bonded hydrogen group, and a curing catalyst. It is known that these silicone compositions show excellent adhesion to various substrates, and on the other hand, the obtained cured products are very soft.

[0005] Furthermore, Patent Document 4 proposes the following invention: a small amount of a resinous polyorganosiloxane not containing alkenyl groups is added to a paste-like curable silicone composition composed of an alkenyl-containing linear polyorganosiloxane, a silicon atom-bonded hydrogen group-containing polyorganosiloxane, an inorganic filler, and a curing catalyst to reduce the viscosity of the composition. However, the amount of the added dendritic polyorganosiloxane not containing alkenyl groups is too small to obtain a curable silicone composition showing excellent adhesion as in Patent Document 3.

[0006] Next, in Patent Document 5, a hot-melt curable silicone sheet is disclosed, which is composed of a straight-chain polyorganosiloxane containing alkenyl groups, a resinous polyorganosiloxane without alkenyl groups, a resinous polyorganosiloxane containing alkenyl groups, a polyorganosiloxane containing a silicon atom-bonded hydrogen group, and a curing catalyst. This composition is expected to form a cured product with a certain degree of hardness and excellent adhesion. However, these compositions are solid at room temperature by nature and cannot be handled in liquid form, so there is a problem that they cannot be used for purposes that require a liquid form. As mentioned above, a silicone composition that can be handled in a liquid form at room temperature and has excellent adhesive properties like silicone pressure-sensitive adhesives and hardness in the elastomer region is not yet known.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2012-12433

[0010] Patent Document 2: Japanese Patent Application Publication No. 2012-12434

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 7-197008

[0012] Patent Document 4: Japanese Patent Application Laid-Open No. 7-179764

[0013] Patent Document 5: Japanese Patent Application No. 2017-512224 Summary of the invention

[0014] Problems to be solved by the invention

[0015] The present invention is proposed to solve the above-mentioned problems. The purpose of the present invention is to provide a curable silicone composition and its use, wherein the curable silicone composition can be handled in a liquid form at room temperature, and its cured product has excellent adhesive properties and mechanical properties and shows high hardness.

[0016] Solutions for solving problems

[0017] The present inventors have conducted intensive studies and have found that the above-mentioned problems can be solved by the following curable silicone composition, its cured product, and its use in semiconductor applications, etc., thereby completing the present invention. The curable silicone composition is characterized in that it contains a polyorganosiloxane resin having a curing reactive functional group containing a carbon-carbon double bond, a polyorganosiloxane resin not having the curing reactive functional group, and a straight-chain polyorganosiloxane that is liquid at 25°C and has the curing reactive functional group in a specific mass % range, and contains a curing agent, the viscosity of the entire composition is 50 Pa·s or less, and the amount of the curing reactive functional group in 100 g of the composition is 1.5 mol% or more.

[0018] From the viewpoint of the technical effect of the present invention, it is particularly preferred that, for the polyorganosiloxane resin having a curing reactive functional group containing a carbon-carbon double bond, its weight average molecular weight is below a certain value, the content of alkenyl groups in the molecule is above a certain value, and the constituent ratio of the siloxane units constituting the polyorganosiloxane resin is within a certain range. In addition, the composition is preferably hydrosilylation curable. Moreover, the cured product obtained by curing the composition of the present invention can be preferably used as a semiconductor component.

[0019] Beneficial Effects

[0020] 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 coating. On the other hand, the obtained cured product also shows good adhesion to various substrates, especially so-called difficult-to-bond substrates represented by polyphenylene sulfone resins, and can therefore be applied to substrates, processes and uses that were previously difficult to apply to conventional silicone elastomer-forming compositions. In addition, the cured product obtained by curing the composition exhibits sufficient mechanical strength and elastomer hardness, so it can be used not only as an adhesive for bonding two substrates, but also as a sealant or protective material for protecting a substrate. It should be noted that the curable silicone composition of the present invention can be added with various inorganic fillers and functional fillers according to arbitrary selection while maintaining the above-mentioned favorable properties, and special functions such as thermal conductivity and light reflectivity can also be imparted to the obtained cured product. Therefore, the cured product is extremely useful as a semiconductor component. DETAILED DESCRIPTION

[0021] Hereinafter, embodiments of the present invention will be described in detail.

[0022] [Curable silicone composition]

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

[0024] (A1) having a curing reactive functional group containing a carbon-carbon double bond in the molecule and containing at least 20 mol % or more of all siloxane units RSiO 3 / 2 (R is a monovalent organic group, hydroxyl or alkoxy) or SiO 4 / 2 A polyorganosiloxane resin having a siloxane unit as shown;

[0025] (A2) does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains at least 20 mol % or more of SiO 4 / 2 A polyorganosiloxane resin having a siloxane unit as shown;

[0026] (B) a linear polyorganosiloxane having at least two curing-reactive functional groups containing a carbon-carbon double bond in the molecule and being liquid at 25° C.;

[0027] (C) one or more curing agents required to cure the composition,

[0028] The viscosity of the composition as a whole is 50 Pa·s or less, and the amount of curing reactive functional groups in 100 g of the composition is 1.5 mol% or more. As required, one or more fillers selected from reinforcing fillers, white pigments, thermally conductive fillers, conductive fillers, or organic fillers may be added to the composition, and further functionality may be imparted to the cured product. In addition, other additives may be used as long as the technical effects of the present invention are not impaired.

[0029] [Polyorganosiloxane resin having curing reactive functional group (A1)]

[0030] The component (A1) is one of the main components of the present composition and has a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains RSiO as a branching unit in an amount of at least 20 mol% of all siloxane units. 3 / 2 or SiO 4 / 2 Here, R is a monovalent organic group, a hydroxyl group or an alkoxy group, and is preferably selected from a curing reactive group having a carbon-carbon double bond described below, a monovalent hydrocarbon group having 1 to 10 carbon atoms and not having a carbon-carbon double bond, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

[0031] The curing reactive group having a carbon-carbon double bond may also be a functional group having a carbon-carbon double bond such as a (meth)acryloyloxy group, and is particularly preferably a functional group reactive to hydrosilylation. Such a functional group can form a cured product when the component (C) described later is an organohydrogenpolysiloxane and a curing agent serving as a hydrosilylation reaction catalyst. Such a curing reactive group may particularly include an alkenyl group having 2 to 10 carbon atoms, and is particularly preferably a vinyl group or a 1-hexenyl group.

[0032] Preferably, in component (A1), the ratio of alkenyl groups to all organic groups bonded to silicon atoms is in the range of 1 to 50 mol%, preferably 2 to 45 mol%, and more preferably 2 to 35 mol%. By making the amount of alkenyl groups in component (A1) within the above range, even when the amount of component (A1) used in the raw material ratio of the present composition is small, a high hardness can be imparted to the obtained cured product.

[0033] The component (A1) may also contain other functional groups without carbon-carbon double bonds, and particularly preferably contains a functional group selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms without carbon-carbon double bonds, particularly alkyl groups having 1 to 10 carbon atoms such as methyl. On the other hand, in the case of attempting to obtain a transparent composition, the ratio of aryl groups such as phenyl groups to all silicon-bonded organic groups in the component (A1) 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 (=0 mol%).

[0034] Preferably, for component (A1), the functional group bonded to the silicon atom is a group selected from alkenyl groups such as methyl and vinyl, preferably 50 mol% to 99 mol% of all organic groups bonded to the silicon atom are methyl, more preferably 55 to 98 mol% are methyl, and particularly preferably 65 to 98 mol% are methyl, and the other organic groups bonded to the silicon atom are alkenyl groups such as vinyl. Within the range, the mutual solubility of component (A1) and other components is improved, and the coloring resistance of the obtained cured product at high temperature is improved. It should be noted that the component (A1) may also contain a small amount of hydroxyl or alkoxy.

[0035] The component (A1) contains at least 20 mol% or more of all siloxane units as branch units. 3 / 2 or SiO 4 / 2 The siloxane units shown in the figure are preferably contained in an amount of at least 40 mol% or more of all siloxane units, more preferably in an amount of at least 50 mol% or more, and particularly in an amount of 50 to 90 mol% as branching units. 3 / 2 or SiO 4 / 2 It should be noted that R is preferably a monovalent organic group, and is particularly preferably a methyl group from the viewpoint of compatibility with other components.

[0036] Preferably, the component (A1) is a polyorganosiloxane resin (A1-1) represented by the following average unit formula.

[0037] (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

[0038] (In the formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein all R 1 1 to 50 mol% are alkenyl groups; each R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d and e are numbers satisfying the following: 0.10≤a≤0.90, 0≤b≤0.70, 0≤c≤0.80, 0≤d≤0.65, 0≤e≤0.05, wherein c+d>0.20, and a+b+c+d=1)

[0039] In the above average unit formula, each R 1 Each of the R groups is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms, such as methyl, particularly preferably methyl; an alkenyl group having 2 to 10 carbon atoms, such as vinyl; an aryl group, such as phenyl; and an aralkyl group, such as benzyl. 1 2 to 45 mol% are alkenyl groups, preferably all R 1 2 to 35 mol% of the alkenyl group is an alkenyl group, and vinyl and / or 1-hexenyl groups are particularly preferred. When the alkenyl content is less than the lower limit of the range, the mechanical strength (hardness, etc.) of the obtained cured product may become insufficient. On the other hand, if the alkenyl content is below the upper limit of the range, the composition containing this component can form a cured product with excellent mechanical strength. It should be noted that each R 1 Preferably, a functional group selected from the above alkyl and alkenyl groups is selected from the above alkyl and alkenyl groups. From the viewpoint of the technical effect of the present invention, R 1 Preferably, no aryl group such as phenyl group is substantially contained.

[0040] In the above formula, R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 2 The group R 2 O 1 / 2 This corresponds to the hydroxyl group or alkoxy group of the polyorganosiloxane resin of the component (A1).

[0041] In the above formula, a represents the general formula: R 1 3SiO 1 / 2a satisfies 0.1≤a≤0.90, and preferably satisfies 0.15≤a≤0.85. When a is within the above range, the composition containing this component can form a cured product with excellent mechanical strength.

[0042] In the above formula, b represents the general formula: R 1 2SiO 2 / 2 b satisfies 0≤b≤0.70, preferably 0≤b≤0.60. When b is below the upper limit of the range, a composition containing the present component having a viscosity that does not become too high can be obtained.

[0043] In the above formula, c represents the general formula: R 3 SiO 3 / 2 c satisfies 0≤c≤0.80, and preferably satisfies 0≤c≤0.75. If c is below the upper limit of the range, the viscosity of the composition containing this component will not become too high, and the obtained cured product has excellent mechanical strength. In the present invention, c can be 0, and c is preferably 0.

[0044] In the above formula, d is the expression formula SiO 4 / 2 The ratio of the siloxane unit should be 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 be too high, and the obtained cured product will have excellent mechanical strength.

[0045] In the present invention, in the above formula, c or d may be 0, but c+d>0.20 is required. If the value of c+d is less than 0.20, the hardness of the obtained cured product may not be increased, and the technical effect of the present invention may not be fully achieved.

[0046] In the above formula, e represents the general formula: R 2 O 1 / 2 The ratio of the units is the number of hydroxyl or alkoxy groups bonded to silicon atoms that may be contained in the polyorganosiloxane resin. e satisfies 0≤e≤0.05, preferably 0≤e≤0.03. It should be noted that in the above formula, the sum of a, b, c and d, which are the sum of the siloxane units, is equal to 1.

[0047] The component (A1) is a polyorganosiloxane resin having the above characteristics, which can be liquid or solid at room temperature, and has a weight average molecular weight (Mw) of preferably 15,000 or less, more preferably 10,000 or less, and particularly preferably in the range of 100 to 10,000, as measured by gel permeation chromatography (GPC) using toluene as a solvent. By using a component (A1) with a relatively low molecular weight, the viscosity of the entire composition can be reduced.

[0048] The addition amount of the component (A1) needs to be in the range of 1 to 50% by mass relative to the total amount (100% by mass) of the components (A1), (A2) and (B). It is preferably in the range of 1 to 45% by mass, and more preferably in the range of 1 to 40% by mass. By setting the addition amount of the component (A1) to this range, a balance of the adhesive properties, mechanical strength and hardness of the cured product obtained from the composition of the present invention can be achieved. In particular, when the molecular weight of the component (A1) and the content of the alkenyl group are within the preferred range, the overall viscosity of the composition and the addition amount of the component (A1) can be suppressed, and the addition amount of the component (A2) can be relatively increased, so that the mechanical strength represented by the adhesiveness and hardness of the cured product can be further improved.

[0049] [Polyorganosiloxane resin (A2) having no curing reactive functional group]

[0050] The component (A2) is one of the main components of the present composition, has no curing reactive functional group containing a carbon-carbon double bond, and contains at least 20 mol % of SiO 4 / 2 A polysiloxane resin having a siloxane unit as shown. By using the component (A2) together with the component (A1) and the component (B) within a prescribed amount, the curable silicone composition as a whole can achieve a low viscosity, and the cured product obtained by curing the curable silicone composition can achieve excellent adhesive properties and mechanical strength. In addition, by using the component (A1) having a curing reactive functional group in combination, the hardness of the obtained curable silicone composition after curing can be adjusted.

[0051] Preferably, component (A2) does not contain curing reactive functional groups containing carbon-carbon double bonds such as alkenyl groups in the molecule, and on the other hand, contains functional groups selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms without carbon-carbon double bonds, particularly alkyl groups having 1 to 10 carbon atoms such as methyl groups, and aryl groups. On the other hand, with respect to component (A2), the proportion of aryl groups such as phenyl groups in all silicon-bonded organic groups is preferably in the range of 0 to 5 mol%, more preferably in the range of 0 to 2 mol%, and most preferably, no aryl groups (= 0 mol%) are contained. If the content of aryl groups in component (A2) exceeds the upper limit, component (A2) becomes hot-melt, and it is difficult to obtain the target liquid composition. In addition, sometimes SiO2 in the molecule causes the component to be hot-melt.4 / 2 The reinforcing effect of the cured product of the siloxane unit is reduced, and the coloring resistance of the cured product at high temperature may deteriorate.

[0052] Preferably, 70 to 100 mol% of the organic groups bonded to silicon atoms in component (A2) are methyl groups, more preferably 80 to 100 mol% are methyl groups, and particularly preferably 88 to 100 mol% are methyl groups. Within the above range, component (A2) may be SiO 4 / 2 The siloxane unit is a component that has a particularly excellent reinforcing effect on the cured product. It should be noted that the polyorganosiloxane resin of the component (A2) may contain a small amount of hydroxyl groups or alkoxy groups.

[0053] The component (A2) is characterized in that it is a polyorganosiloxane resin containing at least 20 mol % or more of SiO as a branched siloxane unit of all siloxane units in the molecule. 4 / 2 Preferably, the SiO 4 / 2 The unit accounts for at least 40 mol % or more of all siloxane units, particularly preferably 50 mol % or more, and particularly preferably in the range of 50 to 65 mol %.

[0054] Preferably, the component (A2) is a polyorganosiloxane resin (A2-1) represented by the following average unit formula.

[0055] (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2)j

[0056] (In the formula, each R 3 R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and no carbon-carbon double bond; 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; f, g, h, i and j are numbers satisfying the following: 0.35≤f≤0.55, 0≤g≤0.20, 0≤h≤0.20, 0.30≤i≤0.65, 0≤j≤0.05, and f+g+h+i=1)

[0057] In the above average unit formula, R 2 is the same group as described above, preferably a hydrogen atom or a methyl group. 3Each of the R groups is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and containing no carbon-carbon double bond, for example, an alkyl group such as a methyl group. 3 70 mol % or more, more preferably 88 mol % or more, of the alkyl groups are methyl groups or other alkyl groups having 1 to 10 carbon atoms, particularly methyl groups. 3 Preferably, no aryl group such as phenyl group is substantially contained.

[0058] In the above formula, f represents the general formula: R 3 3SiO 1 / 2 f satisfies 0.35≤f≤0.55, and preferably satisfies 0.40≤f≤0.50. If f is within the above range, excellent adhesive properties and mechanical strength can be imparted to the cured product formed from the curable silicone composition containing this component.

[0059] In the above formula, g represents the general formula: R 1 2SiO 2 / 2 g satisfies 0≤g≤0.20, and preferably satisfies 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 g is preferably 0.

[0060] In the above formula, h represents the general formula: R 1 SiO 3 / 2 h satisfies 0≤h≤0.20, and preferably satisfies 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 excellent mechanical strength can be imparted to the obtained cured product. In the present invention, h can be 0, and h is preferably 0.

[0061] In the above formula, i represents SiO 4 / 2 The number of the ratio of the siloxane unit is preferably 0.30≤i≤0.65, and particularly preferably 0.50≤i≤0.65. When i is within this numerical range, excellent adhesion and mechanical strength can be imparted to the cured product obtained by curing the curable silicone composition containing this component.

[0062] In the above formula, j represents the general formula: R 2 O 1 / 2 The ratio of the units is the number of hydroxyl or alkoxy groups bonded to silicon atoms that may be contained in the polyorganosiloxane resin. j satisfies 0≤j≤0.05, preferably 0≤j≤0.03. It should be noted that in the above formula, the total of f, g, h and i, which are the sum of the siloxane units, is equal to 1.

[0063] Component (A2) is a polyorganosiloxane resin having the above-mentioned characteristics, which can be either liquid or solid at room temperature. From the viewpoint of being able to impart more excellent adhesive properties and mechanical strength to a cured product formed from the present composition, its weight average molecular weight (Mw) measured by GPC using toluene as a solvent is preferably greater than 15,000, particularly preferably in the range of 15,000 to 100,000.

[0064] The amount of the component (A2) added is in the range of 20 to 70% by mass, preferably 25 to 60% by mass, based on the total amount (100% by mass) of the components (A1), (A2) and (B).

[0065] In addition, in order to achieve a balance in the properties of the composition of the present invention as a whole, the following design method is preferred: the component (A2) is a component with a relatively high molecular weight, and by adding a large amount relative to the total amount of the components (A1), (A2) and (B), it is possible to impart excellent adhesive properties and mechanical strength to the resulting cured product. On the other hand, by adding a small amount of the component (A1) which has a relatively low molecular weight and contains a large number of curing reactive groups, the viscosity of the composition as a whole is reduced, and the hardness of the resulting cured product is increased.

[0066] [(B) ingredient]

[0067] The component (B) is one of the main components of the curable silicone composition and is a linear polyorganosiloxane that is liquid at 25°C and has at least two curing-reactive functional groups containing carbon-carbon double bonds in the molecule. Such a curing-reactive linear polyorganosiloxane can impart mechanical strength to the resulting cured product by being used in combination with the polyorganosiloxane resin as the component (A1) or the component (A2).

[0068] The component (B) needs to have a curing reactive functional group containing a carbon-carbon double bond in the molecule. Such a curing reactive functional group has hydrosilylation reactivity and forms a cured product by a crosslinking reaction with other components. Such a curing reactive functional group is preferably an alkenyl group similar to the curing reactive functional group possessed by the component (A1), particularly a vinyl group or a hexenyl group.

[0069] The component (B) is a linear polyorganosiloxane that is liquid 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 polyorganosiloxane of the component (B) is preferably

[0070] (B1) a linear polydiorganosiloxane represented by the following structural formula:

[0071] R 4 3SiO(SiR 4 2O) kS i 4 3

[0072] (In the formula, each R 4 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein R 4 At least two of the moieties are alkenyl groups, and k is a number from 20 to 1000). Preferably, it is a linear polydiorganosiloxane having an alkenyl group, particularly a vinyl group, at each end of the molecular chain.

[0073] In the above formula, each R 4 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, for example, groups selected from the group consisting of alkyl groups such as methyl, particularly preferably methyl; alkenyl groups such as vinyl, particularly preferably vinyl and / or hexenyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. 4 At least two of R are alkenyl groups, preferably vinyl groups. 4 It is preferably a functional group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms such as methyl group, and an alkenyl group such as vinyl group and hexenyl group. It is preferred that all R 4 In each molecule, at least two are alkenyl groups, and the remaining R 4 It should be noted that, from the perspective of the technical effect of the invention, R 4 It is preferred that the phenyl group or other aromatic group is substantially free of aromatic groups. When a large amount of phenyl group or other aromatic groups are contained, the coloring resistance of the cured product obtained from the curable silicone composition at high temperature may deteriorate. It is particularly preferred that the molecular chain has one vinyl group or other aromatic group at each end, and the other R 4 It is methyl.

[0074] In the above formula, k is 20 to 1000, preferably 30 to 800, and particularly preferably 30 to 500. If k is greater than or equal to the lower limit of the range, sufficient mechanical properties can be imparted to the obtained cured product. On the other hand, if k is less than or equal to the upper limit of the range, the viscosity of the curable silicone composition as a whole can be suppressed from increasing.

[0075] Here, the addition amount of the component (B) is 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 the components (A1), (A2) and (B). By setting the addition amount of the component (B) to this range, a balance can be achieved between the viscosity of the composition of the present invention and the mechanical strength and hardness of the resulting cured product.

[0076] [(C) ingredient]

[0077] The component (C) is a curing agent for curing the components (A1) and (B), and specifically, is one or more curing agents selected from the following (c1) or (c2). It should be noted that two or more of these curing agents may be used in combination, for example, a curing system comprising both the components (c1) and (c2) may be used.

[0078] (c1) Organic peroxides;

[0079] (c2) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst,

[0080] (c1) organic peroxide is a component that cures the above-mentioned (A) component and (B) component by heating, and examples thereof include: alkyl peroxides, diacyl peroxides, peroxyesters, and peroxycarbonates. It should be noted that (c1) component may also react a portion of (A2) component. In addition, the organic peroxide preferably has a half-life of 10 hours at a temperature of 90°C or above, or 95°C or above. Examples of such organic peroxides include: diisopropylbenzene peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, tert-butyl isopropyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane, 1,3-bis(tert-butyl peroxyisopropyl)benzene, di(2-tert-butyl peroxyisopropyl)benzene, and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane.

[0081] The content of the organic peroxide (c1) is not limited, but is preferably in the range of 0.05 to 10 parts by mass, or in 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).

[0082] The (c2) organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule and the hydrosilylation reaction catalyst are components that cure the composition by causing the organohydrogenpolysiloxane as a crosslinking agent to undergo an addition reaction (hydrosilylation reaction) with the carbon-carbon double bonds in the components (A1) and (B) in the presence of the hydrosilylation reaction catalyst.

[0083] The structure of the organohydrogen polysiloxane used as a crosslinking agent is not particularly limited, and may be linear, branched, cyclic or resinous. That is, the component (c2) may be the following organohydrogen polysiloxane: 1 / 2 The organohydrogensiloxy unit (D H R is independently a monovalent organic group) as the main structural unit, and has HR2SiO at its end 1 / 2 The diorganohydrogensiloxy unit (M HIn particular, in the case of uses other than the molding process described later, even if the curable silicone composition is composed of D H Chain organohydrogenpolysiloxanes composed of units such as 1, 2 or 3 can also be cured sufficiently for practical use.

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

[0085] Particularly preferred organohydrogenpolysiloxane is an organohydrogenpolysiloxane resin represented by the following average unit formula.

[0086] (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

[0087] In the formula, each R 5 are the same or different and are monovalent hydrocarbon groups with 1 to 10 carbon atoms or hydrogen atoms without aliphatic unsaturated carbon bonds, wherein at least two R 5 is a hydrogen atom. 5 The monovalent group of methyl group includes alkyl groups such as methyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, and other halogenated alkyl groups. From the industrial viewpoint, methyl group and phenyl group are preferred.

[0088] In the formula, R 6 is a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated carbon bond, and examples thereof include the same groups as those described above.2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples thereof include the following: 2 Same group.

[0089] 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, wherein n+p>0.1, and l+m+n+p=1. Here, when the present composition is used in the molding step, the organohydrogenpolysiloxane resin as a part of the component (d2) is preferably 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.

[0090] It is particularly preferred that the organohydrogenpolysiloxane as a part of the component (c2) is a polysiloxane represented by the following formula: H Q resin.

[0091] (H(CH3)2SiO 1 / 2 ) l1 (SiO 4 / 2 ) p1

[0092] Here, preferably, l1+p1=1, 0.1≤l1≤0.80 and 0.20≤p1≤0.90.

[0093] Similarly, the organohydrogenpolysiloxane as part of the component (c2) may also include a linear polydiorganosiloxane, an organohydrogenpolysiloxane, or a polydiorganosiloxane-organohydrogensiloxane copolymer, the molecular chain ends of which are terminated by silicon-bonded hydrogen atoms or trimethylsiloxy groups. The siloxane polymerization degree of these linear organohydrogenpolysiloxanes is not particularly limited, but is in the range of 2 to 200, preferably in the range of 5 to 100.

[0094] The content of the organohydrogenpolysiloxane as a part of the component (c2) is an amount sufficient for curing the curable silicone composition of the present invention, and is an amount in which the molar ratio of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane relative to the curing reactive functional groups containing carbon-carbon double bonds (e.g., alkenyl groups such as vinyl) in the components (A1) and (B) is 0.9 or more, preferably an amount in the range of 0.9 to 2.0.

[0095] As a catalyst for hydrosilylation reaction as part of component (c2), examples thereof include: platinum catalyst, rhodium catalyst, palladium catalyst, and preferably platinum catalyst from the aspect of being able to significantly promote the curing of the present composition. As the platinum catalyst, examples thereof include: platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, platinum-carbonyl complex, and catalysts in which these platinum catalysts are dispersed or encapsulated by thermoplastic resins such as silicone resin, polycarbonate resin, and acrylic resin, and platinum-alkenylsiloxane complex is particularly preferred. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum is preferred, and it is preferably added in the form of alkenylsiloxane solution of the complex. In addition, from the viewpoint of improving the operability and the pot life of the composition, a microparticle-containing hydrosilylation catalyst dispersed or encapsulated by a thermoplastic resin can also be used. It should be noted that as a catalyst for accelerating the hydrosilylation reaction, a non-platinum metal catalyst such as iron, ruthenium, or iron / cobalt can be used.

[0096] On the other hand, the catalyst for hydrosilylation reaction as a part of component (c2) may be a catalyst for hydrosilylation reaction (component (c2-1)) which shows no activity if not irradiated with high-energy rays, but shows activity in the composition by irradiation with high-energy rays. Component (c2-1) is a catalyst known as a so-called high-energy ray-activated catalyst or a photoactivated catalyst, which is well known in the art. By using component (c2-1), the composition as a whole can achieve the following characteristics: it can be cured even at low temperatures by irradiation with high-energy rays as a trigger, has excellent storage stability, and is easy to control the reaction, so it can be excellent in operability.

[0097] Examples of high-energy rays include ultraviolet rays, gamma rays, X-rays, alpha rays, electron beams, and the like. In particular, ultraviolet rays, X-rays, and electron beams irradiated by commercially available electron beam irradiation devices are included. Ultraviolet rays are preferred from the perspective of catalyst activation efficiency, and ultraviolet rays with a wavelength of 280 to 380 nm are preferred from the perspective of industrial utilization. In addition, the irradiation amount varies depending on the type of high-energy ray-activated catalyst. In the case of ultraviolet rays, the cumulative irradiation amount at a wavelength of 365 nm is preferably 100 mJ / cm 2 ~100J / cm 2 within the range.

[0098] Specific examples of the component (c2-1) 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- bis(hexafluoroacetylacetonate)platinum(II), bis(1-phenyl-1,3-butanedione)platinum(II), bis(1,3-diphenyl-1,3-propanedione)platinum(II), and bis(hexafluoroacetylacetonate)platinum(II). Among them, (methylcyclopentadienyl)trimethylplatinum(IV) and bis(2,4-pentanedione)platinum(II) are preferred from the aspects of versatility and ease of acquisition.

[0099] The amount of the hydrosilylation reaction catalyst added as part of the component (c2) is preferably 0.01 to 500 ppm, 0.01 to 100 ppm, or 0.01 to 50 ppm in terms of metal atoms by mass relative to the entire composition.

[0100] Particularly preferred component (c2) contains at least an organohydrogenpolysiloxane resin represented by the above average unit formula and a hydrosilylation reaction catalyst.

[0101] [(D) ingredient]

[0102] In order to impart functionality to the obtained cured product, the curable silicone composition of the present invention may further contain (D) a functional filler in addition to the above-mentioned components (A1) to (C).

[0103] The functional filler as component (D) is a component that imparts mechanical properties and other properties to the cured product, and examples thereof include inorganic fillers, organic fillers, and mixtures thereof. Examples of the inorganic filler include reinforcing fillers, white pigments, thermally conductive fillers, conductive fillers, phosphors, and mixtures of at least two thereof, and examples of the organic filler include silicone resin fillers, fluororesin fillers, and polybutadiene resin fillers. It should be noted that the shapes of these fillers are not particularly limited, and may be spherical, spindle-shaped, flat, needle-shaped, amorphous, and the like.

[0104] When the present composition is used for applications such as sealants, protective agents, adhesives, etc., a reinforcing filler may be contained in at least a part of the component (D) from the viewpoint of improving the mechanical strength, protective properties, and adhesive properties of the cured product.

[0105] In addition to improving the mechanical strength of the cured product, improving the protective properties and adhesion, reinforcing fillers can also be added as binder fillers for the curable silicone composition before curing for the purpose of maintaining the solid particle state. Examples of such reinforcing fillers include: fumed silica, precipitated silica, fused silica, calcined silica, fumed titanium dioxide, quartz, calcium carbonate, diatomaceous earth, alumina, aluminum hydroxide, zinc oxide, and zinc carbonate. In addition, these reinforcing fillers can also be surface-treated with organic alkoxysilanes such as methyltrimethoxysilane; organic halogen silanes such as trimethylchlorosilane; organic silazanes such as hexamethyldisilazane; siloxane oligomers such as α,ω-silanol-terminated dimethylsiloxane oligomers, α,ω-silanol-terminated methylphenylsiloxane oligomers, and α,ω-silanol-terminated methylvinylsiloxane oligomers. The particle size of the reinforcing filler is not limited, and the median particle size measured based on the laser diffraction scattering particle size distribution is preferably in the range of 1 nm to 500 μm. In addition, as the reinforcing filler, fibrous fillers such as calcium metasilicate, potassium titanate, magnesium sulfate, sepiolite, xonolite, aluminum borate, asbestos, and glass fiber can also be used.

[0106] Furthermore, in order to impart other functions to the cured product obtained using the present composition, a white pigment, a thermally conductive filler, a conductive filler or a phosphor may be added. In addition, in order to improve the stress relaxation properties of the cured product, an organic filler such as silicone particles may be added.

[0107] White pigment is a component that imparts whiteness to the cured product and improves light reflectivity. The cured product formed by curing the present composition by combining this component can be used as a light reflective material for light-emitting / optical devices. Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, and magnesium oxide; hollow fillers such as glass balls and glass beads; and barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, and antimony oxide. Titanium oxide is preferred from the perspective of high light reflectivity and hiding power. In addition, aluminum oxide, zinc oxide, and barium titanate are preferred from the perspective of high light reflectivity in the UV region. The average particle size and shape of the white pigment are not limited, and 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. In addition, the white pigment can also be surface treated with a silane coupling agent, silica, aluminum oxide, or the like.

[0108] Thermally conductive fillers or conductive fillers are added for the purpose of imparting thermal conductivity / electrical conductivity to the cured product. Specifically, examples include: fine powders of metals such as gold, silver, nickel, copper, and aluminum; fine powders of metals such as gold, silver, nickel, and copper deposited or plated on the surface of fine powders such as ceramics, glass, quartz, and organic resins; metal compounds such as aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, and zinc oxide; graphite, and mixtures of two or more thereof. When electrical insulation is required for the present composition, metal oxide powders or metal nitride powders are preferred, and aluminum oxide powders, zinc oxide powders, or aluminum nitride powders are particularly preferred. These thermally conductive fillers or conductive fillers may also be used in combination of type, particle size, and particle shape according to the requirements of thermal conductivity / electrical conductivity.

[0109] The phosphor is a component added to convert the wavelength of light emitted from a light source (optical semiconductor element) when the cured product is used as a wavelength conversion material. The phosphor is not particularly limited, and examples thereof include yellow, red, green, and blue light-emitting phosphors composed 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).

[0110] Examples of the silicone fine particles include non-reactive silicone resin fine particles and silicone elastomer fine particles. From the viewpoint of improving the flexibility and stress relaxation properties of the cured product, silicone elastomer fine particles are preferably used.

[0111] For the purpose of stably combining the functional filler as described above in the present composition, a specific surface treatment agent may be used in the range of 0.1 to 2.0 mass %, 0.1 to 1.0 mass %, or 0.2 to 0.8 mass % relative to the mass of the entire component (D) to perform filler surface treatment. Examples of these surface treatment agents include fluoro compounds such as methyl hydrogen polysiloxane, silicone resin, metal soap, silane coupling agent, perfluoroalkyl silane, and perfluoroalkyl phosphate.

[0112] The content of component (D) is not limited, but is preferably 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 the above-mentioned components (A1) to (C) (100 parts by mass), from the perspective of excellent hardness and mechanical strength of the resulting cured product.

[0113] In addition to the above-mentioned components (A) to (D), the curable silicone composition of the present invention may also contain a curing retarder. The type of curing retarder is not particularly limited, and examples thereof include: 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol and other alkynols; 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne and other alkynyl compounds; tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahexenylcyclotetrasiloxane and other low molecular weight siloxanes containing alkenyl groups; methyl-tris(1,1-dimethylpropynyloxy)silane, vinyl-tris(1,1-dimethylpropynyloxy)silane and other alkynyloxysilanes. Among them, it is particularly preferred to use compounds having a boiling point of 200°C or more at atmospheric pressure. The content of the curing retardant in the curable silicone composition is not particularly limited, but is preferably within a range of 1 ppm to 10000 ppm by mass relative to the composition.

[0114] [Other additives]

[0115] In addition to the above-mentioned components, materials known in the art may be added to the curable silicone composition of the present invention as additives optionally used for silicone compositions. The following additives may be mentioned as usable additives, but are not limited thereto.

[0116] In the composition of the present invention, as long as the purpose of the present invention is not impaired, an adhesion imparting agent may also be contained. Such an adhesion imparting agent is the same as the component preferably exemplified by the applicant in the international patent application (PCT / JP2020 / 12027), except for silane compounds such as 3-glycidoxypropyltrimethoxysilane, organosiloxane oligomers, and alkyl silicates, and the reaction mixture of an amino-containing organoalkoxysilane disclosed in Japanese Patent Publication No. 52-8854 and Japanese Patent Laid-Open No. 10-195085 and an organoalkoxysilane containing an epoxy group, in particular, a cyclocarbon nitrogen siloxane derivative having a silicon atom-bonded alkoxy group or a silicon atom-bonded alkenyl group in one molecule, a silatrane derivative having an organic group containing an alkoxysilyl group, etc.

[0117] Moreover, in the present composition, as long as the purpose of the present invention is not impaired, other arbitrary components may also contain heat-resistant agents such as iron oxide (red iron oxide), cerium oxide, dimethylsilanol cerium, fatty acid cerium salt, cerium hydroxide, zirconium compounds; in addition, dyes, pigments other than white, flame retardant imparting agents, etc.

[0118] The curable silicone composition of the present invention is in liquid or paste form, and thus can be produced by kneading the components (A) to (D) and any components by a known method. The mixing device used for mixing or kneading is not limited, and examples thereof include: a single-shaft or double-shaft continuous mixer, a double-roll mixer, a Ross mixer, a Hobart mixer, a dental material mixer, a planetary mixer, a kneader, a Labo Millser, a small pulverizer, and a Henschel mixer, preferably a Labo Millser and a Henschel mixer.

[0119] The curable silicone composition forms a cured product by any of the methods of heat curing, high energy ray curing, and high energy ray + heat curing. Therefore, before the curing process, it can be applied on or inside the substrate to be cured by dispensing, and then cured, thereby forming a cured product while achieving adhesion to the substrate.

[0120] [Use of the composition]

[0121] The curable silicone composition of the present invention can be used in a liquid form at room temperature, and the cured product obtained by curing the present composition has excellent coloring resistance at high temperatures, adhesion to various substrates, and mechanical strength, and is therefore usefully used in semiconductor components such as sealing materials for light-emitting / optical devices, light-reflecting materials, and optical semiconductors having the cured product. In addition, since the cured product has excellent mechanical properties, it is preferably used as a sealant for semiconductors; a sealant for power semiconductors such as SiC and GaN; an adhesive, potting agent, protective agent, and coating agent for electrical / electronics. In addition, on the other hand, the hardness of the cured product can be freely controlled by adjusting the composition, so the 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 linear expansion coefficients.

[0122] In addition, the cured product formed from the curable silicone composition of the present invention exhibits 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, stress relief layers for bonding two different substrates, etc. That is, the curable silicone composition of the present invention can be a sealant for single-sided sealing or a sealant for double-sided sealing accompanied by bonding between two substrates, and has preferred properties suitable for these uses.

[0123] [Curing conditions of composition]

[0124] As described above, the curable silicone composition of the present invention can be cured by thermosetting, high-energy ray curing such as ultraviolet rays, or a combination thereof, depending on the selection of component (C). In the case of thermosetting, curing can be rapidly performed by generally exposing to a temperature above 100°C, preferably to a temperature above 150°C. In the case of the high-energy ray curing type, curing is performed by leaving it at room temperature and heating it after irradiating the light. Thus, coating the substrate before irradiating the high-energy ray makes it easy to ensure stability as a liquid composition. By applying the composition to the substrate and then irradiating it with high-energy rays, it can be rapidly cured at low temperatures of 25°C or below 100°C.

[0125] [Viscosity of composition]

[0126] The composition of the present invention is characterized in that it can be handled in a liquid form at 25°C, so its viscosity needs to be 50 Pa·s or less at a shear rate of 10 (1 / s). It is preferably 30 Pa·s or less, more preferably 10 Pa·s or less, and particularly preferably in the range of 0.01 to 10 Pa·s. By setting the viscosity of the composition to be below the above range, it can be used in processes requiring low viscosity.

[0127] [Concentration of Curing Reactive Groups Containing Carbon-Carbon Double Bonds in Composition]

[0128] The composition of the present invention contains a curing reactive group containing a carbon-carbon double bond derived from its component (A1), component (B) and other components, but in order to make the hardness of the obtained cured product become the hardness of the elastomer region, the amount of the curing reactive group needs to be set to 1.5 mol% / composition 100g or more, preferably 1.5 to 15.0 mol% / composition 100g. In particular, when the composition of the present invention is cured by a hydrosilylation reaction, the content of the alkenyl group as the curing reactive group is preferably 1.5 mol% or more relative to each 100g of the composition. By setting the range to above the lower limit, the obtained cured product can have a sufficient crosslinking density to increase its hardness.

[0129] [Hardness of cured product]

[0130] The preferred hardness of the cured product obtained by curing the curable hot-melt silicone composition of the present invention is preferably 20 or more in type A durometer hardness as specified in JIS K7215-1986 "Durometer Hardness Test Method for Plastics". More preferably, it is 30 or more. The reason is that if the hardness is below the above lower limit, the cured product is too soft and becomes sticky, and cannot be used for the purpose of sealing the substrate. On the other hand, when the purpose is not to seal the substrate but to bond the adhesive layer of two substrates, the type A durometer hardness may be near the lower limit. The reason is that the lower the hardness, the better the stress relaxation property.

[0131] [Application of cured product]

[0132] The use of the cured product obtained by curing the curable silicone composition of the present invention is not particularly limited. The composition of the present invention is handled in a liquid form at room temperature, and can therefore be preferably used in processes that require liquid. In addition, the obtained cured product shows good bonding properties to various substrates, has excellent mechanical strength, and has low viscosity on the surface of the cured product and has hardness in the elastomeric region. Therefore, the cured product obtained by curing the present composition can be preferably used as a component for semiconductor devices, and can be preferably used as a sealing material for semiconductor elements, IC chips, etc., and an adhesive / bonding component for conductor devices.

[0133] There are no particular restrictions on the semiconductor device having a component composed of a cured product obtained by curing the curable silicone composition of the present invention. 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 according to the purpose. For example, preferably, it is a light-emitting semiconductor device as a light-emitting / optical device, an optical component for display, a component for a solar panel, and especially a sealing material, a housing material or an adhesive component used for these devices. In addition, the cured product of the present invention has excellent coloration resistance at high temperatures, so it can be more preferably used as a sealing material, a housing material or an adhesive component for electronic materials where transparency and light resistance / heat resistance become important.

[0134] Example

[0135] The curable silicone composition of the present invention and the method for producing the same are described in detail below through examples and comparative examples. It should be noted that in the following description, Me, Vi, and Ph in the average unit formula represent methyl, vinyl, and phenyl, respectively. In addition, for the curable silicone composition of each example and comparative example, the hardness, tensile elongation, surface viscosity, and adhesion to polyphenylene sulfone resin of the cured product were measured by the following method. The results are shown in Table 1.

[0136] The weight average molecular weight (Mw) of the polyorganosiloxane resin in each reference example was determined by conversion to standard polystyrene using gel permeation chromatography (GPC) manufactured by Waters Corporation and toluene as a solvent.

[0137] [Hardness of cured product]

[0138] The curable silicone composition was heated at 150° C. for 2 hours to cure, thereby forming a cured product. The hardness of the cured product can be measured using a type A durometer specified in JIS K 7215-1986 “Durometer hardness test methods for plastics”.

[0139] [Tensile elongation of cured product]

[0140] The curable silicone composition was heated at 150° C. for 2 hours to prepare a cured product. The tensile elongation of the cured product was measured by the method specified in JIS K 6251-2010 “Rubber, vulcanized and thermoplastic rubber—Determination of tensile properties”.

[0141] [Surface stickiness]

[0142] The curable silicone composition was heated at 150°C for 2 hours to prepare a cured product. A PET film was placed on the obtained 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, the case where there was no adhesion and it was peeled off smoothly was marked as ○, the case where it was tightly adhered and difficult to peel off was marked as X, and the case where the result was between ○ and X was marked as Δ.

[0143] [Adhesion to polyphenylene sulfone resin]

[0144] On a 25mm×75mm polyphenylene sulfone resin plate, a curable silicone composition was applied at five locations with a dispenser at a rate of about 100mg per location, and a 6mm square aluminum chip with a thickness of 1mm was covered on the composition and crimped with a 1kg plate. Next, it was 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 Seishin Shoji Co., Ltd.), and the failure mode was visually observed to determine cohesive failure or interface peeling.

[0145] The following compounds were used in the Examples and Comparative Examples shown below.

[0146] Component (a1-1): Average unit formula

[0147] (Me2ViSiO 1 / 2 ) 0.08 (Me3SiO1 / 2 ) 0.42 (SiO 4 / 2 ) 0.50 (HO 1 / 2 ) 0.01

[0148] The polyorganosiloxane resin shown (vinyl content = 3.1 mol %, weight average molecular weight (Mw) of 4300 as measured by GPC using toluene as a solvent).

[0149] Component (a1-2): Average unit formula

[0150] (Me2ViSiO 1 / 2 ) 0.65 (SiO 4 / 2 ) 0.35 (HO 1 / 2 ) 0.01

[0151] The polyorganosiloxane resin shown (vinyl content = 19 mol %, weight average molecular weight (Mw) of 1100 as measured by GPC using toluene as a solvent).

[0152] Component (a1-3): Average unit formula

[0153] (Me2ViSiO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.39 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0154] The polyorganosiloxane resin shown (vinyl content = 1.9 mol %, weight average molecular weight (Mw) measured by GPC using toluene as a solvent is 18,000).

[0155] Component (a2-1): Average unit formula:

[0156] (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0157] The polyorganosiloxane resin shown (vinyl content = 0 mol %, weight average molecular weight (Mw) measured by GPC using toluene as a solvent is 18500).

[0158] Component (a2-2): Average unit formula

[0159] (Me2ViSiO 1 / 2 ) 0.08 (Me3SiO 1 / 2 ) 0.42 (SiO 4 / 2 ) 0.50 (HO 1 / 2 ) 0.01

[0160] The polyorganosiloxane resin shown (vinyl content = 3.1 mol %, weight average molecular weight (Mw) of 4300 as measured by GPC using toluene as a solvent).

[0161] Component (b-1): ViMe2SiO (Me2SiO) 300 SiViMe2

[0162] The molecular chain ends of the polydimethylsiloxane shown are terminated with dimethylvinylsiloxy groups (vinyl content = 0.23 mol %).

[0163] Component (b-2): ViMe2SiO (Me2SiO) 45 SiViMe2

[0164] The molecular chain ends of the polydimethylsiloxane shown are terminated with dimethylvinylsiloxy groups (vinyl content = 1.53 mol %).

[0165] Component (b-3): ViMe2SiO (Me2SiO) 140 SiViMe2

[0166] The molecular chain ends of the polydimethylsiloxane shown are terminated with dimethylvinylsiloxy groups (vinyl content = 0.44 mol %).

[0167] Component (b-4): ViMe2SiO (Me2SiO) 800 SiViMe2

[0168] The molecular chain ends of the polydimethylsiloxane shown are terminated with dimethylvinylsiloxy groups (vinyl content = 0.09 mol %).

[0169] ·Composition (c1-1): Me3SiO (Me2SiO) 37 (MeHSiO) 37 SiMe3

[0170] The organohydrogenpolysiloxane shown.

[0171] ·Composition (c1-2): HMe2SiO (Me2SiO) 17SiMe2H

[0172] The organohydrogenpolysiloxane shown.

[0173] ·Composition (c1-3): (HMe2SiO 1 / 2 ) 0.67 (SiO 4 / 2 ) 0.33

[0174] The organohydrogenpolysiloxane shown is the organohydrogenpolysiloxane shown.

[0175] ·Composition (c1-4): Me3SiO (MeHSiO) 55 SiMe3

[0176] The organohydrogenpolysiloxane shown.

[0177] Component (c2): a platinum-containing 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (the amount of platinum metal is 5.0 ppm by mass relative to the present composition).

[0178] Component (d): titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry Co., Ltd.).

[0179] Component (e): 1-ethynylcyclohexanol (the amount of platinum metal is 50 ppm by mass relative to the present composition).

[0180] Component (f): Me2ViSiO(Me2SiO) 29 Si(OMe)3

[0181] The polydimethylsiloxane shown has one molecular chain end-capped with a dimethylvinylsiloxy group and another molecular chain end-capped with a trimethoxysiloxy group.

[0182] [Examples 1 to 6, Comparative Examples 1 to 6]

[0183] The components were mixed in the parts listed in Tables 1 and 2 to prepare a curable silicone composition. The viscosity at a shear rate of 10 (1 / s) at 25°C, the hardness of the cured product, the tensile elongation, the surface tackiness, and the adhesion to the polyphenylene sulfone resin are shown in the table. It should be noted that in Comparative Example 6, the composition was exposed to 150°C for 2 hours, resulting in a hot-melt material, but no cured product was obtained, so the physical property values ​​of the cured product were set to "NA".

[0184] [Table 1]

[0185]

[0186] [Table 2]

[0187]

[0188]

[0189] [Summarize]

[0190] It can be seen that the curable silicone composition of Examples 1 to 6 of the present invention is able to obtain a composition having a viscosity of 50 Pas or less at 25°C by combining a specific polyorganosiloxane resin and a chain polyorganosiloxane in a specific ratio, and its cured product shows excellent adhesive properties and mechanical strength, and has a low surface viscosity in the elastomer region with a hardness of more than Shore A20.

[0191] On the other hand, it can be seen that the curable silicone composition of Comparative Examples 1 to 4 has a low concentration of curing reactive groups in the composition, and the resulting cured product is very soft and sticky on the surface, which is not suitable for use in sealing the substrate. In addition, the curable silicone composition of Comparative Example 5 forms a harder cured product with low surface viscosity and poorer adhesive properties than the composition of the embodiment. Moreover, the curable silicone composition of Comparative Example 6 is not liquid at room temperature, and no cured product can be obtained even if heat is applied.

Claims

1. A curable silicone composition, characterized in that: Contains at least: (A1-1) a polyorganosiloxane resin represented by the following average unit formula: (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2)e In the formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein all R 1 2 to 40 mol% are alkenyl groups; each R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d and e are numbers satisfying the following: 0.10≤a≤0.90, 0≤b≤0.70, 0≤c≤0.80, 0≤d≤0.65, 0≤e≤0.05, wherein c+d>0.20, and a+b+c+d=1, the weight average molecular weight Mw of the component (A1-1) measured by gel permeation chromatography (GPC) using toluene as a solvent is 15,000 or less, and the (A1-1) is an amount in the range of 1 to 50% by mass relative to the total amount of the components (A1-1), (A2-1) and (B1); (A2-1) a polyorganosiloxane resin represented by the following average unit formula: (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2)j In the formula, each R 3 R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and no carbon-carbon double bond; 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; f, g, h, i and j are numbers satisfying the following: 0.35≤f≤0.70, 0≤g≤0.20, 0≤h≤0.20, 0.30≤i≤0.65, 0≤j≤0.05, and f+g+h+i=1, and (A2-1) is 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) a linear polydiorganosiloxane represented by the following structural formula: <h2 style=";text-align:left;direction:ltr">R<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> 3SiO(SiR<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> 2O)<h2 style=";text-align:left;direction:ltr"> k <h2 style=";text-align:left;direction:ltr"> SiR<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> 3 In the formula, each R 4 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein R 4 At least two of them are alkenyl groups, k is a number from 5 to 1000, and (B1) is an amount in the range of 15 to 70% by mass relative to the total amount of components (A1-1), (A2-1) and (B1); (C) one or more curing agents required to cure the present composition, in an amount sufficient to cure the present composition, The viscosity of the entire composition is 50 Pa·s or less, and the amount of curing-reactive functional groups containing carbon-carbon double bonds in 100 g of the composition is 1.5 mol % or more.

2. The curable silicone composition according to claim 1, characterized in that: When the total amount of the components (A1-1) to (C) is 100 parts by mass, the functional filler (D) is further contained in an amount within a range of 1 to 2000 parts by mass.

3. The curable silicone composition according to claim 1, characterized in that: Component (C) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst, The present composition contains an organohydrogenpolysiloxane in an amount providing 0.9 to 2.0 mol of silicon-bonded hydrogen atoms per 1 mol of the total amount of carbon-carbon double bonds in the composition. 4 . A cured product obtained by curing the curable silicone composition according to claim 1 .

5. The cured product according to claim 4, characterized in that The Shore A hardness is 20 or more. 6 . A semiconductor member comprising the cured product according to claim 4 .

7. A semiconductor device comprising the cured product according to claim 4 or 5.

Images