Process for manufacturing silicone encapsulants

Abstract

The present invention is a process for manufacturing a silicone sealant in the shape of a dome with a flat top or a concave dome, (i) A step of preparing an object to be enclosed on a substrate, (ii) A step of extruding a curable silicone composition onto an object by a potting method, (iii) The step of curing the extruded curable silicone composition by heating to form a silicone sealant in the shape of a dome with a flat top or a concave dome, Includes, The invention relates to a process for a curable silicone composition having a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C.

Description

[Technical Field]

[0001] The present invention relates to a process for manufacturing a silicone encapsulant, and more specifically, to a process for manufacturing a encapsulant in the shape of a dome with a flat top or a concave dome using a curable silicone composition. [Background technology]

[0002] Curable silicone compositions form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency, making them suitable for use in a wide range of industrial fields. Compared to other organic materials, the cured products of such curable silicone compositions are less prone to discoloration and exhibit less deterioration in physical properties such as durability, making them suitable as sealants for optical materials such as light-emitting diodes (LEDs).

[0003] In recent years, curable silicone compositions have been used to form dome-shaped silicone encapsulants for optical semiconductor devices such as light-emitting diodes (LEDs).

[0004] For example, (Patent Document 1) contains the following: (A) Average composition formula (1): R n SiO (4-n) / 2 (1) A liquid or solid organopolysiloxane having at least two alkenyl groups per molecule, represented by (1) (wherein each R is independently a substituted or unsubstituted monovalent hydrogenated group, an alkoxy group, or a hydroxyl group, and 0.1 to 80 mol% of the substituted or unsubstituted monovalent hydrocarbon R contains an alkenyl group, and n is a positive number satisfying 1 ≤ n < 2), (B) Average composition formula (2): R' a H b SiO (4-a-b) / 2(2)Organohydrogenpolysiloxanes having at least two Si-H bonds per molecule, represented by (2) (wherein each R' is independently a substituted or unsubstituted monovalent hydrocarbon other than an aliphatic unsaturated hydrocarbon, and a and b are positive numbers satisfying 0.7 ≤ a ≤ 2.1, 0.001 ≤ b ≤ 1.0, and 0.8 ≤ a + b ≤ 2.6, respectively), and / or Formula (3): R' c SiH (4-c) (3) An organohydrogensilane represented by (3) (wherein each R' is as defined above, and c is 1 or 2), (C) Addition reaction catalyst and A silicone resin composition for encapsulating a light-emitting element, comprising: A silicone resin composition is disclosed, comprising (D) 2 to 25 wt% of silica with an average particle size of 1 to 30 nm based on the total amount of components (A) and (B), having a viscosity greater than 10 Pa·s and less than 70 Pa·s (at 23°C) and a thixotropic index of 2.0 to 5.5, and being used for sealing using a potting method.

[0005] Furthermore, (Patent Document 2) describes a method for manufacturing a light-emitting device comprising a substrate, a plurality of light sources arranged on the substrate, and a plurality of sealing members covering each of the plurality of light sources, the method being as follows: To provide a substrate having multiple light sources arranged on the substrate, By supplying sealing material onto a substrate through multiple nozzles of an extrusion device, multiple sealing members are formed to cover each of the multiple light sources, Includes, Forming multiple sealing members includes performing a first formation and a second formation, the second formation being performed following the first formation. When the first formation is carried out, the sealing member is formed while holding a portion of the sealing material hanging from each of the multiple nozzles as a hanging thread-like portion, and A method is disclosed, wherein the second formation is started from a hanging filament portion of a sealing material held in a state of hanging from each of a plurality of nozzles of an ejection device.

[0006] Also, (Patent Document 3) discloses the following: a substrate; a light source having an optical axis, a light source bottom portion, and a light source upper portion opposite to the light source bottom portion along the optical axis, wherein the light source bottom portion is provided on the substrate; a covering member having a bottom surface and a top portion opposite to the bottom surface along the optical axis, the bottom surface being provided on the substrate so as to cover the light source, wherein the covering member has a recessed portion on the top portion above the light source and around the optical axis, and the covering member tapers toward the bottom surface; a light emitting device comprising the above is disclosed.

[0007] In addition, (Patent Document 4) discloses the following: (A) a branched organopolysiloxane having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group per molecule, and having a siloxane unit represented by the general formula: RSiO 3 / 2 wherein R is a substituted or unsubstituted monovalent hydrocarbon group; (B) a linear organopolysiloxane wherein both terminals of the molecular chain are blocked by silicon-bonded hydrogen atoms, and the linear organopolysiloxane has at least one silicon-bonded aryl group per molecule; (C) a hydrosilylation reaction catalyst; (D) an average formula (R 5 3SiO 1 / 2 ) i (R 5 2SiO 2 / 2 ) g (R 5 SiO 3 / 2 ) h (SiO4 / 2) i wherein each R 5These can be the same or different, and are independently selected from substituted or unsubstituted monovalent hydrocarbon groups, with R per molecule. 5 A low molecular weight siloxane having at least one silicon-bonded alkenyl group per molecule, represented by (at least one of which is an alkenyl group, wherein the ratio of the alkenyl group to the silicon atom is 0.3 to 1, f, g, h, and i are independently 0 or positive, and the weight-average molecular weight Mw of the siloxane is less than 1,000 g / mol), A curable organopolysiloxane composition containing is disclosed.

[0008] Some semiconductor device products require unique dome-shaped encapsulants, such as domes with flat top surfaces or concave domes. However, when using conventional curable silicone compositions, there is a problem in that an additional step is required to shape the extruded silicone composition into such a unique shape, for example, by pressing the dome-shaped extruded silicone composition after extruding the curable silicone composition onto the substrate. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2008-231199 [Patent Document 2] Japanese Patent Publication No. 2019-153785 [Patent Document 3] U.S. Patent Application Publication No. 2016-153785 [Patent Document 4] Japanese Patent Publication No. 2019-524959 [Overview of the project] [Problems that the invention aims to solve]

[0010] The object of the present invention is to provide a process for producing a silicone sealant in the shape of a dome with a flat top or a concave dome from a curable silicone composition, which does not require a step, for example, pressing the extruded silicone material, in order to form the sealant into such a unique shape. [Means for solving the problem]

[0011] The above object of the present invention is a process for manufacturing a silicone sealant in the shape of a dome with a flat top or a concave dome, which is described below: (i) A step of preparing an object to be enclosed on a substrate, (ii) A step of extruding a curable silicone composition onto a substrate by a potting method, (iii) The step of curing the extruded curable silicone composition by heating to form a silicone sealant in the shape of a dome with a flat top or a concave dome, Includes, A curable silicone composition having a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C can be achieved by process.

[0012] This process does not necessarily have to include extra steps for physically shaping the extruded curable silicone composition.

[0013] Heating can be carried out at a temperature of 50-150°C for 1-120 minutes.

[0014] Curable silicone compositions, the following: (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B)(A) At least one MQ resin having at least two alkenyl groups per molecule, other than a resinous organopolysiloxane, (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, It may include.

[0015] The curable silicone composition may further contain at least one hydrosilylation reaction inhibitor.

[0016] (C) The organohydrogenpolysiloxane may contain at least one linear organohydrogenpolysiloxane.

[0017] (A) The weight ratio of alkenyl group-containing resinous organopolysiloxane to linear organohydrogenpolysiloxane may be in the range of 1:1 to 10:1.

[0018] The present invention also relates to a curable silicone composition for producing a sealing material in the shape of a dome with a flat top or a concave dome by dispersion, the following: (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B)(A) At least one MQ resin having at least two alkenyl groups per molecule, other than a resinous organopolysiloxane, (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, Includes, This invention relates to a curable silicone composition having a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C.

[0019] The present invention also relates to a sealing material having a flat top and a dome shape or a concave dome shape formed from a curable silicone composition according to the present invention.

[0020] The present invention also relates to an optical semiconductor device provided with a encapsulating material according to the present invention.

[0021] The present invention provides a process for producing a silicone sealant in the shape of a dome with a flat top or a concave dome using a curable silicone composition, without requiring a step to shape the sealant. Therefore, the process according to the present invention can produce such dome-shaped sealants very effectively. [Brief explanation of the drawing]

[0022] [Figure 1] A cross-sectional view of an exemplary semiconductor device of the present invention is shown, including a dome-shaped encapsulant with a flat top (Figure 1A) or a concave dome-shaped encapsulant (Figure 1B). [Modes for carrying out the invention]

[0023] After diligent research, the inventors have surprisingly discovered that, without requiring any steps for fabricating the curable silicone composition, it is possible to fabricate a curable silicone composition having a viscosity and thixotropic index value within a specific range in unique dome shapes, such as a dome shape with a flat top surface or a concave dome shape, by extrusion.

[0024] Therefore, the process according to the present invention is a process for manufacturing a silicone sealant in the shape of a dome with a flat top or a concave dome, and is described below: (i) A step of preparing an object to be enclosed on a substrate, (ii) A step of extruding a curable silicone composition onto a substrate by a potting method, (iii) The step of curing the extruded curable silicone composition by heating to form a silicone sealant in the shape of a dome with a flat top or a concave dome, Includes, The curable silicone composition is a process that has a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C.

[0025] The processes, compositions, and uses according to the present invention will be described in more detail below.

[0026] process The process according to the present invention is a process for manufacturing a silicone encapsulant in the shape of a dome with a flat top or a concave dome, (i) A step of preparing an object to be enclosed on a substrate, (ii) A step of extruding a curable silicone composition onto an object by a potting method, (iii) The step of curing the extruded curable silicone composition by heating to form a silicone sealant in the shape of a dome with a flat top or a concave dome, This process includes [something].

[0027] The process according to the present invention makes it possible to form a silicone sealant in the shape of a dome with a flat top or a concave dome simply by heating the extruded curable silicone composition. Therefore, the process according to the present invention does not need to include an extra step for physically shaping the extruded curable silicone composition, such as pressing the curable silicone composition.

[0028] Encapsulating materials in the shape of a dome with a flat top or a concave dome can broaden the beam angle by preventing uneven illumination patterns when used in optical semiconductor devices. For this reason, the process according to the present invention is very useful for encapsulation in the manufacture of semiconductor packages, and in particular optical semiconductor packages such as LED packages.

[0029] Each step of the curable silicone composition is described below.

[0030] Step (i) Step (i) of the present invention is to prepare an object to be enclosed on a substrate.

[0031] The object to be enclosed may be a semiconductor element, including an optical semiconductor. Examples of semiconductor elements include SiC and GaN. Examples of optical semiconductor elements include devices such as light-emitting diodes (LEDs), photodiodes, phototransistors, and laser diodes.

[0032] The substrate on which the sealing material of the present invention is formed is not particularly limited, but can be selected from, for example, a glass substrate and a PCB substrate. The glass substrate may or may not be surface-coated with a well-known surface treatment agent such as a silicone surface treatment agent.

[0033] Step (ii) Step (ii) of the present invention is to extrude a curable silicone composition onto an object by a potting method.

[0034] In this specification, the term "potting method" means a method of dropping a sealing liquid composition onto a substrate. Therefore, in this invention, the potting method means dropping a curable silicone composition onto a substrate.

[0035] The curable silicone composition can be dispensed using an air dispenser or a jetting machine. The dispenser for dispensing the curable silicone composition is not particularly limited as long as it is capable of dropping the curable silicone composition onto the substrate by the potting method, and any commonly used dispenser can be used. A piezo-type dispenser of a jetting machine is preferred.

[0036] The dispenser may have a single nozzle for injecting or spraying the curable silicone composition onto a substrate. The inner diameter of the nozzle is not particularly limited, but is generally in the range of 10 μm to 1500 μm, preferably 15 μm to 1300 μm, and more preferably 20 μm to 1100 μm.

[0037] The number of dots used to create the shape is not particularly limited, but is generally in the range of 1 to 50 shots, preferably 1 to 40 shots.

[0038] The needle lift or punching stroke is not particularly limited, but is generally in the range of 20-100%, preferably 30-90%.

[0039] The volume of one drop of the curable silicone composition discharged from the dispenser is not particularly limited, but is generally in the range of 1E-10 to 1E-0 cc / drop, preferably 1E-9 to 1E-1 cc / drop.

[0040] The pressure for injecting or spraying the curable silicone composition from the nozzle onto the substrate is not particularly limited, but is generally in the range of 0.5 to 10 bar.

[0041] In one embodiment of the present invention, the temperature of the curable silicone composition can be controlled as it is discharged from the nozzle. The nozzle can be heated for the purpose of heating the curable silicone composition. The temperature of the curable silicone composition during injection or spraying is not particularly limited, but is generally in the range of 20°C to 60°C, preferably 25°C to 50°C.

[0042] The curable silicone composition of the present invention has a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C. The viscosity of the curable silicone composition may be 3,000 to 15,000 mPa·s or 3,000 to 12,000 mPa·s at 25°C. The viscosity as used herein can be measured under atmospheric conditions at 25°C using a rotational viscometer in accordance with JIS K7117-1, for example, using a rheometer with a 40 mm cone plate at a shear rate of 20 / s and an angle of 2 degrees.

[0043] The curable silicone composition of the present invention exhibits a thixotropic index value in the range of 4.0 to 15.0 at 25°C. The thixotropic index value may be in the range of 5.0 to 13.0 at 25°C. In the present invention, the thixotropic index value can be calculated as the viscosity ratio of (viscosity at 25°C, 1 rpm) / (viscosity at 25°C, 10 rpm). This viscosity ratio means the viscosity ratio of (viscosity at 25°C, 1 rpm) / (viscosity at 25°C, 10 rpm). Viscosity can be measured, as described above, for example, under atmospheric conditions at 25°C using a rotational viscometer in accordance with JIS K7117-1, for example, using a rheometer with a 40 mm cone plate at an angle of 2 degrees.

[0044] In one embodiment of the present invention, the curable silicone composition of the present invention (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B)(A) At least one MQ resin having at least two alkenyl groups per molecule, other than a resinous organopolysiloxane, (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, Includes.

[0045] Each component in the curable silicone composition is described below.

[0046] (A) Resinous organopolysiloxane The curable silicone composition contains at least one resinous organopolysiloxane having at least two alkenyl groups per molecule. The curable silicone composition may contain one type of (A) alkenyl group-containing resinous organopolysiloxane, or it may contain a combination of two or more types of (A) alkenyl group-containing resinous organopolysiloxanes.

[0047] (A) Alkenyl group-containing organopolysiloxanes have a resinous structure. The term "resinous" here means that the organopolysiloxane has a branched or three-dimensional network structure within the molecule.

[0048] The alkenyl group included in component (A) is C 2~12 Examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups, preferably vinyl.

[0049] Other silicon atom-bonded organic groups included in component (A), besides the alkenyl group, include C 1~12 Alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, C 6~12Aryl groups, for example, phenyl group, tolyl group, xylyl group, and naphthyl group, C 7~12 Examples include aralkyl groups, such as benzyl, phenethyl, and phenylpropyl groups, and groups obtained by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, chlorine, and bromine atoms. It should be noted that small amounts of alkoxy groups, such as methoxy or ethoxy groups, may be bonded to the silicon atoms of component (A), as long as they do not adversely affect the objective of the present invention. Preferably, silicon-bonded organic groups other than alkenyl groups are C 1~12 Alkyl groups, specifically methyl groups, and C6~12 It contains an aryl group, such as a phenyl group. Component (A) does not have to contain a thiol group or a glycidyl group.

[0050] In one embodiment of the present invention, (A) the alkenyl group-containing resinous organopolysiloxane is the following formula (I): Average unit formula (I): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e (In the formula, R 1 This represents the same or different monovalent hydrocarbons that can be optionally substituted with at least one halogen, and per molecule R 1 At least two of the elements represent alkenyl groups, X represents hydrogen or an alkyl group, and the following conditions are met: 0 ≤ a < 1, 0 ≤ b < 1, 0 ≤ c < 0.95, 0 ≤ d < 0.9, 0 ≤ e < 0.4, a + b + c + d = 1.0, and c + d > 0. It can be expressed by the following: The numerical value e is the number of silicon atoms included (XO) 1 / 2 This indicates the ratio of the number of bases.

[0051] Here, SiO x / 2The formula containing siloxane units, represented by (where x is an integer from 1 to 4), is expressed as the "average unit formula," while SiO x / 2 Formulas that do not contain siloxane units, as represented by this formula, are expressed as "average structural formulas".

[0052] R in equation (I) can be optionally substituted with at least one halogen. 1 As a monovalent hydrocarbon, C 1~12 Alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, C 2~12 Alkenyl groups, for example, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, and dodecenyl group, C 6~12 Aryl groups, for example, phenyl group, tolyl group, xylyl group, and naphthyl group, C 7~12 Aralkyl groups, such as benzyl, phenethyl, and phenylpropyl groups, may include groups obtained by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, chlorine, or bromine. 1 The monovalent hydrocarbon may contain small amounts of alkoxy groups such as methoxy or ethoxy groups, as long as it does not adversely affect the objectives of the present invention. Preferably, R 1 The monovalent hydrocarbon is C 1~12 Alkyl groups, specifically methyl groups, C 2~12 Alkenyl group, specifically vinyl group, or C 6~12 This represents an aryl group, and more specifically, a phenyl group.

[0053] In formula (I), X represents hydrogen or an alkyl group. The alkyl group of X is preferably a methyl group, an ethyl group, or a propyl group, etc. 1~3 Represents an alkyl group.

[0054] In one embodiment of the present invention, in formula (I), a is preferably in the range of 0.05 ≤ a ≤ 0.6, more preferably in the range of 0.1 ≤ a ≤ 0.5, and even more preferably in the range of 0.15 ≤ a ≤ 0.4. In formula (I), b is preferably in the range of 0 ≤ b ≤ 0.3, more preferably in the range of 0 ≤ b ≤ 0.2, and even more preferably in the range of 0 ≤ b ≤ 0.1. In formula (I), c is preferably in the range of 0.3 ≤ c ≤ 0.9, more preferably in the range of 0.45 ≤ c ≤ 0.85, and even more preferably in the range of 0.6 ≤ c ≤ 0.8. In formula (I), d is preferably in the range of 0 ≤ d ≤ 0.3, more preferably in the range of 0 ≤ d ≤ 0.2, and even more preferably in the range of 0 ≤ d ≤ 0.1. In formula (I), e is preferably in the range of 0 ≤ e ≤ 0.2, more preferably in the range of 0 ≤ e ≤ 0.1, and even more preferably in the range of 0 ≤ e ≤ 0.05. In this specification, any combination of upper and lower numerical limits can be used to represent a particular range of numerical values.

[0055] In one embodiment of the present invention, in formula (I), a is greater than 0. That is, (A) resinous organopolysiloxane is (R3SiO 1 / 2 It contains at least one M siloxane unit represented by ). In one embodiment of the present invention, in formula (I), c is greater than 0. That is, (A) resinous organopolysiloxane is (RSiO 3 / 2 It comprises at least one T siloxane unit represented by ). In one embodiment, (A) resinous organopolysiloxane is (R2SiO 2 / 2 It may or may not contain D siloxane units represented by ), but preferably it does not contain any D units. In one embodiment, (A) resinous organopolysiloxane is (SiO 4 / 2 The material may or may not contain Q siloxane units represented by ), but preferably it contains no Q units at all. For this reason, in one preferred embodiment, (A) the resinous organopolysiloxane consists of M and T units and is in the form of an MT resin. Here, R in the siloxane unit represents an organic group bonded to a silicon atom.

[0056] (A) The amount of alkenyl groups relative to the total amount of silicon-bonded organic groups in the organopolysiloxane is not particularly limited, but is, for example, 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and / or generally 30 mol% or less, preferably 20 mol% or less, and more preferably 10 mol% or less, relative to the total amount of silicon-bonded organic groups. The amount of alkenyl groups can be measured, for example, by analytical methods such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR), or by the titration method described below. In this specification, any combination of upper and lower numerical limits can be used to represent a particular numerical range.

[0057] A method for quantifying the amount of alkenyl groups in organopolysiloxanes by titration is described below. The content of alkenyl groups in organopolysiloxanes can be accurately quantified by a titration method known as the Wies process. The principle is described below. First, the alkenyl groups and iodine monochloride present in the organopolysiloxane raw materials are subjected to the addition reaction shown in formula (1). Next, the excess amount of iodine monochloride is reacted with potassium iodide by the reaction shown in formula (2) to release iodine. Then, the free iodine is titrated with a sodium thiosulfate solution. Equation (1) CH2=CH- + 2ICl → CH2I-CHCl- + ICl (excess amount) Formula (2) ICl+KI→I2+KCl The amount of alkenyl groups present in organopolysiloxane can be quantified by the difference between the amount of sodium thiosulfate required for the titration described above and the amount in a separately prepared blank solution.

[0058] (A) The resinous organopolysiloxane may or may not contain an aryl group in the silicon atom-bonded organic group. In one embodiment of the present invention, (A) the resinous organopolysiloxane preferably contains at least one aryl group in the T unit. (A) The organopolysiloxane may or may not contain an aryl group in the M unit, but preferably does not contain an aryl group in the M unit.

[0059] (A) The content of aryl groups in the resinous organopolysiloxane is not particularly limited if present, but is generally 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, and / or generally 40 mol% or less, preferably 30 mol% or less, and more preferably 20 mol% or less, based on the total amount of silicon atom-bonded organic groups. The amount of aryl groups can be measured using analytical methods such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0060] (A) The weight-average molecular weight of the resinous organopolysiloxane is not particularly limited, but is preferably 1,000 to 100,000, more preferably 1,200 to 50,000, and more preferably 1,500 to 10,000. The weight-average molecular weight can be measured (in polystyrene terms) using gel permeation chromatography (GPC).

[0061] In one embodiment, (A) the resinous organopolysiloxane is solid at room temperature (25°C).

[0062] (A) The resinous organopolysiloxane may be present in an amount of 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and / or 80% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, based on the total weight of the composition. Any combination of the upper and lower limits is available.

[0063] (A) The resinous organopolysiloxane may be present in an amount of 10% to 80% by weight, preferably 20% to 70% by weight, more preferably 30% to 60% by weight, or more, based on the total weight of the composition.

[0064] (B)MQ resin The curable silicone composition comprises at least one MQ resin having at least two alkenyl groups per molecule. The curable silicone composition may comprise one type of (B) alkenyl group-containing MQ resin, or a combination of two or more types of (B) alkenyl group-containing MQ resins.

[0065] The term "MQ resin" used here refers to an organopolysiloxane composed of M and Q units.

[0066] (B) MQ resin is different from (A) resinous organopolysiloxane.

[0067] (B) Alkenyl group-containing organopolysiloxanes have a resinous structure. The term "resinous" here means that the organopolysiloxane has a branched or three-dimensional network structure within the molecule.

[0068] The alkenyl group included in component (B) is C 2~12 Examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups, preferably vinyl.

[0069] Other silicon atom-bonded organic groups in component (B), besides the alkenyl group, include C 1~12 Alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, C 6~12 Aryl groups, for example, phenyl group, tolyl group, xylyl group, and naphthyl group, C 7~12Aralkyl groups, such as benzyl group, phenethyl group, and phenylpropyl group, and groups obtained by substituting part or all of hydrogen atoms of these groups with halogen atoms such as fluorine atom, chlorine atom and bromine atom may be mentioned. It should be noted that a small amount of alkoxy groups such as methoxy group and ethoxy group may be bonded to the silicon atom of component (B) as long as the object of the present invention is not adversely affected. Preferably, the silicon-bonded organic group other than alkenyl group is C 1~12 an alkyl group, specifically a methyl group.

[0070] In one embodiment of the present invention, (B) the alkenyl group-containing MQ resin is represented by the following formula (II): Average unit formula (II): (R 1 3SiO 1 / 2 ) s (SiO 4 / 2 ) t (XO 1 / 2 ) u (wherein R 1 represents the same or different monovalent hydrocarbon which can be optionally substituted with at least one halogen, at least two of R 1 per molecule represent an alkenyl group, X represents hydrogen or an alkyl group, and 0<s<1, 0<t<1, 0≦u<0.4, and s+t=1.0 are satisfied) can be represented by The numerical value u represents the ratio of the number of (XO 1 / 2 ) groups contained to the total number of silicon atoms.

[0071] The same definitions for the monovalent hydrocarbon and alkenyl group of R 1 in the above formula (I) can be applied to the definition of R 1 in the formula (II). Also, the same definition for X in the above formula (I) can be applied to X in the formula (II).

[0072] In one embodiment of the present invention, in formula (II), s is preferably in the range of 0.3 ≤ s ≤ 0.9, more preferably in the range of 0.2 ≤ s ≤ 0.8, and even more preferably in the range of 0.4 ≤ s ≤ 0.7. In formula (II), t is preferably in the range of 0.1 ≤ t ≤ 0.7, more preferably in the range of 0.2 ≤ t ≤ 0.6, and even more preferably in the range of 0.3 ≤ t ≤ 0.5. In formula (II), u is preferably in the range of 0 ≤ u ≤ 0.2, more preferably in the range of 0 ≤ u ≤ 0.1, and even more preferably in the range of 0 ≤ u ≤ 0.05.

[0073] (B) The amount of alkenyl groups relative to the total amount of silicon-bonded organic groups in the MQ resin is not particularly limited, but is, for example, 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and / or generally 40 mol% or less, preferably 30 mol% or less, and more preferably 25 mol% or less, relative to the total amount of silicon-bonded organic groups. The amount of alkenyl groups can be measured, for example, by analytical methods such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR), or by the titration method described above.

[0074] (B) The MQ resin may or may not contain an aryl group in the silicon atom-bonded organic group. In one embodiment of the present invention, the (B) MQ resin does not contain an aryl group in the silicon atom-bonded organic group.

[0075] (B) The weight-average molecular weight of the MQ resin is not particularly limited, but is preferably 10 to 10,000, more preferably 100 to 5,000. The weight-average molecular weight can be measured (in polystyrene equivalent) using gel permeation chromatography (GPC).

[0076] (B) The viscosity of the MQ resin is not particularly limited, but may be, for example, 1 mPa·s to 1,000 mPa·s, preferably 3 to 500 mPa·s, at 25°C. The viscosity of the organopolysiloxane components herein can be measured using a rotational viscometer in accordance with JIS K7117-1 under atmospheric conditions.

[0077] (B) Siloxane units (SiO) contained in MQ resin x / 2 The number of ) is not particularly limited, but for example, it is 3 to 2,000, preferably 5 to 1,000.

[0078] (B) The MQ resin may be present in an amount of 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and / or in an amount of 40% by weight or less, preferably 30% by weight or less, more preferably 25% by weight or less, based on the total weight of the composition.

[0079] (B) The MQ resin may be present in an amount of 1% to 40% by weight, preferably 2% to 30% by weight, and more preferably 3% to 25% by weight, based on the total weight of the composition.

[0080] (C) Organohydrogenpolysiloxane The curable silicone composition contains at least one (C) organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule. The curable silicone composition may contain one type of (C) organohydrogenpolysiloxane, or it may contain a combination of two or more types of (C) organohydrogenpolysiloxanes.

[0081] (C) The organohydrogenpolysiloxane may be linear, branched, partially branched, cyclic, or resinous. Preferably, (C) the organohydrogenpolysiloxane is a linear or resinous organohydrogenpolysiloxane, and more specifically, (C) the organohydrogenpolysiloxane is a linear organohydrogenpolysiloxane or an MQ resin-type organohydrogenpolysiloxane.

[0082] In a preferred embodiment, (C) organohydrogenpolysiloxane comprises at least one linear organohydrogenpolysiloxane.

[0083] Other silicon atom-bonded organic groups besides the hydrogen atom in component (C) include monovalent hydrocarbons other than alkenyl groups, for example, C 1~12 Alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, C 6~12 Aryl groups, for example, phenyl group, tolyl group, xylyl group, and naphthyl group, C 7~12 Examples include aralkyl groups, such as benzyl, phenethyl, and phenylpropyl groups, and groups obtained by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, chlorine, and bromine. It should be noted that small amounts of alkoxy groups, such as methoxy or ethoxy groups, may be bonded to the silicon atoms of component (C) as long as they do not adversely affect the objective of the present invention. Preferably, silicon atom-bonded organic groups other than hydrogen atoms are located on C. 1~12 Alkyl groups, specifically methyl groups and C 6~12 It includes aryl groups, and more specifically, phenyl groups.

[0084] In one embodiment of the present invention, (C) organohydrogenpolysiloxane is given by the following formula (III-a): Average structural formula (III-a):R 2 3SiO(R 2 2SiO) m SiR 2 3 (In the formula, R 2 This represents the same or different monovalent hydrocarbon other than an alkenyl group that can be optionally substituted with at least one halogen, and R per molecule 2 (At least two of them represent hydrogen atoms, and m is in the range of 1 to 50.) It can be represented by this.

[0085] R in equation (III-a) can be optionally substituted with at least one halogen. 2 Other monovalent hydrocarbons besides the alkenyl group include C1~12 Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group, C 6~12 Aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group, C 7~12 Aralkyl groups such as benzyl group, phenethyl group, and phenylpropyl group, and groups obtained by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine atom, chlorine atom, and bromine atom. As long as the object of the present invention is not adversely affected, R 2 the monovalent hydrocarbon may contain a small amount of alkoxy groups such as methoxy group and ethoxy group. Preferably, R 2 the monovalent hydrocarbon is C 1~12 alkyl group, specifically methyl group, or C 6~12 aryl group, specifically phenyl group.

[0086] In formula (III-a), m is preferably in the range of 1 to 25, more preferably 1 to 10, still more preferably 1 to 5.

[0087] In a preferred embodiment, the linear organohydrogenpolysiloxane according to formula (III-a) comprises at least one aryl group, preferably a phenyl group, in a side chain of the molecular chain. In other words, the linear organohydrogenpolysiloxane according to formula (III-a) has (R2SiO 2 / 2 ) may comprise at least one aryl group in the D siloxane unit represented by . In another preferred embodiment, the linear organohydrogenpolysiloxane according to formula (III-a) comprises at least one (Ar2SiO 2 / 2 ) unit, wherein Ar represents an aryl group, preferably a phenyl group.

[0088] When (C) organohydrogenpolysiloxane contains a plurality of aryl groups per molecule, the content of aryl groups in (C) organohydrogenpolysiloxane is not particularly limited, but is generally 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and generally 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, based on the total amount of silicon-bonded organic groups. The amount of aryl groups can be measured, for example, using an analysis method such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0089] In one embodiment of the present invention, (C) organohydrogenpolysiloxane is represented by the following formula (III-b): Average unit formula (III-b): (R 2 ₃SiO 1 / 2 ) s (SiO 4 / 2 ) t (XO 1 / 2 ) u (wherein R 2 represents the same or different monovalent hydrocarbons other than alkenyl groups optionally substituted with at least one halogen, at least two of R 2 per molecule represent a hydrogen atom, X represents hydrogen or an alkyl group, and 0<s<1, 0<t<1, 0≦u<0.4, and s+t=1.0 are satisfied) comprises at least one MQ resin-type organohydrogenpolysiloxane (or MQ resin-form organohydrogenpolysiloxane) that can be represented by the above. The numerical value u represents the ratio of the number of (XO₁ / ₂) groups contained to the total number of silicon atoms.

[0090] The same definitions for the monovalent hydrocarbon and alkenyl groups of R 2 in the above formula (III-a) can be applied to the definition of R 2 in formula (III-b).

[0091] In formula (III-b), X represents hydrogen or an alkyl group. The alkyl group for X is preferably C such as methyl, ethyl, propyl 1~3 alkyl group.

[0092] In one embodiment of the present invention, in formula (III-b), s is preferably within the range of 0.3 < s ≤ 0.9, more preferably within the range of 0.4 < s ≤ 0.8, and even more preferably within the range of 0.5 < s ≤ 0.7. In formula (III-b), t is preferably within the range of 0.1 ≤ t ≤ 0.7, more preferably 0.2 ≤ t ≤ 0.6, and even more preferably 0.3 ≤ t ≤ 0.5. In formula (III-b), u is preferably within the range of 0 ≤ u ≤ 0.2, more preferably 0 ≤ u ≤ 0.1, and even more preferably 0 ≤ u ≤ 0.05.

[0093] The weight average molecular weight of (C) organohydrogenpolysiloxane is not particularly limited, but is preferably 10 to 10,000, more preferably 100 to 5,000.

[0094] The viscosity of (C) organohydrogenpolysiloxane is not particularly limited, and for example, may be 1 mPa·s to 500 mPa·s at 25°C, preferably 3 to 100 mPa·s.

[0095] The siloxane units (SiO contained in MQ resin-type organohydrogenpolysiloxane x / 2 ) is not particularly limited, and for example, is 5 to 2,000, preferably 10 to 1,000.

[0096] (C) organohydrogenpolysiloxane may be present in an amount of 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, based on the total weight of the composition, and / or may be present in an amount of 50% by weight or less, preferably 40% by weight or less, more preferably 35% by weight or less.

[0097] (C) Organohydrogenpolysiloxane may be present in an amount of 5% to 50% by weight, preferably 10% to 40% by weight, and more preferably 15% to 35% by weight, based on the total weight of the composition.

[0098] In a preferred embodiment of the present invention, the (C) organohydrogenpolysiloxane can be included in the curable silicone composition such that the molar ratio of silicon-bonded hydrogen atoms derived from component (C) to silicon-bonded alkenyl groups in the organopolysiloxane component, i.e., the H / Vi molar ratio, is 0.5 or higher, preferably 0.65 or higher, more preferably 0.8 or higher, and / or 3.0 or lower, preferably 2.0 or lower, more preferably 1.5 or lower.

[0099] In one embodiment of the present invention, (C) organohydrogenpolysiloxane includes linear organohydrogenpolysiloxane. In a preferred embodiment, the weight ratio of (A) alkenyl group-containing resinous organopolysiloxane to linear organohydrogenpolysiloxane is in the range of 1:1 to 10:1, preferably 1:1 to 5:1, and more preferably 1:1 to 4:1.

[0100] (D) Inorganic filler The curable silicone composition contains at least one inorganic filler. The curable silicone composition may contain one type of (D) inorganic filler, or it may contain two or more types of (D) inorganic fillers in combination.

[0101] The term "filler" should be understood to mean mineral or synthetic particles of any shape that are insoluble in the medium of the composition.

[0102] (D) The inorganic filler may be any shape, regardless of its crystallographic morphology (e.g., lamellar, cubic, hexagonal, orthorhombic): plate-like, spherical, or elongated. Preferably, the highly reflective inorganic filler is spherical.

[0103] (D) Examples of inorganic fillers include metal oxides, such as silica, such as fumed silica, precipitated silica, fused silica, calcined silica, quartz, and titanium dioxide, aluminum oxide, zinc oxide, and aluminum oxides, zirconium oxides, titanium oxides, zinc oxides, carbonates, such as calcium carbonate, zinc carbonate, metal hydroxides, such as aluminum hydroxide, and diatomaceous earth. Preferably, (D) the inorganic filler is selected from silica.

[0104] (D) The inorganic filler may be subjected to surface hydrophobic treatment with an organosilicon compound, such as an organoalkoxysilane compound, organochlorosilane compound, organosilazane compound, or low molecular weight siloxane compound, or a silane coupling agent, titanate coupling agent, etc., before being used in the present invention.

[0105] (D) The inorganic filler may have an average primary particle size in the range of 1 nm to 100 nm, preferably 2 nm to 50 nm, more preferably 3 nm to 30 nm. The term “average primary particle size” as used herein refers to the number-average size-average diameter given by the statistical particle size distribution for half of the population, and is referred to as D50. For example, the number-average size-average diameter can be measured by a laser diffraction particle size distribution analyzer.

[0106] (D) The inorganic filler may be present in an amount of 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight or more, and 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, based on the total weight of the composition.

[0107] (D) Inorganic fillers may be present in an amount of 1% to 20% by weight, preferably 2% to 15% by weight, and more preferably 3% to 10% by weight, based on the total weight of the composition.

[0108] (E) Hydrosilylation catalyst The curable silicone composition contains at least one (E) hydrosilylation catalyst that promotes the hydrosilylation curing reaction of organopolysiloxane components. The curable silicone composition may contain one type of (E) hydrosilylation catalyst, or a combination of two or more types of (E) hydrosilylation catalysts.

[0109] Examples of hydrosilylation catalysts include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts. Platinum-based catalysts are preferred. Examples of platinum-based catalysts include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, chloroplatinic acid alcohol solution, platinum olefin complexes, and platinum alkenylsiloxane complexes. Platinum alkenylsiloxane complexes are particularly preferred. Examples of alkenylsiloxanes include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which some of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups, etc.

[0110] The amount of (E) hydrosilylation catalyst used is an effective amount and is not particularly limited. For example, the (E) hydrosilylation catalyst may be present in an amount of 0.1 ppm or more, preferably 1 ppm or more, more preferably 2 ppm or more, based on the total weight of the (E) curing reactive organopolysiloxane, and / or in an amount of 20 ppm or less, preferably 15 ppm or less, more preferably 10 ppm or less. Any combination of the upper and lower limits is available.

[0111] Other organopolysiloxanes In one embodiment of the present invention, the curable silicone composition may or may not contain at least one linear alkenyl group-containing organopolysiloxane. The alkenyl group-containing linear organopolysiloxane contains at least two alkenyl groups per molecule, which are represented by the following formula (IV): Average structural formula (IV):R 1 3SiO(R 1 2SiO) m SiR 1 3 (In the formula, R 1 This represents the same or different monovalent hydrocarbons that can be optionally substituted with at least one halogen, and per molecule R 1 (At least two of these represent alkenyl groups, and m is in the range of 1 to 1,000) It can be represented by: One type of linear organopolysiloxane or two or more types of linear organopolysiloxanes can be included in the curable silicone composition.

[0112] R in equation (I) 1 The same definition applies to R in equation (IV). 1 It can be applied to [this].

[0113] In formula (IV), m is preferably in the range of 5 to 500, more preferably 20 to 300, and even more preferably 50 to 200.

[0114] In one embodiment of the present invention, the alkenyl group-containing linear organopolysiloxane can be a linear dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of the molecular chain.

[0115] Alkenyl group-containing linear organopolysiloxanes may contain at least one aryl group in the silicon atom-bonded organic group. In a preferred embodiment of the present invention, the alkenyl group-containing linear organopolysiloxane contains at least one aryl group in the D unit, i.e., in the side chain. The alkenyl group-containing linear organopolysiloxane may or may not contain an aryl group in the M unit, i.e., at the molecular end, but preferably the M unit does not contain an aryl group.

[0116] The content of aryl groups in alkenyl group-containing linear organopolysiloxanes is not particularly limited, but is generally 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, and / or generally 70 mol% or less, preferably 60 mol% or less, and more preferably 50 mol% or less, based on the total amount of silicon atom-bonded organic groups. The amount of aryl groups can be measured, for example, by analytical methods such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR), or by the titration method described below.

[0117] The weight-average molecular weight of the alkenyl group-containing linear organopolysiloxane is not particularly limited, but is preferably 100 to 100,000, and more preferably 1,000 to 50,000.

[0118] The viscosity of the alkenyl group-containing linear organopolysiloxane is not particularly limited, but can be, for example, 100 mPa·s to 100,000 mPa·s at 25°C, preferably 1,000 to 50,000 mPa·s.

[0119] The alkenyl group-containing linear organopolysiloxane may be present in an amount of 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and / or 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, based on the total weight of the composition. Any combination of the upper and lower limits is available.

[0120] In another embodiment of the present invention, the curable silicone composition may or may not contain at least one epoxy group-containing resinous organopolysiloxane. The epoxy group-containing resinous organopolysiloxane is defined by the following formula (V): Average structural formula (V):(R 3 3SiO 1 / 2 ) a (R 3 2SiO 2 / 2 ) b (R 3 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e (In the formula, R 3 This represents the same or different monovalent hydrocarbons that can be optionally substituted with at least one halogen, and per molecule R 3 At least two of them represent an alkenyl group, and each molecule contains R 3 At least one of the elements represents an epoxy group-containing organic group, X represents hydrogen or an alkyl group, and the following conditions are met: 0 ≤ a < 1, 0 ≤ b < 1, 0 ≤ c < 0.95, 0 ≤ d < 0.9, 0 ≤ e < 0.4, a + b + c + d = 1.0, and c + d > 0. It can be expressed by the following: The numerical value e is the number of silicon atoms included (XO) 1 / 2 This indicates the ratio of the number of groups. It is possible to use one type of epoxy group-containing resinous organopolysiloxane or two or more types of epoxy group-containing resinous organopolysiloxane.

[0121] R in equation (I) 1 The same definition as monovalent hydrocarbons in formula (V) is applied to R 3 It can be applied to monovalent hydrocarbons.

[0122] R in equation (V) 3The epoxy group-containing organic group includes glycidoxyalkyl groups such as 2-glycidoxyethyl group, 3-glycidoxypropyl group and 4-glycidoxybutyl group; epoxycycloalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl group and 3-(3,4-epoxycyclohexyl)propyl group; epoxyalkyl groups such as 3,4-epoxybutyl group and 7,8-epoxyoctyl group; and groups obtained by substituting part or all of hydrogen atoms of these groups with halogen atoms such as fluorine atom, chlorine atom and bromine atom.

[0123] Preferably, R in formula (V) 3 represents C 1~12 alkyl group, specifically methyl group, C 2~12 alkenyl group, specifically vinyl group, C 6~12 aryl group, specifically phenyl group, and glycidoxyalkyl group, specifically 3-glycidoxypropyl group.

[0124] In formula (V), X represents hydrogen or an alkyl group. The alkyl group for X is preferably C 1~3 alkyl group such as methyl group, ethyl group and propyl group.

[0125] In one embodiment of the present invention, in formula (V), a is preferably in the range of 0≦a≦0.4, more preferably in the range of 0.05<a≦0.3, still more preferably in the range of 0.1<a≦0.2. In formula (V), b is preferably in the range of 0.1≦b≦0.5, more preferably in the range of 0.15≦b≦0.4, still more preferably in the range of 0.2≦b≦0.3. In formula (V), c is preferably in the range of 0.1≦c≦0.7, more preferably in the range of 0.2≦c≦0.6, still more preferably in the range of 0.3≦c≦0.55. In formula (V), d is preferably in the range of 0≦d≦0.3, more preferably in the range of 0≦d≦0.2, still more preferably in the range of 0≦d≦0.1. In formula (V), e is preferably in the range of 0≦e≦0.4, more preferably in the range of 0.05≦e≦0.3, still more preferably in the range of 0.1≦e≦0.2.

[0126] The weight-average molecular weight of the epoxy group-containing resinous organopolysiloxane is not particularly limited, but is preferably 100 to 100,000.

[0127] The viscosity of epoxy group-containing resinous organopolysiloxane is not particularly limited, but can be, for example, 100 mPa·s to 100,000 mPa·s at 25°C.

[0128] The epoxy group-containing resinous organopolysiloxane may be present in an amount of 0.5% by weight or more, preferably 1% by weight or more, more preferably 1.5% by weight or more, and / or in an amount of 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition. Any combination of the upper and lower limits is available.

[0129] In another embodiment of the present invention, the curable silicone composition is of the following formula (VI): Average structural formula (VI):(R 1 SiO) n (In the formula, R 1 This represents the same or different monovalent hydrocarbons that can be optionally substituted with at least one halogen, and per molecule R 1 (At least two of these represent alkenyl groups, and n is an integer between 4 and 50.) It may contain or not contain at least one organopolysiloxane containing a cyclic alkenyl group that can be represented by . It is possible to use one type of organopolysiloxane containing a cyclic alkenyl group or two or more types of organopolysiloxanes containing cyclic alkenyl groups.

[0130] R in equation (I) 1 The same definition as in equation (VI) R 1 It can be applied to [this].

[0131] In formula (VI), n can be an integer between 4 and 30, preferably between 4 and 20, more preferably between 4 and 10, and specifically between 4 and 8.

[0132] The weight-average molecular weight of the cyclic alkenyl group-containing organopolysiloxane is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less, and specifically 500 or less. The lower limit of the weight-average molecular weight of the cyclic organopolysiloxane is not particularly limited, but is, for example, 100 or more.

[0133] The viscosity of organopolysiloxanes containing cyclic alkenyl groups is not particularly limited, but can be, for example, 1 mPa·s to 3,000 mPa·s at 25°C.

[0134] In one embodiment of the present invention, the cyclic alkenyl group-containing organopolysiloxane may be present in an amount of 0.5% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more, and / or 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition.

[0135] Other ingredients The curable silicone composition may or may not contain a hydrosilylation inhibitor as an additional component. One type of hydrosilylation inhibitor or two or more types of hydrosilylation inhibitors may be used.

[0136] As hydrosilylation reaction inhibitors, acetylene alcohols, such as methylbutynol, ethinylcyclohexanol, dimethylhexinol, 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyne-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentin-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octin-3-ol, 1-ethynyl-1-cyclohexanol, and combinations thereof; cycloalkenylsiloxanes, such as methylvinylcyclosiloxanes exemplified by 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7 Examples include -tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and combinations thereof, en-yne compounds, e.g., 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, triazoles, e.g., benzotriazole, phosphines, mercaptans, hydrazines, amines, e.g., tetramethylethylenediamine, dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, maleates, e.g., diallyl maleate, nitriles, ethers, carbon monoxide, alkenes, e.g., cyclooctadiene, divinyltetramethyldisiloxane, alcohols, e.g., benzyl alcohol, and combinations thereof. Alternatively, the hydrosilylation inhibitor may be selected from the group consisting of acetylene alcohols (e.g., 1-ethynyl-1-cyclohexanol), maleates (e.g., diallyl maleate, bismaleate, or n-propyl maleate), and two or more combinations thereof.

[0137] The amount of hydrosilylation reaction inhibitor present in the curable silicone composition may be 0.001% to 3% by weight, preferably 0.005% to 1% by weight, and more preferably 0.01% to 0.5% by weight, based on the total weight of the composition.

[0138] The curable silicone composition according to the present invention may also include, for example, any optional additive commonly used in the art selected from organopolysiloxanes other than the components described above, organic fillers, inorganic fillers other than component (C) above, pigments, adhesion promoters, resistance promoters, mold release agents, heat resistance agents, dyes, flame retardants, and mixtures thereof.

[0139] The curable silicone composition according to the present invention can be prepared by mixing the essential and optional components described above in a conventional manner. The method of mixing each component can be carried out by conventionally known methods and is not particularly limited. For example, mixing can be carried out by simple stirring or mixing using a mixing device such as a uniaxial or twin-screw continuous mixer, a double roll mixer, a Hobart mixer, a dental mixer, a planetary mixer, a kneader mixer, or a Henschel mixer.

[0140] Step (III) Step (iii) of the present invention is to cure the extruded curable silicone composition by heating to form a silicone sealant in the shape of a dome with a flat top or a concave dome.

[0141] The inventors of the present invention have surprisingly discovered that, because the extruded curable silicone composition has given high thixotropic properties, it is possible to fabricate the curable silicone composition into unique dome shapes, such as dome shapes with flat top surfaces or concave dome shapes, by simply injecting the curable silicone composition from a single nozzle.

[0142] Curable silicone compositions can be cured at relatively low temperatures. For example, a cured sealant can be formed by heating at a temperature of 50 to 150°C, preferably 80 to 120°C, for 1 to 120 minutes, preferably 5 to 60 minutes, and more preferably 10 to 30 minutes.

[0143] Figure 1 shows a cross-sectional view of an example of a semiconductor device of the present invention equipped with a dome-shaped encapsulant having a flat top (Figure 1A) or a concave dome-shaped encapsulant (Figure 1B).

[0144] In this specification, the term “dome” may mean a hemispherical or hemispherical shape. For example, in Figures 1A and 1B, the bottom surface of the dome has the longest diameter, but is not limited to the bottom surface having the longest diameter. For example, the top surface of the dome may have the longest diameter, or the portion between the top and bottom surfaces of the dome may have the longest diameter. In one embodiment, the dome may have a tapered bottom surface.

[0145] The diameter of the sealing material at the dome-shaped bottom surface is not particularly limited, but is generally in the range of 0.01 mm to 20 mm, preferably 0.1 mm to 15 mm. When the bottom surface does not have the longest diameter of the dome, for example when the dome has a tapered bottom surface, the ratio of the bottom diameter to the longest diameter of the dome is not limited.

[0146] The height of the sealing material from the bottom to the top of the dome shape is not particularly limited, but is generally in the range of 0.001 mm to 14 mm, preferably 0.003 mm to 7 mm.

[0147] When the sealing material is in the form of a concave dome, the depth of the dome's recess is not particularly limited, but is generally in the range of 0% to 100% of the height, preferably 2% to 80% of the height.

[0148] The sealing material of the present invention can be light-transmitting. Specifically, the sealing material of the present invention has a light transmittance of preferably 50% or more, more preferably 70% or more, at wavelengths of 400 nm to 700 nm, for example, at 450 nm. The light transmittance of the sealing material can be determined, for example, by measuring a cured product having an optical path length of 1 using a spectrophotometer.

[0149] Curable silicone composition The present invention also relates to a curable silicone composition, more particularly to a curable silicone composition for producing a silicone sealant in the shape of a dome with a flat top or a concave dome, as described above.

[0150] Therefore, the curable silicone composition according to the present invention is a curable silicone composition for manufacturing a sealing material in the shape of a dome with a flat top or a concave dome by extrusion, and is described below: (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B)(A) At least one MQ resin having at least two alkenyl groups per molecule, other than a resinous organopolysiloxane, (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, Includes, The curable silicone composition has a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C.

[0151] The curable silicone composition according to the present invention can be used to manufacture a sealing material in the shape of a dome with a flat top or a concave dome by the process according to the present invention, as described above.

[0152] The components, viscosity, heating conditions, etc., are as described in the process of the present invention.

[0153] Sealing material The present invention also relates to a encapsulant produced by a process according to the present invention, that is, by curing a curable silicone composition according to the present invention.

[0154] Therefore, the sealing material according to the present invention may be a silicone sealing material in the shape of a dome with a flat top or a concave dome, manufactured by the process according to the present invention and / or using a curable silicone composition according to the present invention.

[0155] The encapsulating material of the present invention is preferably used to encapsulate semiconductor elements including optical semiconductors. Examples of semiconductor elements include SiC and GaN. Examples of optical semiconductor elements include elements represented by light-emitting diodes (LEDs), photodiodes, phototransistors, and laser diodes.

[0156] Optical semiconductor devices The present invention also relates to optical semiconductor devices to which the encapsulating material of the present invention is provided. Examples of optical semiconductor elements include light-emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state imaging devices, and light-emitting and light-receiving elements for photocouplers, with light-emitting diodes (LEDs) being particularly preferred.

[0157] Since light-emitting diodes (LEDs) emit light from above, below, left, and right of the optical semiconductor element, it is preferable that the components constituting the LED have high light transmittance. Examples of substrates on which such optical semiconductor elements are mounted include conductive metals such as silver, gold, and copper; non-conductive metals such as aluminum and nickel; thermoplastic resins such as PPA and LCP (containing white pigment); thermosetting resins such as epoxy resin, BT resin, polyimide resin, and silicone resin (containing white pigment); and ceramics such as alumina and alumina nitride.

[0158] Specific embodiments of the present invention are shown below.

[0159] Embodiment 1: A process for manufacturing a silicone encapsulant in the shape of a dome with a flat top or a concave dome, (i) A step of preparing an object to be enclosed on a substrate, (ii) A step of extruding a curable silicone composition onto an object by a potting method, (iii) The step of curing the extruded curable silicone composition by heating to form a silicone sealant in the shape of a dome with a flat top or a concave dome, Includes, The curable silicone composition has a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C, according to the process.

[0160] Embodiment 2: The process according to Embodiment 1, wherein the process does not include an extra step for physically shaping the extruded curable silicone composition.

[0161] Embodiment 3: The process according to Embodiment 1 or 2, wherein heating is performed at a temperature of 50°C to 150°C for 1 to 120 minutes.

[0162] Embodiment 4: A curable silicone composition, (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B)(A) At least one MQ resin having at least two alkenyl groups per molecule, other than a resinous organopolysiloxane, (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, A process according to any one of embodiments 1 to 3, including the process described in each of embodiments 1 to 3.

[0163] Embodiment 5: The process according to any one of Embodiments 1 to 4, wherein the curable silicone composition comprises at least one hydrosilylation reaction inhibitor.

[0164] Embodiment 6: The process according to any one of Embodiment 4 or 5, wherein (C) the organohydrogenpolysiloxane comprises at least one linear organohydrogenpolysiloxane.

[0165] Embodiment 7: The process according to Embodiment 6, wherein the weight ratio of alkenyl group-containing resinous organopolysiloxane to linear organohydrogenpolysiloxane is in the range of 1:1 to 10:1.

[0166] Embodiment 8: A curable silicone composition for producing a sealing material in the shape of a dome with a flat top or a concave dome by dispersion, (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B)(A) At least one MQ resin having at least two alkenyl groups per molecule, other than a resinous organopolysiloxane, (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, Includes, A curable silicone composition having a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C.

[0167] Embodiment 9: A sealing material having a dome shape with a flat top or a concave dome shape, formed from the curable silicone composition described in Embodiment 8.

[0168] Embodiment 10: An optical semiconductor device provided with the sealing material described in Embodiment 9. [Examples]

[0169] The present invention will be described in more detail by the examples provided, but this should not be construed as limiting the scope of the invention.

[0170] The process of the present invention is described in detail by examples and comparative examples. In the examples and comparative examples, the present invention is carried out using the following components. In the formulas, Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Ep represents a 3-glycidoxypropyl group. In addition, the chemical formulas of the organopolysiloxane components are shown in a simplified form in the table, and organic groups other than Me in the M, D, or T units are shown in parentheses. All numerical values ​​of the components shown in the table are based on "parts by weight" as active raw materials.

[0171] Component elements: (a) Formula (Me3SiO 1 / 2 ) 0.14 (Me2ViSiO 1 / 2 ) 0.11 (MeSiO 3 / 2 ) 0.53 (PhSiO 3 / 2 ) 0.22 A resinous alkenyl group-containing organopolysiloxane represented by [formula], Mw: 4,600, solid at 25°C. Formula (b-1) (ViMe2SiO 1 / 2 )4(SiO 4 / 2 ) Alkenyl group-containing MQ resin, Mw: 433, viscosity: 5 mPa·s at 25°C Formula (b-2) (Me3SiO 1 / 2 ) 0.45 (Me2ViSiO 1 / 2 ) 0.15 (SiO 4 / 2 ) 0.4 An alkenyl group-containing MQ resin represented by [formula], Mw: 1,100, viscosity: 210 mPa·s at 25°C. Formula (b-3) (Me3SiO 1 / 2 ) 0.25 (Me2ViSiO 1 / 2 ) 0.37 (SiO 4 / 2 ) 0.38 An alkenyl group-containing MQ resin represented by [formula], Mw: 1.600, viscosity: 300 mPa·s at 25°C. (c-1) A linear organohydrogen polysiloxane represented by formula HMe2SiO(Ph2SiO)SiMe2H, Mw: 333, viscosity: 4 mPa·s at 25°C. Formula (c-2) (HMe2SiO 1 / 2 ) 0.62 (SiO 4 / 2 ) 0.38 This is an MQ resin type organohydrogen polysiloxane, represented by Mw: 1.600, viscosity: 30 mPa·s at 25°C. Formula (c-3) (HMe2SiO 1 / 2 ) 0.6 (PhSiO 3 / 2 ) 0.4 A resinous organohydrogen polysiloxane represented by [formula], Mw: 750, viscosity: 25 mPa·s at 25°C. (d) Fumed silica (average primary particle size: 7 nm) (e) Complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum concentration: 3.0% by weight) (f) 1-Ethynyl-1-cyclohexanol (g-1) Formula: ViMe2SiO(Me2SiO) 60 (Ph2SiO) 30 A linear alkenyl group-containing organopolysiloxane represented by SiMe2Vi, Mw: 10,600, viscosity: 10,000 mPa·s at 25°C. (g-2) Formula (Me2ViSiO 1 / 2 ) 0.13 (MeEpSiO 2 / 2 ) 0.24 (PhSiO 3 / 2 ) 0.46 (OMe) 0.17 A resinous organopolysiloxane containing alkenyl and epoxy groups, represented by [formula], Mw: 3,000, viscosity: 5,000 mPa·s at 25°C. (g-3) A cyclic alkenyl group-containing organopolysiloxane represented by formula (MeViSiO)4, Mw: 344, viscosity: 3 mPa·s at 25°C. (g-4) Equation ViMe2SiO(PhMeSiO) 20A linear alkenyl group-containing organopolysiloxane represented by SiMe2Vi, Mw: 2,900, viscosity: 3,000 mPa·s at 25°C.

[0172] evaluation viscosity The viscosity of the curable silicone compositions prepared in each example was measured at 25°C and a shear rate of 20 / s using a rheometer with a 40 mm cone plate (Antonpaar MCR302) at a 2-degree angle.

[0173] To achieve the inventive dome shape of the present invention, a viscosity of 3,000 to 20,000 at 25°C is required.

[0174] Thixotropic The viscosity of each prepared curable silicone composition in the examples was measured at 25°C at shear rates of 10 / s and 1 / s using a rheometer with a 40 mm cone plate (Antonpaar MCR302) at a 2-degree angle. The thixotropic index was calculated as the viscosity ratio (viscosity at 1 / s) / (viscosity at 10 / s).

[0175] To achieve the formation of the inventive dome shape of the present invention, a thixotropic index value of 4.0 to 15.0 is required.

[0176] light transmittance Each of the curable silicone compositions of the examples was filled into a mold having a recess of a predetermined shape, and then cured at 100°C for 30 minutes. The resulting 1 mm thick plate-like cured material was subjected to transmittance measurement at 450 nm at 25°C.

[0177] When the cured material exhibited a light transmittance of over 70%, its light transmittance was considered "OK".

[0178] formability Using a jetting machine equipped with a piezo valve by the potting method, each prepared curable silicone composition of the Examples was discharged onto a glass substrate. The nozzle temperature was set to 30°C. The inner diameter of the nozzle was 300 µm. The nozzle pressure was 4.6 bar. The needle lift was 50%. The number of dots was one shot. Then, the discharged curable silicone composition was cured by heating at 100°C for 30 minutes. The shape of the cured product was observed, and Examples in which a cured product in the shape of a dome with a flat top or a concave dome was obtained were marked "OK".

[0179] Curable 6 g of the prepared curable composition from each Example was measured by MDR testing at 100°C for 30 minutes. If the material cured sufficiently within 30 minutes (MDR torque reached saturation), the composition was marked "OK".

[0180] The results are summarized in the table below.

[0181]

Table 1

[0182]

Table 2

[0183] As can be seen from the results in the tables, the process according to the present invention described in Examples 1 to 4 achieved formation of a unique dome-shaped light-transmissive encapsulant by heating. In contrast, in the processes of Comparative Examples 1 to 4, the curable silicone compositions had a viscosity and / or thixotropic index outside the specified ranges, and failed to achieve formation of a unique dome-shaped encapsulant by heating.

[0184] Since encapsulating materials in the shape of a dome with a flat top or a concave dome can increase the light output rate when used in optical semiconductor devices, it can be concluded that the process according to the present invention is very useful for encapsulation in the manufacture of semiconductor packages, particularly optical semiconductor packages such as LED packages.

Claims

1. A process for manufacturing a silicone sealant in the shape of a dome with a flat top or a concave dome, (i) A step of preparing an object to be enclosed on a substrate, (ii) A step of extruding a curable silicone composition onto the object by a potting method, (iii) The step of curing the extruded curable silicone composition by heating to form the silicone sealant in the shape of a dome having a flat top or a concave dome, Includes, The curable silicone composition has a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C, according to the process.

2. The process according to claim 1, wherein the process does not include an extra step for physically forming the extruded curable silicone composition.

3. The process according to claim 1 or 2, wherein the heating is performed at a temperature of 50 to 150°C for 1 to 120 minutes.

4. The curable silicone composition is (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B) At least one MQ resin having at least two alkenyl groups per molecule, other than the resinous organopolysiloxane described in (A), (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, The process according to claim 1, including the process described in claim 1.

5. The process according to claim 4, wherein the curable silicone composition further comprises at least one hydrosilylation reaction inhibitor.

6. The process according to claim 4, wherein the (C) organohydrogenpolysiloxane comprises at least one linear organohydrogenpolysiloxane.

7. The process according to claim 6, wherein the weight ratio of (A) alkenyl group-containing resinous organopolysiloxane to the linear organohydrogenpolysiloxane is in the range of 1:1 to 10:

1.

8. A curable silicone composition for manufacturing a sealing material in the shape of a dome with a flat top or a concave dome by extrusion, (A) At least one resinous organopolysiloxane having at least two alkenyl groups per molecule, (B) At least one MQ resin having at least two alkenyl groups per molecule, other than the resinous organopolysiloxane described in (A), (C) At least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, (D) at least one inorganic filler, (E) at least one hydrosilylation catalyst, Includes, A curable silicone composition having a viscosity in the range of 3,000 to 20,000 mPa·s at 25°C and a thixotropic index value in the range of 4.0 to 15.0 at 25°C.

9. A sealing material having a flat top and a dome shape or a concave dome shape, formed from the curable silicone composition according to claim 8.

10. An optical semiconductor device provided with the sealing material described in claim 9.

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