Curable silicone composition and cured product thereof

Abstract

The present invention relates to a curable silicone composition comprising: (A) at least one resinous organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule; (B) at least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule; (C) at least one inorganic filler, the at least one inorganic filler having a reflectance of 1.50 or more; (D) two or more kinds of polyether modified organopolysiloxanes, the two or more polyether-modified organopolysiloxanes include a combination of (d-1) at least one polyether-modified organopolysiloxane having at least one terminal-OH group in the polyether chain and (d-2) at least one polyether-modified organopolysiloxane having at least one terminal alkoxy or acyloxy group in the polyether chain; and (E) at least one hydrosilylation catalyst.

Description

Technical Field

[0001] The present invention relates to a curable silicone composition suitable for encapsulation of optical semiconductor devices and a cured product thereof. Background Art

[0002] Curable silicone compositions are used in a wide range of industrial fields because they form cured products having excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. The cured product of such a curable silicone composition is also suitable as a sealant for optical materials such as light emitting diodes (LEDs) because it hardly fades and has less deterioration in physical properties such as durability compared to other organic materials.

[0003] In recent years, various curable silicone compositions have been reported for use as silicone encapsulants in optical semiconductor devices such as light emitting diodes (LEDs).

[0004] For example, JP-T-2012-507582 discloses a hydrosilylation reaction-curable organopolysiloxane composition comprising:

[0005] (A) a methylphenylalkenyl polysiloxane having at least two silicon-bonded alkenyl groups per molecule, wherein the diphenylsiloxane units are no more than 5 mole % of the total siloxane units and the phenyl groups are at least 20 mole % of the total silicon-bonded organic groups in the molecule,

[0006] (B) a methylphenylhydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, wherein the diphenylsiloxane units are no more than 5 mole % of the total siloxane units and the phenyl groups are at least 20 mole % of the total silicon-bonded organic groups in the molecule, and

[0007] (C) a hydrosilylation reaction catalyst, wherein the diphenylsiloxane units are no more than 5 mole % of the total siloxane units in the composition.

[0008] In addition, JP-A-2014-159586 discloses a silicone resin composition for coating a light-transmitting surface of an optoelectronic device, comprising:

[0009] A plurality of liquid components, the plurality of liquid components comprising:

[0010] A linear organopolysiloxane component, wherein the linear organopolysiloxane component molecule contains at least one unsaturated aliphatic group that participates in a hydrosilylation reaction;

[0011] an organohydrogenpolysiloxane component; and

[0012] Platinum metal catalyst;

[0013] The linear organopolysiloxane component has a sufficiently low proportion of organosiloxane having a molecular weight of up to about 1000 such that when the silicone resin product is cured, the cured product contains less than about 10% of the organosiloxane having a molecular weight of up to about 1000.

[0014] Furthermore, JP-A-2017-036416 discloses a curable silicone resin composition comprising component (A), component (B), component (C), component (D), and component (E):

[0015] (A) a polyorganosiloxane having one or more hydrosilyl groups and no aliphatic unsaturated groups in the molecule;

[0016] (B) a hydrosilylation catalyst comprising a platinum group metal;

[0017] (C) a branched polyorganosiloxane having one or more alkenyl groups in the molecule;

[0018] (D) a silica filler having an average primary particle size of 5 to 5000 nm; and

[0019] (E) Polyether modified leveling agent.

[0020] Furthermore, JP-A-2020-100683 discloses a curable silicone resin composition comprising component (A), component (B), component (C), and component (D):

[0021] (A) a polyorganosiloxane having one or more hydrosilyl groups and no aliphatic unsaturated groups in the molecule;

[0022] (B) a branched polyorganosiloxane having one or more alkenyl groups in the molecule (except component (C));

[0023] (C) a branched polyorganosiloxane having three or more alkenyl groups in the molecule and having a molecular weight of 1000 or less; and

[0024] (D) A hydrosilylation catalyst comprising a platinum group metal.

[0025] However, since a conventional curable silicone composition may have insufficient thixotropic properties, there may be a problem in which, although an appropriate amount of the silicone composition is applied to the optical semiconductor on the supporting substrate using a dispenser, the applied curable silicone composition may flow, and a cured product having a desired shape may not be obtained.

[0026] Therefore, there is a need for a curable silicone composition that has high thixotropic properties and can provide a cured product having high transparency and high reflectivity for light extraction of an optical semiconductor device. Summary of the invention

[0027] An object of the present invention is to provide a curable silicone composition which has high thixotropic properties and can provide a cured product having high transparency and high reflectivity.

[0028] The above object of the present invention can be achieved by a curable silicone composition, which comprises:

[0029] (A) at least one resinous organopolysiloxane having at least two alkenyl groups and at least one aromatic group per molecule;

[0030] (B) at least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule;

[0031] (C) at least one inorganic filler having a reflectivity of 1.50 or more;

[0032] (D) two or more polyether-modified organopolysiloxanes comprising a combination of (d-1) at least one polyether-modified organopolysiloxane having at least one terminal -OH group in the polyether chain and (d-2) at least one polyether-modified organopolysiloxane having at least one terminal alkoxy or acyloxy group in the polyether chain; and

[0033] (E) at least one hydrosilylation catalyst.

[0034] The (A) resinous organopolysiloxane may contain aromatic groups in silicon atom-bonded organic groups in an amount of 30 mol % or more and 90 mol % or less relative to the total amount of the silicon atom-bonded organic groups.

[0035] The (A) resinous organopolysiloxane may be composed of: (R2SiO 2 / 2 ) and the D siloxane unit represented by (RSiO 3 / 2 ) represents a T siloxane unit.

[0036] The (B) organohydrogenpolysiloxane may contain at least one aromatic group in the silicon atom-bonded organic group.

[0037] The (C) inorganic filler may be selected from aluminum oxides.

[0038] The (D) polyether-modified organopolysiloxane including the (d-1) and (d-2) components may be present in a total amount of 0.1 wt % or more and 10 wt % or less relative to the total weight of the composition.

[0039] The present invention also relates to a sealing material formed using the curable silicone composition according to the present invention.

[0040] The invention also relates to an optical semiconductor device provided with the sealing material according to the invention.

[0041] Effects of the Invention

[0042] The present invention can provide a curable silicone composition having high thixotropic properties and can provide a cured product having high transparency and high reflectivity. DETAILED DESCRIPTION

[0043] After diligent studies, the inventors have unexpectedly found that the combination of components (A) to (E) of the present invention can provide a curable silicone composition with good thixotropic properties and provide a cured product with high transparency and high reflectivity, and thus completed the present invention.

[0044] In addition, the inventors unexpectedly found that the silicone curable composition according to the present invention has good wettability on a substrate, especially an organic substrate, and thus can provide a reliable material for a semiconductor device.

[0045] Therefore, the composition according to the present invention is a curable silicone composition comprising:

[0046] (A) at least one resinous organopolysiloxane having at least two alkenyl groups and at least one aromatic group per molecule;

[0047] (B) at least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule;

[0048] (C) at least one inorganic filler having a reflectivity of 1.50 or more;

[0049] (D) two or more polyether-modified organopolysiloxanes comprising a combination of (d-1) at least one polyether-modified organopolysiloxane having at least one terminal -OH group in the polyether chain and (d-2) at least one polyether-modified organopolysiloxane having at least one terminal alkoxy or acyloxy group in the polyether chain; and

[0050] (E) at least one hydrosilylation catalyst.

[0051] Hereinafter, the composition, method and use according to the present invention will be explained in a more detailed manner.

[0052] [Curable silicone composition]

[0053] The curable silicone composition according to the present invention comprises (A) at least one resinous organopolysiloxane having at least two alkenyl groups and at least one aromatic group per molecule; (B) at least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule; (C) at least one inorganic filler, the at least one inorganic filler having a reflectivity of 1.5 or more; (D) two or more polyether-modified organopolysiloxanes, the two or more polyether-modified organopolysiloxanes comprising a combination of (d-1) at least one polyether-modified organopolysiloxane having at least one terminal -OH group in the polyether chain and (d-2) at least one polyether-modified organopolysiloxane having at least one terminal alkoxy or acyloxy group in the polyether chain; and (E) at least one hydrosilylation catalyst.

[0054] Each component of the curable silicone composition will be explained below.

[0055] (A) Resinous organopolysiloxane containing alkenyl and aromatic groups

[0056] The curable silicone composition according to the present invention comprises at least one resinous organopolysiloxane having at least two alkenyl groups and at least one aryl group per molecule. The composition according to the present invention may comprise one type of (A) resinous organopolysiloxane containing alkenyl groups and aryl groups or may comprise a combination of two or more types of (A) resinous organopolysiloxane containing alkenyl groups and aryl groups.

[0057] (A) The organopolysiloxane containing alkenyl and aryl groups has a resinous structure. The term "resinous" herein means that the organopolysiloxane has a branched or three-dimensional network structure in the molecule. In one embodiment, in the context of the present invention, the term "resinous" means that the total amount of T units and Q units in one organopolysiloxane molecule relative to the amount ratio of all siloxane units is 5% or more, or 10% or more. Generally speaking, the resinous organopolysiloxane has a viscosity of at least 1 mPa at 25°C. The viscosity of the organopolysiloxane component herein can be measured using a rotational viscometer that complies with JIS K7117-1. In addition, generally speaking, the resinous organopolysiloxane has a weight average molecular weight of at least 1,000. The weight average molecular weight can be measured using gel permeation chromatography (GPC) (relative to polystyrene).

[0058] The alkenyl group contained in component (A) may include C 2-12 Alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl; and preferably vinyl.

[0059] The aromatic groups contained in component (A) may include C 6-12 Aryl groups such as phenyl, tolyl, xylyl and naphthyl.

[0060] The other silicon-bonded organic groups contained in component (A) besides alkenyl and aryl groups may include C 1-12 Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; C 7-12 Aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups obtained by replacing some or all of the hydrogen atoms in these groups with halogen atoms such as fluorine, chlorine or bromine atoms. It should be noted that a small amount of alkoxy groups (such as methoxy or ethoxy) may be bonded to the silicon atoms in component (A), provided that this does not adversely affect the purpose of the present invention. Preferably, the silicon atom-bonded organic groups other than alkenyl groups include C 1-12 Alkyl groups, in particular methyl groups. Component (A) may not contain thiol groups or glycidyl groups.

[0061] In one embodiment of the present invention, (A) the resinous organopolysiloxane containing alkenyl and aryl groups may be represented by the following formula (Ia):

[0062] Average unit formula (Ia): (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

[0063] Among them, R 1 indicates identical or different monovalent hydrocarbons, which may be optionally substituted by at least one halogen, wherein at least two R 1 represents an alkenyl group, and at least one R 1 represents an aryl group; X represents hydrogen or an alkyl group; and 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 are satisfied. The value e indicates that (XO 1 / 2 ) groups relative to the total number of silicon atoms.

[0064] Here, including SiO x / 2 The formula of the siloxane unit represented by (wherein x indicates an integer of 1 to 4) is expressed as the “average unit formula”, excluding the formula composed of SiO x / 2 The formula of the siloxane unit represented is expressed as an "average structural formula".

[0065] In formula (Ia), for R 1 The monovalent hydrocarbon (which may be optionally substituted by at least one halogen) may include C 1-12 Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; C 2-12 Alkenyl, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl; C 6-12 Aryl, such as phenyl, tolyl, xylyl and naphthyl; C 7-12 Aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups obtained by replacing some or all of the hydrogen atoms in these groups with halogen atoms such as fluorine, chlorine, or bromine atoms. 1 The monovalent hydrocarbon in may include a small amount of alkoxy groups (such as methoxy or ethoxy), provided that this does not adversely affect the purpose of the present invention. 1 The monovalent hydrocarbon in C 1-12 Alkyl, especially methyl, C 2-12 Alkenyl, especially vinyl, or C 6-12 Aryl, especially phenyl.

[0066] In formula (Ia), X represents hydrogen or alkyl. The alkyl group in X preferably represents C 1-3 Alkyl groups such as methyl, ethyl, or propyl.

[0067] In one embodiment of the present invention, in formula (Ia), the range of a is preferably 0≤a≤0.3, more preferably in the range of 0≤a≤0.2, and even more preferably in the range of 0≤a≤0.1. In formula (Ia), the range of b is preferably 0.2≤b≤0.8, more preferably 0.3≤b≤0.7, and even more preferably 0.4≤b≤0.6. In formula (Ia), the range of c is preferably 0.2≤c≤0.8, more preferably 0.3≤c≤0.7, and even more preferably 0.4≤c≤0.6. In formula (Ia), the range of d is preferably 0≤d≤0.3, more preferably 0≤d≤0.2, and even more preferably 0≤d≤0.1. In formula (Ia), the range of e is preferably 0≤e≤0.2, more preferably 0≤e≤0.1, and even more preferably 0≤e≤0.05. In formula (Ia), the range of c+d is preferably 0.1≤c+d≤0.8, more preferably 0.2≤c+d≤0.7, and even more preferably 0.3≤c+d≤0.6. In the present specification, any combination of numerical upper limits and numerical lower limits may be used to express a certain numerical range.

[0068] In one embodiment of the present invention, in formula (I-a), b is greater than 0, that is, (A) the resinous organopolysiloxane contains at least one D siloxane unit represented by (R2SiO 2 / 2 ).

[0069] In one embodiment of the present invention, in formula (I-a), c is greater than 0, that is, (A) the resinous organopolysiloxane contains at least one T siloxane unit represented by (RSiO 3 / 2 ). In one embodiment, (A) the resinous organopolysiloxane may or may not contain a Q siloxane unit represented by (SiO 4 / 2 ), however, it preferably does not contain any Q units. In one embodiment, (A) the resinous organopolysiloxane may or may not contain an M siloxane unit represented by (R3SiO 1 / 2 ), however, it preferably does not contain any M units. Here, R in the siloxane unit indicates an organic group attached to the silicon atom.

[0070] In another embodiment of the present invention, (A) the resinous organopolysiloxane containing alkenyl and aryl groups includes at least one resinous organopolysiloxane composed of D units and T units, which can be represented by the following formula (I-b):

[0071] Average unit formula (I-b): (R 1 2SiO 2 / 2 ) s (R 1 SiO 3 / 2 ) t

[0072] Wherein, R 1 indicates the same or different monovalent hydrocarbons, which may optionally be substituted by at least one halogen, wherein at least two Rs 1 per molecule represent alkenyl groups, and at least one R 1 represents an aryl group; and 0 < s < 1, 0 < t < 1, and s + t = 1.0. One type of resinous organopolysiloxane composed of D units and T units or two or more types of resinous organopolysiloxanes composed of D units and T units can be used as component (A) the organopolysiloxane.

[0073] The definition of R 1 in formula (I-a) can also be applied to R 1 in formula (I-b).

[0074] In one embodiment of the present invention, in formula (Ib), the range of s is preferably 0.2≤s≤0.8, more preferably in the range of 0.3≤s≤0.7, and even more preferably in the range of 0.3≤s≤0.6. In formula (Ib), the range of t is preferably 0.2≤t≤0.8, more preferably 0.3≤t≤0.7, and even more preferably 0.4≤t≤0.6.

[0075] In one embodiment of the present invention, the (A) resinous organopolysiloxane comprises an alkenyl group in the D siloxane unit. The (A) resinous organopolysiloxane may or may not comprise an alkenyl group in the M or T siloxane unit, however, it preferably does not comprise an alkenyl group in the M or T unit.

[0076] The amount of alkenyl groups in the (A) organopolysiloxane relative to the total amount of silicon-bonded organic groups is not particularly limited, but is, for example, 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 40 mol% or less, preferably 30 mol% or less, and more preferably 20 mol% or less, relative to the total amount of silicon-bonded organic groups. The amount of alkenyl groups can be measured, for example, by an analytical method such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR) or the following titration method.

[0077] In the present specification, any combination of upper numerical limits and lower numerical limits can be used to express a certain numerical range.

[0078] A method for quantifying the amount of alkenyl groups in an organopolysiloxane by titration will be described below. The content of alkenyl groups in an organopolysiloxane can be accurately quantified by a titration method known as the Wijs method. The principle is described as follows. First, alkenyl groups present in an organopolysiloxane raw material and iodine monochloride are subjected to an addition reaction as shown in equation (1). Next, excess iodine monochloride reacts with potassium iodide to be released as iodine through a reaction represented by equation (2). Free iodine is then titrated with a sodium thiosulfate solution.

[0079] Equation (1) CH2=CH-+2ICl→CH2I-CHCl-+ICl(excess)

[0080] Equation (2)ICl+KI→I2+KCl

[0081] The amount of alkenyl groups present in the organopolysiloxane can be quantified from the difference between the amount of sodium thiosulfate required for the above titration and a separately prepared blank solution.

[0082] The (A) resinous organopolysiloxane contains at least one aromatic group in the silicon-bonded organic group. In a preferred embodiment of the present invention, the (A) resinous organopolysiloxane contains at least one aromatic group in the D unit or the T unit. The (A) organopolysiloxane may or may not contain an aromatic group in the M unit, but preferably does not contain any aromatic group in the M unit.

[0083] The content of the aryl group in the (A) resinous organopolysiloxane is not particularly limited, but is generally 30 mol% or more, preferably 40 mol% or more, more preferably 55 mol% or more, and even more preferably 60 mol% or more, and is generally 90 mol% or less, preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less, relative to the total amount of silicon atom-bonded organic groups. The amount of the aryl group can be measured, for example, by an analytical method such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR) or the following titration method.

[0084] The weight average molecular weight of the (A) resinous organopolysiloxane is not particularly limited, but is preferably 1,000 to 100,000, and more preferably 1,000 to 10,000, and more preferably 1,500 to 5,000. The weight average molecular weight can be measured using gel permeation chromatography (GPC) (relative to polystyrene).

[0085] The viscosity of the (A) resinous organopolysiloxane is not particularly limited, but may be, for example, 300 mPa to 100,000 mPa at 25° C. On the other hand, the (A) resinous organopolysiloxane may be in a solid form at 25° C. The viscosity of the organopolysiloxane component herein may be measured with a rotational viscometer conforming to JIS K7117-1.

[0086] (A) the resinous organopolysiloxane may be present in an amount of 1 wt % or more, preferably 10 wt % or more, more preferably 20 wt % or more, and even more preferably 30 wt % or more, relative to the total weight of the composition, and may be present in an amount of 80 wt % or less, preferably 70 wt % or less, and more preferably 50 wt % or less. Any combination of upper and lower limits may be used.

[0087] (B) Organohydrogenpolysiloxane

[0088] Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule. The composition according to the present invention may contain one type of (B) organohydrogenpolysiloxane or may contain a combination of two or more types of (B) organohydrogenpolysiloxanes.

[0089] The (B) organohydrogenpolysiloxane may be linear, branched, partially branched, cyclic or resinous. Preferably, the (B) organohydrogenpolysiloxane is a linear organohydrogenpolysiloxane.

[0090] The silicon-bonded organic groups other than hydrogen atoms contained in component (B) may include monovalent hydrocarbons other than alkenyl groups, such as C 1-12 Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; C 6-12 Aryl, such as phenyl, tolyl, xylyl and naphthyl; C 7-12 Aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups obtained by replacing some or all of the hydrogen atoms in these groups with halogen atoms such as fluorine, chlorine or bromine atoms. It should be noted that a small amount of alkoxy groups (such as methoxy or ethoxy) may be bonded to the silicon atoms in component (B), provided that this does not adversely affect the purpose of the present invention. Preferably, the silicon atom-bonded organic groups other than alkenyl groups include C 1-12 Alkyl groups, especially methyl groups and C 6-12 Aryl, especially phenyl.

[0091] In one embodiment of the present invention, (B) the organohydrogenpolysiloxane includes at least one linear organohydrogenpolysiloxane which can be represented by the following formula (II):

[0092] Average structural formula (II): R 2 3SiO(R 2 2SiO) m S i 2 3

[0093] Among them, R 2 indicates the same or different monovalent hydrocarbons other than alkenyl, which may be optionally substituted by at least one halogen, wherein at least two R 2 represents a hydrogen atom; and m ranges from 1 to 50. One type of linear organohydrogenpolysiloxane or two or more types of linear organohydrogenpolysiloxanes according to formula (II) may be used as the (B) organohydrogenpolysiloxane.

[0094] In formula (II), for R 2 The monovalent hydrocarbon other than alkenyl (which may be optionally substituted by at least one halogen) may include C 1-12 Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; C 6-12 Aryl, such as phenyl, tolyl, xylyl and naphthyl; C 7-12Aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups obtained by replacing some or all of the hydrogen atoms in these groups with halogen atoms such as fluorine, chlorine, or bromine atoms. 2 The monovalent hydrocarbon in may include a small amount of alkoxy groups (such as methoxy or ethoxy), provided that this does not adversely affect the purpose of the present invention. 2 The monovalent hydrocarbon in C 1-12 Alkyl, especially methyl or C 6-12 Aryl, especially phenyl.

[0095] In formula (II), m preferably ranges from 1 to 25, and more preferably ranges from 1 to 10, and even more preferably ranges from 1 to 5.

[0096] In a preferred embodiment, the linear organohydrogenpolysiloxane according to formula (II) comprises at least one aromatic group, preferably a phenyl group, in the side chain of the molecular chain. In other words, the linear organohydrogenpolysiloxane according to formula (II) comprises at least one aromatic group, preferably a phenyl group, in the side chain of the molecular chain. 2 / 2 ) may contain at least one aromatic group. In another preferred embodiment, the linear organohydrogenpolysiloxane according to formula (II) contains at least one (Ar2SiO 2 / 2 ) unit, wherein Ar indicates an aryl group, preferably a phenyl group.

[0097] In the case where (B) the organohydrogenpolysiloxane contains an aryl group per molecule, the content of the aryl group in the (B) organohydrogenpolysiloxane is not particularly limited, but is generally 5 mol% or more, preferably 10 mol% or more, and more preferably 15 mol% or more, and is generally 50 mol% or less, preferably 40 mol% or less, and more preferably 30 mol% or less, relative to the total amount of silicon atom-bonded organic groups. The amount of the aryl group can be measured, for example, by an analytical method such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR).

[0098] (B) organohydrogenpolysiloxane may be present in an amount of 1 wt % or more, preferably 5 wt % or more, and more preferably 10 wt % or more, relative to the total weight of the composition, and may be present in an amount of 40 wt % or less, preferably 30 wt % or less, and more preferably 20 wt % or less. Any combination of upper and lower limits may be used.

[0099] In a preferred embodiment of the present invention, (B) the organohydrogenpolysiloxane may be contained in the composition such that the molar ratio of silicon-bonded hydrogen atoms derived from component (B) to silicon-bonded alkenyl groups in the organopolysiloxane component (i.e., the H / Vi molar ratio) is 0.6 or greater, preferably 0.7 or greater, and more preferably 0.75 or greater; and / or may be 2.0 or less, preferably 1.6 or less, more preferably 1.4 or less, and even more preferably 1.2 or less.

[0100] (C) Highly reflective inorganic filler

[0101] The composition according to the present invention comprises at least one highly reflective inorganic filler having a reflectivity of at least 1.50 or higher.One type of (C) highly reflective inorganic filler or a combination of two or more types of (C) highly reflective inorganic fillers may be used.

[0102] The term "filler(s)" is understood to mean mineral or synthetic particles of any shape which are insoluble in the medium of the composition.

[0103] (C) The highly reflective inorganic filler may have any shape: flake, spherical or rectangular, regardless of the crystallographic form (eg, lamellar, cubic, hexagonal, orthorhombic, etc.) Preferably, the highly reflective inorganic filler is in the shape of a spherical form.

[0104] The refractive index of the (C) highly reflective inorganic filler is at least 1.50. Preferably, the refractive index of the (C) highly reflective inorganic filler is 1.55 or higher, more preferably 1.60 or higher, even more preferably 1.65 or higher, and particularly 1.70 or higher. The upper limit of the reflectivity is not particularly limited, but is generally 2.0 or less. The refractive index of the (C) inorganic filler can indicate, for example, a value measured at 25° C. and at a wavelength of 589 nm.

[0105] (C) Highly reflective inorganic fillers may include metal oxides, such as aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, antimony oxide and cerium oxide; metal hydroxides, such as aluminum hydroxide; nitrides, such as silicon nitride, boron nitride and aluminum nitride. Preferably, (C) Highly reflective inorganic fillers may be selected from aluminum oxide.

[0106] (C) Highly reflective inorganic fillers may also be selected from metal oxides such as talc, clay, bentonite and mica. As commercially available products, mention may be made of BYK 7305, 7303, 1958 or 2578 (which is an organically modified bentonite), and Nippon talc D600 / D300 (which is talc).

[0107] Before the (C) highly reflective inorganic filler is used in the present invention, it may be subjected to surface hydrophobic treatment using an organic silicon compound such as an organic alkoxysilane compound, an organic chlorosilane compound, an organic silazane compound, or a low molecular weight siloxane compound, or a silane coupling agent, a titanate coupling agent, or the like.

[0108] (C) high reflective inorganic filler can have an average primary particle size of 1 nm or more, and preferably 5 nm or more. (C) high reflective inorganic filler can have an average primary particle size of 50 μm or less, and preferably 30 μm or less. The term "average primary particle size" used herein means a number average size mean diameter, which is given by the statistical particle size distribution (referred to as D50) of half a population. For example, the number average size mean diameter can be measured by a laser diffraction particle size distribution analyzer.

[0109] In one embodiment of the present invention, (C) highly reflective inorganic filler has an average primary particle size of 1 μm or less, preferably 200 nm or less, more preferably 50 nm or less, and even more preferably 25 nm or less. Therefore, in this embodiment, the average primary particle size of (C) highly reflective inorganic filler can range from 1 nm to 1 μm, 1 nm to 200 nm, 5 nm to 50 nm, or 5 nm to 25 nm.

[0110] (C) The highly reflective inorganic filler may have a 1 m 2 / g or more, preferably 5m 2 / g or more, more preferably 10m 2 / g or more, and even more preferably 20m 2 / g or more. (C) The highly reflective inorganic filler may have a specific surface area of ​​500 m 2 / g or less, preferably 300m 2 / g or less, and more preferably 250m 2 / g or less. In the present invention, "specific surface area determined by the BET method" may mean a value determined by: drying a sample for measurement at 200°C for not less than three hours under a reduced pressure of not more than 1 kPa; thereafter, measuring an adsorption isotherm of only nitrogen adsorption at liquid nitrogen temperature; and analyzing the adsorption isotherm by the BET method. The pressure range used for analysis is a relative pressure of 0.1 to 0.25.

[0111] Relative to the gross weight of the composition, (C) the highly reflective inorganic filler may be present in an amount of 1 wt % or more, preferably 2 wt % or more, and more preferably 3 wt % or more, and may be present in an amount of 30 wt % or less, preferably 20 wt % or less, and more preferably 15 wt % or less. Any combination of upper and lower limits may be used.

[0112] (D) Polyether-modified organopolysiloxane

[0113] The composition according to the present invention comprises two or more polyether-modified organopolysiloxanes. Specifically, (D) polyether-modified organopolysiloxane comprises a combination of (d-1) at least one polyether-modified organopolysiloxane having at least one terminal -OH group in the polyether chain and (d-2) at least one polyether-modified organopolysiloxane having at least one terminal alkoxy or acyloxy group in the polyether chain.

[0114] The (D) polyether-modified organopolysiloxane is an organopolysiloxane with side chains and / or terminal polyethers modified. In other words, the (D) polyether-modified organopolysiloxane has at least one organic group including at least one polyether structure or at least one polyether unit in a molecular side chain and / or a molecular terminal. This means that the (D) organopolysiloxane is an organopolysiloxane in which at least one side chain and / or a molecular terminal is modified with at least one polyether structure or polyether unit.

[0115] The molecular structure of the (D) polyether-modified organopolysiloxane may be linear, branched, partially branched, cyclic or resinous, and is preferably linear.

[0116] The (d-1) component of the polyether-modified organopolysiloxane is a polyether-modified organopolysiloxane having at least one terminal -OH group in the polyether chain. One type of (d-1) polyether-modified organopolysiloxane or a combination of two or more types of (d-1) polyether-modified organopolysiloxanes may be used.

[0117] In one embodiment of the present invention, the (d-1) polyether-modified organopolysiloxane may be a linear organopolysiloxane having at least one terminal -OH group in the polyether chain, which may be represented by the following formula (III-a):

[0118] Average structural formula (III-a): R 3 3SiO(R 3 2SiO) m S i 3 3

[0119] Among them, R 3indicates the same or different organic groups including a polyoxyalkylene group having a terminal -OH group or a monovalent hydrocarbon which may be optionally substituted with at least one halogen, wherein at least one R 3 represents an organic group including a polyoxyalkylene group having a terminal -OH group; and m ranges from 1 to 1,000.

[0120] In formula (III-a), R 3 The polyoxyalkylene group with terminal-OH group included in the organic group can include two or more ethylene oxide units, propylene oxide units, butylene oxide units, or a combination thereof. The polyoxyalkylene group preferably contains 4 or more, more preferably 6 or more, still more preferably 8 or more oxyalkylene units, and / or 100 or less, preferably 60 or less, more preferably 40 or less, even more preferably 20 or less oxyalkylene units. The alkylene moiety of the oxyalkylene group can be straight or branched.

[0121] In formula (III-a), R 3 The organic group including a polyoxyalkylene group can be represented by the following formula (IV):

[0122] Formula (IV): -R 4 -O-(C2H4O) t1 (C3H6O) t2 (C4H8O) t3 -OH

[0123] Among them, R 4 It is a divalent organic group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which is bonded to the silicon atom; satisfies 0≤t1≤60, 0≤t2≤50, 0≤t3≤50, and 2≤t1+t2+t3≤110; and Y is a group selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a COCH3 group.

[0124] In formula (IV), R 4 It may represent, for example, an alkylene group, an alkenylene group, or an arylene group, and more specifically, it may represent a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, or a phenylene group.

[0125] In formula (IV), t1, t2 and t3 are the numbers of ethylene oxide units, propylene oxide units and butylene oxide units constituting the polyoxyalkylene group, and satisfy 0≤t1+t2+t3≤110, and preferably satisfy 6≤t1+t2+t3≤50, more preferably 8≤t1+t2+t3≤20.

[0126] In one embodiment of the present invention, in formula (IV), t1 is an integer of 2 or more, preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and is an integer of 50 or less, preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. In one embodiment of the present invention, in formula (IV), t2 is an integer of 0 or more and 50 or less, preferably 30 or less, more preferably 10 or less, and even more preferably 3 or less. In another embodiment, t2 may be 0. In one embodiment of the present invention, in formula (IV), t3 is an integer of 0 or more and 50 or less, preferably 30 or less, more preferably 10 or less, and even more preferably 3 or less. In another embodiment, t3 may be 0.

[0127] In a preferred embodiment of the present invention, the polyoxyalkylene group is selected from polyethylene oxide (POE), linear and / or branched polyethylene oxide (POP), and combinations thereof. The polyether structure may contain at least one polyethylene oxide unit and may only contain at least one polyethylene oxide unit. In another embodiment, the polyether structure may contain a combination of at least one polyethylene oxide (POE) unit and at least one polyethylene oxide (POP) unit.

[0128] In formula (III-a), for R 3 The monovalent hydrocarbon (which may be optionally substituted by at least one halogen) may include C 1-12 Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; C 6-12 Aryl, such as phenyl, tolyl, xylyl and naphthyl; C 7-12 Aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups obtained by replacing some or all of the hydrogen atoms in these groups with halogen atoms such as fluorine, chlorine, or bromine atoms. 3 The monovalent hydrocarbon in may include a small amount of hydroxyl or alkoxy (such as methoxy or ethoxy), provided that this does not adversely affect the purpose of the present invention. 3 The monovalent hydrocarbon in C 1-12 Alkyl, especially methyl.

[0129] In formula (III-a), m indicates the degree of siloxane polymerization of the polyether-modified linear organopolysiloxane. Preferably, m is 1 or more and 500 or less, more preferably 150 or less, still more preferably 100 or less, even more preferably 50 or less, and particularly preferably 10 or less.

[0130] In one embodiment of the present invention, (d-1) a polyether-modified linear organopolysiloxane having at least one terminal -OH group in a polyether chain may have at least one organic group including an ether bond at a molecular end, and may be represented by the following formula (III-b):

[0131] Average structural formula (III-b): R 6 R 5 2SiO(R 5 2SiO) m S i 5 2R 6

[0132] Among them, R 5 indicates the same or different monovalent hydrocarbons other than alkenyl, which may be optionally substituted by at least one halogen; R 6 indicates an organic group including a polyoxyalkylene group having a terminal -OH group; and m ranges from 0 to 1,000.

[0133] The descriptions regarding the monovalent hydrocarbon, the organic group including the polyoxyalkylene group having a terminal -OH group, and m for the above formula (III-a) can be applied equally to those for formula (III-b).

[0134] In one embodiment of the present invention, (d-1) a polyether-modified linear organopolysiloxane having at least one terminal -OH group in the polyether chain may have at least one organic group including an ether bond in a molecular side chain, and may be represented by the following formula (III-c):

[0135] Average structural formula (III-c): R 5 3SiO(R 5 2SiO) m (R 5 R 6 SiO) n S i 5 3

[0136] Among them, R 5 indicates the same or different monovalent hydrocarbons other than alkenyl, which may be optionally substituted by at least one halogen; R 6 indicates an organic group including a polyoxyalkylene group having a terminal -OH group; m ranges from 0 to 1,000; and n ranges from 1 to 1,000.

[0137] The descriptions regarding the monovalent hydrocarbon, the organic group including the polyoxyalkylene group having a terminal -OH group, and m for the above formula (III-a) can be applied to those for formula (III-c) as well.

[0138] In formula (III-c), n may be an integer ranging from 500 or less, more preferably 150 or less, still more preferably 100 or less, even more preferably 50 or less, and particularly preferably 20 or less.

[0139] In a specific embodiment, (d-1) the polyether-modified linear organopolysiloxane can be represented by the following general formula:

[0140]

[0141] Among them, m ranges from 1 to 1000, preferably 5 to 500, and n ranges from 1 to 40. In addition, the ratio m:n ranges preferably from 200:1 to 1:1. In addition, a ranges from 5 to 50, preferably 8 to 30, and more preferably 10 to 20, and b ranges from 0 to 50, preferably 0 to 50, and more preferably 0 to 10, and may be 0.

[0142] Commercially available examples of (d-1) organopolysiloxane include the following products:

[0143] - Product name: BYK-377 (manufactured by BYK), i.e., a side chain polyether-modified organopolysiloxane having -OH terminal in the polyether chain, the EO / PO ratio in the polyether chain being 10:4.2;

[0144] -Product Name: E608 (manufactured by Siltech), i.e., EO-OH terminated linear polyether-modified organopolysiloxane (PEG-8 polydimethylsiloxane);

[0145] - Product name: ABE-3642 (manufactured by Gelest), namely (30%-35% dodecyl methyl siloxane)-[7%-10% hydroxy (polyethyleneoxy (6-9) propyl) methyl siloxane]-(55%-65% dimethyl siloxane) terpolymer - Product name: Di-15-I (manufactured by Styrotechnics, Inc.), a PO-OH terminated linear polyether-modified organopolysiloxane; and

[0146] - Product Name CR 1115 (manufactured by Styrotechnics), EO / PO polyether-modified linear organopolysiloxane (PEG / PPG 18 / 18 polydimethylsiloxane).

[0147] The (d-1) polyether-modified organopolysiloxane may be present in an amount of 0.1 wt % or more, preferably 0.25 wt % or more, and more preferably 0.5 wt % or more, relative to the total weight of the composition, and / or may be present in an amount of 10 wt % or less, preferably 5 wt % or less, and more preferably 3 wt % or less. Any combination of upper and lower limits may be used.

[0148] The (d-2) component of the polyether-modified organopolysiloxane is a polyether-modified organopolysiloxane having at least one terminal alkoxy group or acyloxy group in the polyether chain. One type of (d-2) polyether-modified organopolysiloxane or a combination of two or more types of (d-2) polyether-modified organopolysiloxanes may be used.

[0149] The alkoxy groups in the polyether chain may include C 1-10 Alkoxy, such as C 1-6 Alkoxy or C 1-4 Alkoxy groups such as methoxy, ethoxy, propoxy and butoxy. Terminal alkoxy groups can also be represented by -OR, where R indicates C 1-10 Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl. Alkoxy groups are preferably methoxy groups.

[0150] The acyl group in the polyether chain may include C 1-10 Acyloxy, such as C 1-6 Acyloxy or C 1-4 An acyloxy group, such as an acetoxy group, may also be represented by -O(C=O)R, where R indicates C 1-10 Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl. The acyloxy group is preferably an acetoxy group.

[0151] In one embodiment of the present invention, the (d-2) polyether-modified organopolysiloxane may be a linear organopolysiloxane having at least one terminal alkoxy group or acyloxy group in the polyether chain, which may be represented by the following formula (Va):

[0152] Average structural formula (Va): R 7 3SiO(R 7 2SiO) m S i 7 3

[0153] Among them, R 7 indicates the same or different organic groups including polyoxyalkylene groups having terminal alkoxy (or -OR) or acyloxy (or -C(=O)OR) groups or monovalent hydrocarbons which may be optionally substituted with at least one halogen, wherein at least one R per molecule 7represents an organic group including a polyoxyalkylene group having a terminal -OR group; and m ranges from 1 to 1,000.

[0154] In formula (Va), R 7 The polyoxyalkylene group with a terminal -OR or -C(=O)OR group included in the organic group may contain two or more oxyethylene units, oxypropylene units, oxybutylene units, or a combination thereof. The polyoxyalkylene group preferably contains 4 or more, more preferably 6 or more, still more preferably 8 or more oxyalkylene units, and / or 100 or less, preferably 60 or less, more preferably 40 or less, even more preferably 20 or less oxyalkylene units. The alkylene portion of the oxyalkylene group may be linear or branched.

[0155] In formula (Va), R 7 The organic group including a polyoxyalkylene group may be represented by the following formula (VI-a) or (VI-b):

[0156] Formula (VI-a): -R 4 -O-(C2H4O) t1 (C3H6O) t2 (C4H8O) t3 -OR

[0157] Formula (VI-b): -R 4 -O-(C2H4O) t1 (C3H6O) t2 (C4H8O) t3 -C(=O)OR

[0158] Among them, R 4 is a divalent organic group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which is bonded to a silicon atom; satisfies 0≤t1≤90, 0≤t2≤80, 0≤t3≤50, and 2≤t1+t2+t3≤170; Y is a group selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a COCH3 group; and R indicates C 1-10 Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

[0159] In formula (VI-a) and (VI-b), R 4 It may represent, for example, an alkylene group, an alkenylene group, or an arylene group, and more specifically, it may represent a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, or a phenylene group.

[0160] In formulas (VI-a) and (VI-b), t1, t2 and t3 are the numbers of ethylene oxide units, propylene oxide units and butylene oxide units constituting the polyoxyalkylene group, and satisfy 0≤t1+t2+t3≤170, and preferably satisfy 6≤t1+t2+t3≤160, more preferably 8≤t1+t2+t3≤150.

[0161] In one embodiment of the present invention, in formula (VI-a) and (VI-b), t1 is an integer of 2 or more, preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and is an integer of 80 or less, and preferably 75 or less. In one embodiment of the present invention, in formula (VI-a) and (VI-b), t2 is an integer of 0 or more and 70 or less, and preferably 65 or less. In another embodiment, t2 may be 0. In one embodiment of the present invention, in formula (VI-a) and (VI-b), t3 is an integer of 0 or more and 50 or less, preferably 30 or less, more preferably 10 or less, and even more preferably 3 or less. In another embodiment, t3 may be 0.

[0162] In a preferred embodiment of the present invention, the polyoxyalkylene group is selected from polyethylene oxide (POE), linear and / or branched polyethylene oxide (POP), and combinations thereof. The polyether structure may contain at least one polyethylene oxide unit and may only contain at least one polyethylene oxide unit. In another embodiment, the polyether structure may contain a combination of at least one polyethylene oxide (POE) unit and at least one polyethylene oxide (POP) unit.

[0163] In formula (Va), for R 7 The monovalent hydrocarbon (which may be optionally substituted by at least one halogen) may include C 1-12 Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; C 6-12 Aryl, such as phenyl, tolyl, xylyl and naphthyl; C 7-12 Aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups obtained by replacing some or all of the hydrogen atoms in these groups with halogen atoms such as fluorine, chlorine, or bromine atoms. 3 The monovalent hydrocarbon in may include a small amount of hydroxyl or alkoxy (such as methoxy or ethoxy), provided that this does not adversely affect the purpose of the present invention. 7 The monovalent hydrocarbon in C 1-12 Alkyl, especially methyl.

[0164] In formula (Va), m indicates the degree of siloxane polymerization of the polyether-modified linear organopolysiloxane. Preferably, m is 1 or more and 500 or less, more preferably 150 or less, still more preferably 100 or less, even more preferably 50 or less, and particularly preferably 10 or less.

[0165] In one embodiment of the present invention, (d-2) a polyether-modified linear organopolysiloxane having at least one terminal alkoxy group or acyloxy group in the polyether chain may have at least one organic group including an ether bond at a molecular end, and may be represented by the following formula (Vb):

[0166] Average structural formula (Vb): R 9 R 8 2SiO(R 8 2SiO) m S i 8 2R 9

[0167] Among them, R 8 indicates the same or different monovalent hydrocarbons other than alkenyl, which may be optionally substituted by at least one halogen; R 9 indicates an organic group including a polyoxyalkylene group having a terminal -OR or -C(=O)OR group; and m ranges from 0 to 1,000.

[0168] The descriptions regarding the monovalent hydrocarbon, organic group including the polyoxyalkylene group having a terminal -OR or -C(=O)OR group, and m for the above formula (Va) are equally applicable to those for formula (Vb).

[0169] In one embodiment of the present invention, (d-2) a polyether-modified linear organopolysiloxane having at least one terminal alkoxy group or acyloxy group in the polyether chain may have at least one organic group including an ether bond in a molecular side chain and may be represented by the following formula (Vc):

[0170] Average structural formula (Vc): R 8 3SiO(R 8 2SiO) m (R 8 R 9 SiO) n S i 8 3

[0171] Among them, R 8 indicates the same or different monovalent hydrocarbons other than alkenyl, which may be optionally substituted by at least one halogen; R 9indicates an organic group including a polyoxyalkylene group having a terminal -OR or -C(=O)OR group; m ranges from 0 to 1,000; and n ranges from 1 to 1,000.

[0172] The descriptions regarding the monovalent hydrocarbon, organic group including a polyoxyalkylene group having a terminal -OR or -C(=O)OR group, and m for the above formula (Va) are equally applicable to those for formula (Vc).

[0173] In formula (Vc), n may be an integer ranging from 500 or less, more preferably 150 or less, still more preferably 100 or less, even more preferably 50 or less, and particularly preferably 20 or less.

[0174] Commercially available examples of (d-2) organopolysiloxane include the following products:

[0175] -Product Name: SL3288 (manufactured by BASF), i.e., MeO-(PO) m -(EO) m’ -(Me2SiO) n -(EO) m’ -(PO) m -OMe, a polyether-terminally modified linear polydimethylsiloxane having -OCH3 termini in the polyether chain,

[0176] - Product name KF6011 (manufactured by Shin-Etsu Chemical), i.e., composed of the formula Me3SiO(Me2SiO) m (Me(POE)SiO) n SiMe3 represents a polydimethylsiloxane modified with a side chain PEG-11 methyl ether having an -OCH3 terminal in the polyether chain,

[0177] - Product name SL-3030 (manufactured by BASF), i.e., Me3SiO(Me2SiO) n (Me(POE)(POP)RSiO) m SiMe3 represents a linear polydimethylsiloxane modified with a side chain polyether having -OCH3 terminal in the polyether chain.

[0178] - Product name BYK-378 (manufactured by BYK), i.e., composed of the formula Me3SiO(Me2SiO) n (Me(POE)(POP)RSiO) mSiMe3 represents a linear polydimethylsiloxane modified with EO / PO (1:1) side chain polyether having -OC(=O)CH3 terminal in the polyether chain.

[0179] The number average molecular weight of (D) the polyether-modified organopolysiloxane including components (d-1) and (d-2) is not particularly limited, but may range from 3,000 to 60,000, and preferably from 3,000 to 40,000.

[0180] The (d-2) polyether-modified organopolysiloxane may be present in an amount of 0.1 wt % or more, preferably 0.25 wt % or more, and more preferably 0.5 wt % or more, relative to the total weight of the composition, and / or may be present in an amount of 10 wt % or less, preferably 5 wt % or less, and more preferably 3 wt % or less. Any combination of upper and lower limits may be used.

[0181] In a preferred embodiment of the present invention, the (d-1) polyether-modified organopolysiloxane and the (d-2) polyether-modified organopolysiloxane may be contained in the composition such that a weight ratio of the (d-1) polyether-modified organopolysiloxane to the (d-2) polyether-modified organopolysiloxane ranges from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 3:1 to 1:3, and even more preferably from 2:1 to 1:2.

[0182] (D) The polyether-modified organopolysiloxane comprising components (d-1) and (d-2) may be present in a total amount of 0.1 wt % or more, preferably 0.5 wt % or more, and more preferably 1 wt % or more, relative to the total weight of the composition, and / or may be present in a total amount of 10 wt % or less, preferably 5 wt % or less, and more preferably 3 wt % or less. Any combination of upper and lower limits may be used.

[0183] (E) Curing catalyst

[0184] Component (E) is a curing catalyst that promotes the hydrosilylation reaction of the organopolysiloxane component of the present invention. The composition according to the present invention may contain one type of (E) hydrosilylation catalyst or may contain a combination of two or more types of (E) hydrosilylation catalysts.

[0185] 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-based compounds, such as platinum fine powder, platinum black, platinum-loaded silica fine powder, platinum-loaded activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, etc. Alkenylsiloxane complexes of platinum 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 part of the methyl groups in alkenylsiloxanes are replaced by ethyl, phenyl, etc., and alkenylsiloxanes in which the vinyl groups in alkenylsiloxanes are replaced by allyl, hexenyl, etc.

[0186] The amount of the (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, and more preferably 2 ppm or more, relative to the total weight of the (E) curing reactive organopolysiloxane, and / or may be present in an amount of 20 ppm or less, preferably 15 ppm or less, and more preferably 10 ppm or less. Any combination of upper and lower limits may be used.

[0187] (Other organopolysiloxanes)

[0188] In one embodiment of the present invention, the curable silicone composition according to the present invention may or may not contain at least one alkenyl-containing linear organopolysiloxane. The alkenyl-containing linear organopolysiloxane contains at least two alkenyl groups per molecule and can be represented by the following formula (VII):

[0189] Average structural formula (VII): R 1 3SiO(R 1 2SiO) m S i 1 3

[0190] Among them, R 1 indicates identical or different monovalent hydrocarbons, which may be optionally substituted by at least one halogen, wherein at least two R 1 represents an alkenyl group; and m ranges from 1 to 1,000. One type of linear organopolysiloxane or two or more types of linear organopolysiloxanes may be contained in the curable silicone composition.

[0191] For R in formula (Ia) 1 The definition of can also be applied to R in formula (VII) 1 .

[0192] In formula (VII), m preferably ranges from 5 to 500, more preferably from 10 to 100, and even more preferably ranges from 15 to 50.

[0193] In a preferred embodiment of the present invention, the alkenyl-containing linear organopolysiloxane may be a linear dimethylpolysiloxane containing dimethylvinylsiloxy groups at both ends of the molecular chain.

[0194] The alkenyl-containing linear organopolysiloxane may contain at least one aryl group in the organic group bonded to the silicon atom. In a preferred embodiment of the present invention, the alkenyl-containing linear organopolysiloxane contains at least one aryl group in the D unit, i.e., in the side chain. The alkenyl-containing linear organopolysiloxane may or may not contain an aryl group in the M unit, i.e., at the molecular end, but preferably does not contain any aryl group in the M unit.

[0195] The content of the aryl group in the alkenyl-containing linear organopolysiloxane is not particularly limited, but is generally 10 mol% or more, preferably 20 mol% or more, and 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, relative to the total amount of silicon-bonded organic groups. The amount of the aryl group can be measured, for example, by an analytical method such as Fourier transform infrared spectroscopy (FT-IR) or nuclear magnetic resonance (NMR) or the following titration method.

[0196] The alkenyl-containing linear organopolysiloxane may be present in an amount of 5 wt % or more, preferably 10 wt % or more, and more preferably 15 wt % or more, relative to the total weight of the composition, and / or may be present in an amount of 50 wt % or less, preferably 40 wt % or less, and more preferably 30 wt % or less. Any combination of upper and lower limits may be used.

[0197] In another embodiment of the present invention, the curable silicone composition according to the present invention may or may not contain at least one epoxy-containing resinous organopolysiloxane. The epoxy-containing resinous organopolysiloxane may be represented by the following formula (VIII):

[0198] Average structural formula (VIII): (R 10 3SiO 1 / 2 ) a (R 10 2SiO 2 / 2 ) b (R 10 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 )e

[0199] Among them, R 10 indicates identical or different monovalent hydrocarbons, which may be optionally substituted by at least one halogen, wherein at least two R 10 represents an alkenyl group, and at least one R 10 represents an organic group containing an epoxy group; X represents hydrogen or an alkyl group; and satisfies 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. The value e indicates that (XO 1 / 2 ) groups relative to the total number of silicon atoms. One type of epoxy-containing resinous organopolysiloxane or two or more types of epoxy-containing resinous organopolysiloxanes may be used.

[0200] For R in formula (Ia) 1 The definition of monovalent hydrocarbon can be applied to R in formula (VIII) in the same manner. 10 of monovalent hydrocarbons.

[0201] In formula (VIII), for R 10 The epoxy-containing organic groups include glycidyloxyalkyl groups such as 2-glycidyloxyethyl, 3-glycidyloxypropyl, and 4-glycidyloxybutyl; epoxycycloalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)-propyl; epoxyalkyl groups such as 3,4-epoxybutyl and 7,8-epoxyoctyl; and groups obtained by replacing some or all of the hydrogen atoms in these groups with halogen atoms such as fluorine, chlorine or bromine atoms.

[0202] Preferably, R in formula (VIII) 10 Represents C 1-12 Alkyl, especially methyl, C 2-12 Alkenyl, especially vinyl, C 6-12 Aryl, especially phenyl, and glycidyloxyalkyl, especially 3-glycidyloxypropyl.

[0203] In formula (VIII), X represents hydrogen or an alkyl group. The alkyl group in X preferably represents C 1-3 Alkyl groups such as methyl, ethyl, or propyl.

[0204] In one embodiment of the present invention, in formula (VIII), the range of a is preferably 0≤a≤0.4, more preferably in the range of 0.05≤a≤0.3, and even more preferably in the range of 0.1≤a≤0.2. In formula (VIII), the range of b is preferably 0.1≤b≤0.5, more preferably 0.15≤b≤0.4, and even more preferably 0.2≤b≤0.3. In formula (VIII), the range of c is preferably 0.1≤c≤0.7, more preferably 0.2≤c≤0.6, and even more preferably 0.3≤c≤0.55. In formula (VIII), the range of d is preferably 0≤d≤0.3, more preferably 0≤d≤0.2, and even more preferably 0≤d≤0.1. In formula (VIII), the range of e is preferably 0≤e≤0.4, more preferably 0.05≤e≤0.3, and even more preferably 0.1≤e≤0.2.

[0205] The epoxy-containing resinous organopolysiloxane may be present in an amount of 0.5 wt % or more, preferably 1 wt % or more, and more preferably 1.5 wt % or more, relative to the total weight of the composition, and / or may be present in an amount of 10 wt % or less, preferably 7 wt % or less, and more preferably 5 wt % or less. Any combination of upper and lower limits may be used.

[0206] (Other ingredients)

[0207] The curable silicone composition may contain a hydrosilylation reaction inhibitor as an additional component.One type of hydrosilylation reaction inhibitor or two or more types of hydrosilylation reaction inhibitors may be used.

[0208] As hydrosilylation reaction inhibitors, there may be mentioned acetylenic alcohols such as methyl butynol, ethynyl cyclohexanol, dimethyl hexynol, 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, 1-ethynyl-1-cyclohexanol, and combinations thereof; cycloalkenyl siloxanes such as methylvinylcyclosiloxane, which are exemplified by 1,3,5,7-tetramethyl 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and combinations thereof; enyne compounds, such as 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne; triazoles, such as benzotriazole; phosphines; thiols; hydrazines; amines, such as tetramethylethylenediamine, dialkyl fumarates, dienyl fumarates, dialkoxyalkyl fumarates, maleates such as diallyl maleate; nitriles; ethers; carbon monoxide; olefins, such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols, such as benzyl alcohol; and combinations thereof. Alternatively, the hydrosilylation-reaction inhibitor may be selected from the group consisting of alkynols (eg, 1-ethynyl-1-cyclohexanol) and maleates (eg, diallyl maleate, bismaleate, or n-propyl maleate), and combinations of two or more thereof.

[0209] The amount of the hydrosilylation-reaction inhibitor present in the curable silicone composition may be 0 to 5 wt %, preferably 0.001 to 3 wt %, and more preferably 0.005 to 1 wt %, relative to the total weight of the composition.

[0210] The curable silicone composition according to the present invention may further comprise any optional one or more additives commonly used in the art, the one or more additives being selected, for example, from organopolysiloxanes other than the components described above, organic fillers, inorganic fillers other than the above component (C), pigments, adhesion-imparting agents, resistance imparting agents, anti-adhesive agents, heat-resistant agents, dyes, flame retardancy imparting agents, and mixtures thereof.

[0211] The curable silicone composition according to the present invention can be prepared by mixing the above-mentioned necessary and optional components in a conventional manner. The mixing method of each component can be carried out by conventional known methods, and is not particularly limited. For example, mixing is carried out by simple stirring or mixing using a mixing device, such as a single-axis or double-axis continuous mixer, a double roller, a Hobart mixer, a dental mixer, a planetary mixer, a kneader mixer, and a Henschel mixer.

[0212] The curable silicone composition according to the present invention may have a viscosity ranging from 3 to 50 Pa·s, preferably 5 to 40 Pa·s, and more preferably 10 to 30 Pa·s, and even more preferably 12 to 35 Pa·s at 25° C. The viscosity herein can be measured with a rheometer from Antonpaar with a 40 mm cone plate at an angle of 2 degrees at a shear rate of 10 / s.

[0213] The curable silicone composition according to the present invention can be cured to form a cured product having good transparency. Specifically, the cured product of the curable silicone composition of the present invention preferably has a light transmittance of 70% or more, more preferably 80% or more, and more preferably 85% or more at a wavelength of 400nm to 700nm, for example 450nm. The light transmittance of the cured product can be determined, for example, by measuring the cured product with an optical path length of 1 using a spectrophotometer.

[0214] The curable silicone composition according to the present invention can be used to encapsulate or seal semiconductor elements including optical semiconductors when manufacturing semiconductor devices. In such an embodiment, the curable silicone composition can be applied to a substrate, which is selected from a glass substrate and a PCB substrate, such as those made of epoxy-based polymers. The glass substrate may be surface-coated with or without a well-known surface treatment agent, such as a silicone surface treatment agent.

[0215] [Sealing material]

[0216] The present invention also relates to a sealing material obtained by curing the curable silicone composition according to the present invention. The sealing material of the present invention is preferably used for sealing semiconductor elements including optical semiconductors. The shape of the sealing material is not limited, but is preferably in a dome shape, a lens shape or a sheet form. Examples of semiconductor elements include SiC, GaN, etc. Examples of optical semiconductor elements include elements represented by light emitting diodes (LEDs), photodiodes, phototransistors, laser diodes, etc.

[0217] The substrate on which the sealing material of the present invention is formed is not particularly limited, but for example, the substrate can be selected from a glass substrate and a PCB substrate. The glass substrate may be surface-coated with or without a well-known surface treatment agent, such as a silicone surface treatment agent.

[0218] [Optical semiconductor device]

[0219] The present invention also relates to an optical semiconductor device provided with the sealing material of the present invention. Examples of optical semiconductor elements include light emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state imaging devices, and light emitters and light receivers for photocouplers, and light emitting diodes (LEDs) are particularly preferred.

[0220] Since the light emitting diode (LED) emits light from the top, bottom, left and right of the optical semiconductor element, it is preferred that the parts constituting the light emitting diode (LED) have high light transmittance. As a substrate on which such an optical semiconductor element is mounted, there can be mentioned conductive metals such as silver, gold and copper; non-conductive metals such as aluminum and nickel; thermoplastic resins containing white pigments such as PPA and LCP; thermosetting resins containing white pigments such as epoxy resins, BT resins, polyimide resins, and silicone resins; ceramics such as aluminum oxide and aluminum nitride.

[0221] The specific method according to the present invention is as follows.

[0222] Aspect 1: A curable silicone composition comprising:

[0223] (A) at least one resinous organopolysiloxane having at least two alkenyl groups and at least one aromatic group per molecule;

[0224] (B) at least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule;

[0225] (C) at least one inorganic filler having a reflectivity of 1.50 or more;

[0226] (D) two or more polyether-modified organopolysiloxanes comprising a combination of (d-1) at least one polyether-modified organopolysiloxane having at least one terminal -OH group in the polyether chain and (d-2) at least one polyether-modified organopolysiloxane having at least one terminal alkoxy or acyloxy group in the polyether chain; and

[0227] (E) at least one hydrosilylation catalyst.

[0228] Aspect 2: The composition according to aspect 1, wherein the (A) resinous organopolysiloxane contains aromatic groups in an amount of 30 mol% or more and 90 mol% or less in the silicon atom-bonded organic groups relative to the total amount of the silicon atom-bonded organic groups.

[0229] Aspect 3: The composition according to aspect 1 or 2, wherein the (A) resinous organopolysiloxane is composed of: (R2SiO 2 / 2 ) and the D siloxane unit represented by (RSiO 3 / 2 ) represents a T siloxane unit.

[0230] Aspect 4: The composition according to any one of Aspects 1 to 3, wherein the (B) organohydrogenpolysiloxane contains at least one aromatic group in the organic group bonded to a silicon atom.

[0231] Aspect 5: The composition according to any one of Aspects 1 to 4, wherein the (C) inorganic filler is selected from aluminum oxides.

[0232] Aspect 6: The composition according to any one of Aspects 1 to 5, wherein the (D) polyether-modified organopolysiloxane comprising components (d-1) and (d-2) is present in a total amount of 0.1 wt % or more and 10 wt % or less relative to the total weight of the composition.

[0233] Aspect 7: A sealing material formed using the curable silicone composition according to any one of Aspects 1 to 6.

[0234] Aspect 8: An optical semiconductor device provided with the sealing material according to aspect 7.

[0235] Examples

[0236] The present invention is described in more detail by way of examples, however these examples should not be construed as limiting the scope of the present invention.

[0237] Curable silicone composition of the present invention will be described in detail by examples and comparative examples. In these examples and comparative examples, the following components are used to prepare the curable silicone composition. In the formula, Vi indicates vinyl, Me indicates methyl, Ph indicates phenyl, and Ep indicates 3-glycidyloxypropyl. In addition, the chemical formula of the organopolysiloxane component is shown in the table in a simplified manner, and the organic groups except Me in the M, D or T units are shown in brackets. The numerical values ​​of the amounts of the components shown in the table are all based on "parts by weight" as active raw materials.

[0238] Components:

[0239] (a-1) an alkenyl-containing resinous organopolysiloxane represented by the following formula: 2 / 2 )0.28 (Ph2SiO 2 / 2 ) 0.23 (PhSiO 3 / 2 ) 0.49

[0240] (a-2) an alkenyl-containing resinous organopolysiloxane represented by the following formula: 2 / 2 ) 0.25 (Ph2SiO 2 / 2 ) 0.3 (PhSiO 3 / 2 ) 0.45

[0241] (a-3) Alkenyl-containing linear organopolysiloxane represented by the following formula: ViMe2SiO(MePhSiO) 20 SiMe2Vi

[0242] (a-4) a resinous organopolysiloxane containing an alkenyl group and an epoxy group represented by the following formula: 1 / 2 ) 0.13 (MeEpSiO 2 / 2 ) 0.24 (PhSiO 3 / 2 ) 0.46 (OMe) 0.17

[0243] (b) A linear organohydrogenpolysiloxane represented by the formula HMe2SiO(Ph2SiO)SiMe2H

[0244] (c) Alumina filler (D50: 10 to 20 nm)

[0245] (d-1-1) Formula Me3SiO(Me2SiO) n (Me(EO) m (PO) m' OHMeSiO) m Side chain polyether-modified organopolysiloxane having -OH terminal in the polyether chain represented by SiMe3 (product name: BYK-377 sold by BYK)

[0246] (d-1-2) by formula HO(PO) m (EO) m' Me2SiO(Me2SiO) t SiMe2(EO) n (PO) n' OH-represented polyether chain-terminated organopolysiloxane (product name: sold by Sty Chemical Co., Ltd. E608)

[0247] (d-2-1) is composed of the formula MeO(PO) m (EO) m’ (Me2SiO) n (EO) m’ (PO) m OMe represented by EO / PO polyether-terminated linear organopolysiloxane (product name: sold by BASF SL-3288)

[0248] (d-2-2) is composed of the formula Me3SiO(Me2SiO) m (Me(POE)SiO) n SiMe3-represented polydimethylsiloxane having a side chain PEG-11 methyl ether-modified polydimethylsiloxane having -OCH3 terminal in the polyether chain, product name KF6011 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0249] (d-2-3) is composed of the formula Me3SiO(Me2SiO) n (Me(POE)(POP)RSiO) m SiMe3 represented by a side chain polyether-modified linear polydimethylsiloxane having -OCH3 terminal in the polyether chain, product name SL-3030 (manufactured by BASF Corporation),

[0250] (d-2-4) is composed of the formula Me3SiO(Me2SiO) n (Me(POE)(POP)RSiO) m SiMe3-represented linear polydimethylsiloxane having a side chain polyether-modified straight chain polydimethylsiloxane having -OC(=O)CH3 terminal in the polyether chain, product name BYK-378 (manufactured by BYK), EO / PO (1:1)

[0251] (e) Complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum concentration: 3.0 wt%)

[0252] (f) 1-ethynyl-1-cyclohexanol

[0253] [Evaluate]

[0254] (Viscosity and thixotropic properties)

[0255] The viscosity of the prepared curable silicone composition of each example was measured at a shear rate of 10 / s and 1 / s at 25° C. using a rheometer (Antonpaar MCR302) with a 40 mm cone plate at a 2 degree angle. The thixotropic index was calculated as the viscosity ratio of (viscosity at 1 / s) / (viscosity at 10 / s).

[0256] (Refractive Index)

[0257] The refractive index of the curable silicone composition at 25° C. was measured at a wavelength of 589 nm using an Abbe-type refractometer.

[0258] (Transmittance)

[0259] The curable silicone composition was filled into a mold having a predetermined shape of concavity, and then cured for 60 minutes at 150° C. The obtained plate-shaped cured product having a thickness of 1 mm was subjected to transmittance measurement at 25° C. at 450 nm.

[0260] (Wettability on PCB)

[0261] The curable silicone composition was dispensed on a PCB substrate made of an epoxy resin-based polymer so as to form a straight line shape having a height of about 1 mm. After the composition was left to stand at 25°C for 3 hours, the dispensed curable silicone composition was then cured at 150°C for 60 minutes. Wettability on the PCB substrate was analyzed by observing whether there was delamination between the cured composition and the PCB substrate. When there was no delamination, the result was displayed as "OK", and when there was delamination, the result was displayed as "NG".

[0262] The results are summarized in the table below.

[0263] Table 1

[0264]

[0265]

[0266] Table 2

[0267]

[0268]

[0269] As can be seen from the results from Tables 1 and 2, the examples of the curable silicone composition according to the present invention have sufficient thixotropic properties and show higher transmittance properties than the comparative examples, which indicates that the composition according to the present invention can provide a cured product with high transparency. In addition, the curable silicone composition according to the present invention shows improved wettability on a PCB substrate, thereby providing a reliable material for a semiconductor device.

[0270] Therefore, it can be said that the curable silicone composition according to the present invention is very useful for encapsulation applications in manufacturing semiconductor packages, especially LED packages.

Claims

1. A curable silicone composition comprising: (A) at least one resinous organopolysiloxane having at least two alkenyl groups and at least one aromatic group per molecule; (B) at least one organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule; (C) at least one inorganic filler, the at least one inorganic filler having a reflectivity of 1.50 or more; (D) two or more polyether-modified organopolysiloxanes comprising a combination of (d-1) at least one polyether-modified organopolysiloxane having at least one terminal -OH group in the polyether chain and (d-2) at least one polyether-modified organopolysiloxane having at least one terminal alkoxy or acyloxy group in the polyether chain; and (E) at least one hydrosilylation catalyst.

2. The composition according to claim 1, wherein The (A) resinous organopolysiloxane contains aromatic groups in silicon atom-bonded organic groups in an amount of 30 mol % or more and 90 mol % or less relative to the total amount of the silicon atom-bonded organic groups.

3. The composition according to claim 1, wherein The (A) resinous organopolysiloxane is composed of: (R2SiO 2 / 2 ) and the D siloxane unit represented by (RSiO 3 / 2 ) represented by a T siloxane unit.

4. The composition according to claim 1, wherein The (B) organohydrogenpolysiloxane contains at least one aromatic group in the silicon-bonded organic group.

5. The composition according to claim 1, wherein The (C) inorganic filler is selected from aluminum oxides.

6. The composition according to claim 1, wherein The (D) polyether-modified organopolysiloxane including the (d-1) and (d-2) components is present in a total amount of 0.1 wt % or more and 10 wt % or less relative to the total weight of the composition.

7. A sealing material formed using the curable silicone composition according to any one of claims 1 to 6. 8 . An optical semiconductor device provided with the sealing material according to claim 7 .

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