JP6657037B2 - Addition-curable silicone resin composition and semiconductor device - Google Patents

Description

  The present invention relates to an addition-curable silicone composition, particularly an addition-curable silicone composition containing an alkenyl group-containing branched organopolysiloxane having a long siloxane branched chain, and a semiconductor encapsulated by the cured product. Semiconductor device.

  The addition-curable silicone resin has been used as a sealing material for sealing a semiconductor element such as an LED since it is excellent in heat resistance, light resistance, rapid curing property and the like. For example, Patent Literature 1 describes an addition-curable silicone resin having a high adhesive strength to an LED package made of a thermoplastic resin such as PPA. Patent Document 2 describes a method of sealing an optical semiconductor element by compression molding of an addition-curable silicone resin composition.

As described above, addition-curable silicone resins are widely and generally used as semiconductor encapsulating materials, but their properties are still unsatisfactory. In particular, since the LED encapsulant is exposed to external stresses such as changes in temperature and humidity in addition to internal stresses due to temperature changes due to ON / OFF of the optical semiconductor device, it has cold resistance in addition to heat resistance and light resistance. Is also important. However, the conventional addition-curable silicone resin has a problem in that it has insufficient low-temperature characteristics, cannot withstand the stress of temperature change, and causes cracks.

As one means for improving low-temperature characteristics, it is known that it is effective to have a branched structure in a linear silicone chain, and various studies have been made on its production method. (Patent Documents 1, 2, and 3). However, such a method of condensing and equilibrating a hydrolyzable silane containing R ³ SiO _1/2 unit [M unit] and RSiO _3/2 unit [T unit] using an acid catalyst or an alkali catalyst is mainly used. Since the chain lengths of the chains and side chains cannot be controlled independently, it has been difficult to obtain a siloxane having a desired structure.

JP 2006-256603 A JP 2006-93354 A JP-A-2002-348377 JP 2001-163981 A JP 2000-351949 A

  The present invention has been made in view of the above problems, and has an addition-curable silicone composition that provides a cured product having good low-temperature characteristics and excellent temperature change resistance, and a semiconductor element is encapsulated by a cured product of the composition. It is another object of the present invention to provide a highly reliable semiconductor device.

（式中、Ｒ^１は、互いに独立に、炭素数１から１２の置換または非置換の飽和炭化水素基もしくは炭素数６から１２の置換または非置換の芳香族炭化水素基から選ばれる基であり、Ｒ^２は、互いに独立に、炭素数１から１２の置換または非置換の飽和炭化水素基もしくは炭素数６から１２の置換または非置換の芳香族炭化水素基、炭素数２から１０のアルケニル基から選ばれる基であり、各々のＲ^１、Ｒ^２は同一であっても異なっていても良く、ただし該オルガノポリシロキサンは前記アルケニル基を主鎖の両末端のみに有し、ａは２〜１００の整数、ｂは５〜１００の整数、ｃは５〜１００の整数、0.03≦a／(a+b)＜1.0、（Ｒ^１ _２Ｒ^２ＳｉＯ_１／２）単位の数／（Ｒ^２ＳｉＯ_３／２）単位の数≦2であり、ａ、ｂおよびｃのシロキサン鎖の並びはランダムであってもブロックであっても良い）
で示される分岐状オルガノポリシロキサン、
（Ｂ）下記式（２）
（Ｒ^２ _３ＳｉＯ_１／２）_ｒ（Ｒ^２ _２ＳｉＯ_２／２）_ｓ（Ｒ^２ＳｉＯ_３／２）_ｔ（ＳｉＯ_４／２）_ｕ （２）
（式中、Ｒ^２の定義は上記と同じであり、Ｒ^２の少なくとも２つはアルケニル基であり、ｒは０から１００の整数、ｓは０から３００の整数、ｔは０から２００の整数、ｕは０から２００の整数であり、１≦ｔ＋ｕ≦４００、２≦ｒ＋ｓ＋ｔ＋ｕ≦８００である）
で示されるオルガノポリシロキサン
（Ａ）成分１００質量部に対して５〜９００重量部の量、
（Ｃ）ヒドロシリル基を分子内に少なくとも２つ有するオルガノポリシロキサン
（Ａ）成分と（Ｂ）成分中のアルケニル基の合計数に対して（Ｃ）成分中のヒドロシリル基の数が０．４〜４．０となる量、および
（Ｄ）ヒドロシリル化触媒
ヒドロシリル化反応を進行させるのに十分な量
を含む、半導体素子封止用付加硬化性シリコーン樹脂組成物。 That is, the present invention provides an addition-curable silicone composition for encapsulating a semiconductor device , comprising the following components (A) to (D).
(A) Formula (1) below

(Wherein, R ^{1 s} are each independently a group selected from a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. , R ² are each independently a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Wherein each of R ¹ and R ² may be the same or different, provided that the organopolysiloxane has the alkenyl group only at both ends of the main chain, 100 integers, b is 5 to 100 integer, c is 5-100 integer, 0.03 ≦ a / (a + b) <1.0, (R 1 2 R 2 SiO 1/2) units of several / ^{(R 2} SiO _3/2 ) The number of units ≦ 2, and a, b, and c siloxanes (The arrangement of chains may be random or block.)
A branched organopolysiloxane represented by
(B) The following formula (2)
_{^{(R 2 3 SiO 1/2) r}} (R 2 2 SiO 2/2) s (R 2 SiO 3/2) t (SiO 4/2) u (2)
(Wherein, R ² is the same as defined above, at least two of R ² are alkenyl groups, r is an integer of 0 to 100, s is an integer of 0 to 300, and t is an integer of 0 to 200. , U is an integer from 0 to 200, and 1 ≦ t + u ≦ 400 and 2 ≦ r + s + t + u ≦ 800)
An amount of 5 to 900 parts by weight based on 100 parts by weight of the organopolysiloxane (A) component represented by
(C) Organopolysiloxane having at least two hydrosilyl groups in the molecule The number of hydrosilyl groups in the component (C) is from 0.4 to the total number of alkenyl groups in the component (A) and the component (B). 4.0, and
(D) Hydrosilylation catalyst An addition-curable silicone resin composition for encapsulating a semiconductor element , comprising an amount sufficient to allow the hydrosilylation reaction to proceed.

According to the present invention, by using an alkenyl group-containing branched organopolysiloxane containing many side chains sufficiently longer than the siloxane chain length of the main chain in combination with a specific other component, the same degree of main chain can be obtained. As compared with the case where a linear organopolysiloxane having a chain length is used, the glass transition point of the cured product is lowered, and crack resistance and the like are improved.

4 is a graph of the storage elastic modulus and a graph of Tan δ of the cured products of Example 1 (solid line) and Comparative Example 1 (dotted line).

（式中、Ｒ^１は、互いに独立に、炭素数１から１２の置換または非置換の飽和炭化水素基もしくは炭素数６から１２の置換または非置換の芳香族炭化水素基から選ばれる基であり、Ｒ^２は、互いに独立に、炭素数１から１２の置換または非置換の飽和炭化水素基もしくは炭素数６から１２の置換または非置換の芳香族炭化水素基、炭素数２から１０のアルケニル基から選ばれる基であり、各々のＲ^１、Ｒ^２は同一であっても異なっていても良く、ただしＲ^２のうち少なくとも２つはアルケニル基、ａは２〜１００の整数、ｂは５〜１００の整数、ｃは５〜１００の整数、0.03≦a／(a+b)＜1.0、（Ｒ^１ _２Ｒ^２ＳｉＯ_１／２）単位の数／（Ｒ^２ＳｉＯ_３／２）単位の数≦2であり、ａ、ｂおよびｃのシロキサン鎖の並びはランダムであってもブロックであっても良い）
で示される分岐状オルガノポリシロキサン。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
(A) Branched polyorganosiloxane One of the features of the present invention, (A) the branched polyorganosiloxane is represented by the following formula.
(A) Formula (1) below

(Wherein, R ^{1 s} are each independently a group selected from a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. , R ² are each independently a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. R ¹ and R ² may be the same or different, provided that at least two of R ² are alkenyl groups, a is an integer of 2 to 100, and b is 5 to 100 integers, c is 5-100 integer, 0.03 ≦ a / (a + b) <1.0, the number of _{^{(R 1 2 R 2 SiO 1/2}} ) units of several ^/ (R _{2 SiO 3/2)} units ≦ 2, and the arrangement of the siloxane chains of a, b and c is random, Or a block)
A branched organopolysiloxane represented by the formula:

a is an integer of 2 to 100, preferably an integer of 2 to 75, more preferably an integer of 2 to 50, b is an integer of 5 to 100, preferably an integer of 5 to 75 , More preferably an integer of 10 to 50, c is an integer of 5 to 100, preferably an integer of 5 to 75, and more preferably an integer of 10 to 50. ^{_{(R 1 2 R 2 SiO 1/2}} ) units of several ^/ (R _{2 SiO 3/2)} a number ≦ 2 units, a, the arrangement of the siloxane chain of b be a block be a random good.
In the formula (1), it is preferable that 0.03 ≦ a / (a + b) <1.0 and 0.09 ≦ a / (a + b) ≦ 0.9.

R ¹ , independently of each other, is a group selected from a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms; Specific examples of the group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; and a hydrogen atom bonded to a carbon atom of these groups. Those in which some or all of the atoms have been substituted with halogen atoms such as fluorine, bromine and chlorine or cyano groups, for example, halogenated monovalent hydrocarbon groups such as trifluoropropyl and chloropropyl groups; β-cyanoethyl groups, γ A cyanoalkyl group such as a cyanopropyl group, a 3-methacryloxypropyl group, a 3-glycidyloxypropyl group, a 3-mercaptopropyl group, Aminopropyl groups. Among these, a methyl group and a cyclohexyl group are preferred, and a methyl group is particularly preferred. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, and a naphthyl group, and an aralkyl group such as a benzyl group, a phenylethyl group, and a phenylpropyl group. Some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms such as fluorine, bromine, and chlorine, or cyano groups. Among them, a phenyl group and a tolyl group are preferable, and a phenyl group is particularly preferable. Preferably, at least one of R ¹ is an aromatic hydrocarbon group having 6 to 12 carbon atoms.

R ² , independently of each other, is a substituted or unsubstituted saturated hydrocarbon group having 1 to 12, preferably 1 to 8 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12, preferably 6 to 10 carbon atoms. It is a group selected from a hydrogen group and an alkenyl group having 2 to 10, preferably 2 to 8 carbon atoms. Saturated hydrocarbon group and aromatic hydrocarbon group include the same as those exemplified for the above R ^1. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a hexenyl group, and a styryl group. A vinyl group and an allyl group are preferable, and a vinyl group is particularly preferable.
a is an integer of 2 to 100, preferably an integer of 2 to 75, more preferably an integer of 2 to 50, b is an integer of 5 to 100, preferably an integer of 5 to 75 , More preferably an integer of 10 to 50, c is an integer of 5 to 100, preferably an integer of 5 to 75, and more preferably an integer of 10 to 50. _{^{(R 1 2 R 2 SiO 1/2}} ) units of several ^/ (R _{2 SiO 3/2)} a number ≦ 2 units, a, the arrangement of the siloxane chain of b be a block be a random good. 0.03 ≦ a / (a + b) <1.0, and preferably 0.09 ≦ a / (a + b) ≦ 0.9.
In the component (A), the proportion of the number of monovalent aromatic hydrocarbon groups in the total number of all the substituents bonded to the silicon atom is 3% or more, particularly 5% or more, 90% or less, particularly 80%. The following is preferred. Within this range, the branched organopolysiloxane of the component (A) has a high refractive index and low gas permeability, so that the composition can be suitably used for semiconductor device sealing applications and the like. .

（式中、Ｒ^１、Ｒ^２、ｃは上記と同じであり、Ｒ^３は水素原子または炭素数１〜６の飽和炭化水素基である）で示されるオルガノポリシロキサンと、シロキサン類、たとえば、下記式（５）

（式中、Ｒ^２、Ｒ^３は上記と同じであり、ｂ’は1以上かつｂ以下であり、ｂは上記と同じである）で示される、両末端にアルコキシシリル基またはヒドロキシシリル基（シラノール基）を有するオルガノポリシロキサンとを共縮合させ、次にシラン、たとえば下記式（６）

（式中、Ｒ^１、Ｒ^２は上記と同じであり、Ｘはハロゲン原子またはＲ^３Ｏ−［Ｒ^３は上記と同じである］で示される基である）で示される加水分解性基含有シラン化合物によって末端封鎖を行うことによって製造することができる。
式（4）において、Ｒ^３は水素原子または炭素数１〜６の飽和炭化水素基でから選ばれる基であり、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ヘキシル基、シクロヘキシル基が例示される。この中でも、メチル基、エチル基などが好ましく、メチル基が特に好ましい。
（式中、Ｒ^１、Ｒ^２、ｃは上記と同じであり、Ｒ^３は水素原子または炭素数１〜６の飽和炭化水素基である）で示されるオルガノポリシロキサンと、他のシラン、シロキサン類とを用いて、公知の方法によって共縮合や末端封鎖を行うことによって製造することができる。ここで、Ｒ^１、Ｒ^２、ｃは上記と同じであり、Ｒ^３は水素原子または炭素数１〜６の飽和炭化水素基でから選ばれる基であり、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ヘキシル基、シクロヘキシル基が例示される。この中でも、メチル基、エチル基などが好ましく、メチル基が特に好ましい。 (A) The branched organopolysiloxane is represented by the following formula (4)

(Wherein R ¹ , R ² , and c are the same as above, and R ³ is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms), and siloxanes, for example, The following equation (5)

(Wherein, R ² and R ³ are the same as above, b ′ is 1 or more and b or less, and b is the same as above), and an alkoxysilyl group or a hydroxysilyl group ( With an organopolysiloxane having a silanol group) and then a silane, for example

(Wherein, R ¹ and R ² are the same as above, and X is a halogen atom or a group represented by R ³ O— [R ³ is the same as above]). It can be produced by performing terminal blocking with a silane compound.
In the formula (4), R ³ is a group selected from a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a hexyl group, a cyclohexyl group. Is exemplified. Among these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
(Wherein R ¹ , R ² , and c are the same as above, and R ³ is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms), and another silane or siloxane. And co-condensation or terminal blocking by a known method. Here, R ¹ , R ² , and c are the same as above, and R ³ is a group selected from a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples thereof include a butyl group, an isopropyl group, a hexyl group, and a cyclohexyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The organopolysiloxane having a dialkoxy group at one end represented by the above formula (4) may be synthesized by a known method. For example, as disclosed in JP-A-59-78236, a method comprising subjecting a cyclic silicon compound to ring-opening polymerization using a metal silanolate as an initiator, terminating the terminal with an acid, and then reacting with a trialkoxysilane, or JP-A-7-224168. As disclosed in Japanese Patent Application Laid-Open No. H10-209, there is a method in which a cyclic silicon compound is polymerized using a silanol compound as an initiator and pentacoordinate silicon as a catalyst, and the terminal is reacted with trialkoxysilane.

(B) Organosiloxane (B) The organosiloxane is represented by the following formula (2).
^{_{(R 2 3 SiO 1/2) r}} (R 2 2 SiO 2/2) s (R 2 SiO 3/2) t (SiO 4/2) u (2)
(Wherein, R ² is the same as defined above, at least two of R ² are alkenyl groups, r is an integer of 0 to 100, s is an integer of 0 to 300, and t is an integer of 0 to 200. , U is an integer from 0 to 200, and 1 ≦ t + u ≦ 400 and 2 ≦ r + s + t + u ≦ 800)
Here, r is an integer of 0 to 100, preferably an integer of 0 to 75, more preferably an integer of 0 to 50, s is an integer of 0 to 300, and preferably an integer of 0 to 200. And more preferably an integer of 0 to 100, t is an integer of 0 to 200, preferably an integer of 0 to 100, more preferably an integer of 0 to 50, and u is 0 to 200. , Preferably an integer of 0 to 100, more preferably an integer of 0 to 50, 1 ≦ t + u ≦ 400, preferably 1 ≦ t + u ≦ 200, more preferably 1 ≦ t + u ≦ 100, 2 ≦ r + s + t + u ≦ 800, preferably 2 ≦ r + s + t + u ≦ 400, and more preferably 2 ≦ r + s + t + u ≦ 200.
Examples of R ² are as exemplified for R ² in component (A).

In the component (B), the proportion of the number of monovalent aromatic hydrocarbon groups in the total number of all the substituents bonded to the silicon atom is 3% or more, particularly 5% or more, 90% or less, particularly 80%. The following is preferred. Within this range, the branched organopolysiloxane of the component (B) has a high refractive index, low gas permeability, and is well compatible with the component (A), and cures a composition containing the same. The material is excellent in transparency and has excellent mechanical strength. Therefore, the composition can be suitably used for sealing use of a semiconductor device and the like.

  The compounding amount of the component (B) is 5 to 900 parts by mass, preferably 10 to 800 parts by mass, and more preferably 20 to 600 parts by mass based on 100 parts by mass of the component (A). It is preferable to include the component (D) in an amount falling within the above range since a rubber-like cured product can be obtained.

(C) Organopolysiloxane having at least two hydrosilyl groups in the molecule (C) The organopolysiloxane having at least two hydrosilyl groups in the molecule is not particularly limited, but is represented by the following formula (3). Are preferred.
^{_{(R 3 3 SiO 1/2) r}} '(R 3 2 SiO 2/2) s' (R 3 SiO 3/2) t '(SiO 4/2) u' (3)
(Wherein R ³ is a hydrogen atom, a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, and at least one of R ³ Two are hydrogen atoms, r ′ is an integer from 0 to 100, s ′ is an integer from 0 to 300, t ′ is an integer from 0 to 200, u ′ is an integer from 0 to 200, and 2 ≦ r ′ + s '+ T' + u '≦ 800.)

Here, the substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or the substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms can be the groups exemplified for R ^1. . At least two of R ³ are a hydrogen atom, and the others are preferably a methyl group or a phenyl group. r ′ is an integer of 0 to 100, preferably an integer of 0 to 75, more preferably an integer of 0 to 50, and s ′ is an integer of 0 to 300, preferably an integer of 0 to 200. , More preferably an integer of 0 to 100, t 'is an integer of 0 to 200, preferably an integer of 0 to 100, more preferably an integer of 0 to 50, and u' is an integer of 0 to 200. , Preferably an integer of 0 to 100, more preferably an integer of 0 to 50, and preferably in the range of 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 800, preferably 2 ≦ r ′ + S ′ + t ′ + u ′ ≦ 400 is more preferable, and 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 200 is more preferable.

Further, the proportion of the silicon-bonded monovalent aromatic hydrocarbon group in all the substituents of the component (C) is preferably at least 3 mol%, more preferably at least 5 mol% and at most 80 mol%. . Within this range, the organopolysiloxane of the component (C) not only has a high refractive index and low gas permeability, but also is well compatible with the components (A) and (B). Thus, a composition having excellent transparency of the cured product is obtained. Therefore, it can be suitably used for sealing applications of semiconductor devices.

The amount of the organopolysiloxane having at least two component (C) hydrosilyl groups in the molecule is such that the number of hydrosilyl groups of component (C) is based on the total number of alkenyl groups of component (A) and component (B). The amount is 0.4 to 4.0, preferably 0.6 to 2.0, and more preferably 0.8 to 1.6. When the ratio is less than 0.4, the curing is insufficient due to insufficient SiH groups, which is not preferable. When the ratio is more than 4.0, side reactions such as dehydrogenation due to the remaining SiH groups tend to occur, which is not preferable.

(D) Hydrosilylation catalyst
The catalyst is not particularly limited as long as it has the ability to allow the hydrosilylation reaction to proceed. Among them, a catalyst selected from a platinum group metal alone and a platinum group metal compound is preferable. Examples include platinum (including platinum black), platinum chloride, chloroplatinic acid, platinum-olefin complexes such as platinum-divinylsiloxane complex, platinum catalysts such as platinum-carbonyl complex, palladium catalyst, rhodium catalyst and the like. These catalysts may be used alone or in combination of two or more. Of these, particularly preferred are chloroplatinic acid and platinum-olefin complexes such as platinum-divinylsiloxane complex.
The amount of the component (D) may be a catalytic amount. The amount of the catalyst may be an amount capable of promoting the hydrosilylation reaction, and may be appropriately adjusted according to a desired curing speed. For example, in the case of a platinum group metal catalyst, from the viewpoint of the reaction rate, 1.0 × 10 4 based on 100 parts by mass of the above components (A) to (C) on a mass basis converted to platinum group metal atoms. ^The amount is preferably ^{−4 to} 1.0 part by mass, more preferably 1.0 × 10 ^{−3 to} 1.0 × 10 ⁻¹ part by mass.

Optional components In addition to the above-mentioned components (A) to (D), the curable composition of the present invention may contain, if necessary, other components such as a phosphor, an inorganic filler, an adhesion aid, and a curing agent. You may contain an inhibitor etc. Hereinafter, each component will be described.

[Phosphor]
The phosphor is not particularly limited, and a conventionally known phosphor may be used. For example, it is preferable to absorb light from a semiconductor element, particularly a semiconductor light-emitting diode having a nitride-based semiconductor as a light-emitting layer, and convert the wavelength into light having a different wavelength. Such phosphors include, for example, nitride phosphors / oxynitride phosphors mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid phosphors such as Eu, and transition metal phosphors such as Mn. Alkaline earth metal halogenapatite phosphor, alkaline earth metal borate halogen phosphor, alkaline earth metal aluminate phosphor, alkaline earth metal silicate phosphor, alkaline earth metal activated mainly by elements Sulfide phosphor, alkaline earth metal thiogallate phosphor, alkaline earth metal silicon nitride phosphor, germanate phosphor, or rare earth aluminate phosphor mainly activated by a lanthanoid element such as Ce, rare earth Organic and organic complex phosphors mainly activated by lanthanoid-based elements such as silicate phosphors or Eu, and Ca-Al-Si-ON-based oxynitride glass phosphors It is preferably at least one member selected from.

The nitride phosphor mainly activated by a lanthanoid element such as Eu or Ce is M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn). Is). _{Further, MSi 7 N 10: Eu,} M 1.8 Si 5 O 0.2 N 8: Eu, and _{M 0.9 Si 7 O 0.1 N 10} : Eu (M is, Sr, Ca, Ba, Mg , Zn).

As an oxynitride phosphor mainly activated by a lanthanoid element such as Eu or Ce, MSi ₂ O ₂ N ₂ : Eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn) Is).

As an alkaline earth metal halogen apatite phosphor mainly activated by a lanthanoid-based element such as Eu or a transition metal-based element such as Mn, M ₅ (PO ₄ ) ₃ X: R (M is Sr, Ca, Ba) , Mg, and Zn. X is at least one selected from F, Cl, Br, and I. R is at least one of Eu, Mn, Eu, and Mn.) Is mentioned.

As the alkaline earth metal borate halogen phosphor, M ₂ B ₅ O ₉ X: R (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F, Cl, At least one selected from Br and I. R is at least one of Eu, Mn, Eu and Mn).

The alkaline earth metal aluminate phosphors include SrAl ₂ O ₄ : R, Sr ₄ Al ₁₄ O ₂₅ : R, CaAl ₂ O ₄ : R, BaMg ₂ Al ₁₆ O ₂₇ : R, BaMg ₂ Al ₁₆ O _12. : R, and BaMgAl ₁₀ O ₁₇ : R (R is at least one of Eu, Mn, Eu and Mn).

Examples of the alkaline earth metal sulfide _{phosphor, La 2 O 2 S: Eu} , Y 2 O 2 S: Eu, and _Gd 2 _O 2 S: Eu, and the like.
Rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ YAG-based phosphors represented by a composition formula of (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce and (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ are mentioned. In addition, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce in which part or all of Y is substituted with Tb, Lu, or the like.

Other _{phosphor, ZnS: Eu, Zn 2 GeO} 4: Mn, MGa 2 S 4: Eu (M is at least one selected Sr, Ca, Ba, Mg, from Zn .X is F , Cl, Br, and I).
The phosphor contains one or more selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti instead of or in addition to Eu, if desired. Can be.

The Ca-Al-SiO-N-based oxynitride glass phosphor, by mol%, 20-50 mol% in terms of CaCO ₃ to CaO, the _Al 2 _{O 3} 0 to 30 mol%, SiO Oxynitride glass having 25 to 60 mol%, AlN of 5 to 50 mol%, rare earth oxide or transition metal oxide of 0.1 to 20 mol%, and the total of the five components being 100 mol%. This is a phosphor. In a phosphor using oxynitride glass as a base material, the nitrogen content is preferably 15 wt% or less, and other rare earth element ions serving as a sensitizer in addition to rare earth oxide ions are used as rare earth oxides. It is preferable that the fluorescent glass be contained as a co-activator in a content of 0.1 to 10 mol%.

  Further, a phosphor other than the above-mentioned phosphors and having the same performance and effect can also be used.

  The amount of the phosphor is preferably 0.1 to 2,000 parts by mass, more preferably 0.1 to 100 parts by mass, per 100 parts by mass of components other than the phosphor, for example, components (A) to (D). Department. When the cured product of the present invention is used as a phosphor-containing wavelength conversion film, the phosphor content is preferably 10 to 2,000 parts by mass. The phosphor preferably has an average particle diameter of 10 nm or more, more preferably 10 nm to 10 μm, and further preferably 10 nm to 1 μm. The average particle size is measured by a particle size distribution measurement using a laser diffraction method such as a Cirrus laser measuring device.

[Inorganic filler]
Examples of the inorganic filler include silica, fumed silica, fumed titanium dioxide, alumina, calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, and zinc oxide. These can be used alone or in combination of two or more. The blending amount of the inorganic filler is not particularly limited, but may be appropriately blended in an amount of 20 parts by mass or less, preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total of components (A) to (D).

上記式（７）中、Ｒ^４は互いに独立に、下記（８）で示される有機基、又は脂肪族不飽和結合を含有する一価炭化水素基である。

Ｒ^５は水素原子又は炭素数１〜６の一価炭化水素基であり、ｋは１〜６の整数、好ましくは１〜４の整数である。 [Adhesion aid]
The curable composition of the present invention may contain an adhesion aid as needed in order to impart adhesiveness. Examples of the adhesion aid include an organosiloxane oligomer having at least two, and preferably three, functional groups selected from a hydrogen atom, an alkenyl group, an alkoxy group, and an epoxy group bonded to a silicon atom in one molecule. . The organosiloxane oligomer preferably has 4 to 50 silicon atoms, more preferably 4 to 20 silicon atoms. Further, an organooxysilyl-modified isocyanurate compound represented by the following general formula (7) and a hydrolytic condensate thereof (organosiloxane-modified isocyanurate compound) can be used as the adhesion aid.

In the above formula (7), R ⁴ is independently an organic group represented by the following (8) or a monovalent hydrocarbon group containing an aliphatic unsaturated bond.

R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and k is an integer of 1 to 6, preferably 1 to 4.

  The compounding amount of the adhesion aid is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, and particularly preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total of the components (A) to (D). 5 parts by mass. When the amount is less than the above upper limit, the hardness of the cured product becomes high and the surface tackiness is suppressed.

[Curing inhibitor]
The curable composition of the present invention may contain a curing inhibitor to control the reactivity and increase the storage stability. The curing inhibitor is selected from the group consisting of triallyl isocyanurate, alkyl maleate, acetylene alcohols, and silane-modified and siloxane-modified products thereof, hydroperoxide, tetramethylethylenediamine, benzotriazole, and mixtures thereof. Compounds. The compounding amount of the curing inhibitor is preferably 0.001 to 1.0 part by mass, more preferably 0.005 to 0.5 part by mass, per 100 parts by mass of the total of the components (A) to (D).

[Other additives]
The curable composition of the present invention may contain other additives in addition to the above components. Other additives include, for example, an antioxidant, a radical inhibitor, a flame retardant, a surfactant, an antiozonant, a light stabilizer, a thickener, a plasticizer, an antioxidant, a heat stabilizer, and a conductive agent. Examples include an imparting agent, an antistatic agent, a radiation blocking agent, a nucleating agent, a phosphorus-based peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a physical property modifier, and an organic solvent. These optional components may be used alone or in combination of two or more.

  The simplest embodiment of the curable composition of the present invention is a composition comprising the components (A), (B), (C), and (D). Preferably, it is a composition comprising component (A), component (B), component (C), component (D), and a phosphor. In particular, in order to obtain a cured product having high transparency, it is preferable not to contain an inorganic filler such as a silica filler. Examples of the inorganic filler are as described above.

  The method for preparing the curable composition of the present invention is not particularly limited, and may be a conventionally known method. For example, it can be prepared by mixing the component (A), the component (B), the component (C), and the component (D) by an arbitrary method. Alternatively, the components (A), (B), (C), and (D) are mixed with the phosphor, or the components (A), (B), (C), (D), and any component are mixed by any method. It may be prepared by adjusting. For example, it can be prepared by placing it in a commercially available stirrer (THINKY CONDITIONING MIXER (manufactured by Shinky Corporation) or the like) and mixing uniformly for about 1 to 5 minutes.

  The method for curing the curable composition of the present invention is not particularly limited, and may be a conventionally known method. For example, it can be cured at 60 to 180 ° C. for about 1 to 12 hours. In particular, it is preferable to cure by a step cure at 60 to 150 ° C. In the step cure, it is more preferable to go through the following two steps. First, the curable composition is heated at a temperature of 60 to 100 ° C. for 0.5 to 2 hours to sufficiently remove bubbles. Next, the curable composition is cured by heating at a temperature of 120 to 180 ° C. for 1 to 10 hours. Through these steps, even when the cured product is thick, it is fully cured, has no bubbles, and can be colorless and transparent. In the present invention, the colorless and transparent cured product means one having a light transmittance at 450 nm with respect to a thickness of 1 mm of 80% or more, preferably 85% or more, particularly preferably 90% or more.

  The curable composition of the present invention gives a cured product having high optical transparency. Therefore, the curable composition of the present invention is useful for encapsulating LED elements, particularly for encapsulating blue LEDs and ultraviolet LEDs. The method for sealing an LED element or the like with the curable composition of the present invention may be in accordance with a conventionally known method. For example, it can be performed by a dispensing method, a compression molding method, or the like.

  The curable composition and the cured product of the present invention, in addition, to provide a cured product having properties such as excellent crack resistance, heat resistance, light resistance, and transparency, display materials, optical recording medium materials, It is also useful for applications such as optical equipment materials, optical component materials, optical fiber materials, organic materials for optical and electronic functions, and peripheral materials for semiconductor integrated circuits.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The weight average molecular weight (Mw) shown in the following Examples is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are shown below.
[GPC measurement conditions]
Developing solvent: tetrahydrofuran Flow rate: 0.6 mL / min
Column: TSK Guardcolumn SuperHL
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(All manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (sample concentration: 0.5 wt% -tetrahydrofuran solution)
Detector: Differential refractometer (RI)

The Vi value (mol / 100 g) and the SiH value (mol / 100 g) shown in the following Examples were measured by measuring the ¹ H-NMR spectrum of the compound at 400 MHz, and the integrated values of hydrogen atoms obtained using dimethyl sulfoxide as an internal standard. It is calculated from. ¹ H-NMR measurement was performed using ULTRASHIELD ^™ 400PLUS (manufactured by BRUKER), and ²⁹ Si-NMR measurement was performed using RESONANCE 500 (manufactured by JEOL).

  The synthesis examples and comparative examples of the component (A) used in the examples are shown below. In the following, Me indicates a methyl group and Ph indicates a phenyl group.

（式中、ｃ＝ｃ’＝２０） [Synthesis Example 1]
(A-1)
96.3 g of lithium trimethylsilanolate, 1,560 g of hexamethylcyclotrisiloxane, and 4,160 g of hexaphenylcyclotrisiloxane were added to a toluene solvent, followed by stirring at 100 ° C. for 12 hours. Thereafter, 90.0 g of acetic acid was added for neutralization, and the obtained product was filtered. Then, methyltrimethoxysilane _{408g, Sr (OH) 2 ·} 8H 2 O was added 8.10 g, was stirred for 3 hours at 60 ° C.. Thereafter, 12.2 g of acetic acid was added to neutralize the mixture, and the obtained product was filtered, and methanol and toluene were distilled off under reduced pressure to obtain the following organopolysiloxane having two alkoxy groups at one end (a- 1) was synthesized. It was found that Mw = 6,000.

(Where c = c ′ = 20)

(A-1)
(A-1) synthesized in organopolysiloxane 600 g, polymethylphenylsiloxane-.alpha., .omega.-diol (Mw = 530) 140g, Sr (OH) 2 · 8H 2 O was added 0.810 g, 18 h at 60 ° C. Stirred. Thereafter, 1.22 g of acetic acid was added to neutralize, 17.1 g of chlorodimethylvinylsilane was added, and the mixture was stirred at 60 ° C. for 8 hours. The obtained product was filtered, washed with water, azeotropically dehydrated, and distilled under reduced pressure to synthesize the following branched silicone oil. Organopolysiloxane having Mw = 27,000, Vi value = 7.41 × 10 ⁻³ mol / 100 g, and a = 4, b = 40, c = 20, c ′ = 20 from a ²⁹ Si-NMR spectrum. (A-1) was found to be.

（式中、ｃ＝ｃ’＝３） [Synthesis Example 2]
(A-2)
96.3 g of lithium trimethylsilanolate, 222 g of hexamethylcyclotrisiloxane and 595 g of hexaphenylcyclotrisiloxane were added to a toluene solvent, and the mixture was stirred at 100 ° C. for 3 hours. Thereafter, 90.0 g of acetic acid was added for neutralization, and the obtained product was filtered. Then, methyltrimethoxysilane _{408g, Sr (OH) 2 ·} 8H 2 O was added 8.10 g, was stirred for 3 hours at 60 ° C.. Thereafter, 12.2 g of acetic acid was added for neutralization, and the obtained product was filtered, and methanol and toluene were distilled off under reduced pressure to synthesize the following one-end dialkoxyorganopolysiloxane (a-2). It was found that Mw = 1,000.

(Where c = c ′ = 3)

(A-2)
(A-2) synthesized in organopolysiloxane 100 g, polymethylphenylsiloxane-.alpha., .omega.-diol (Mw = 530) 27.9g, Sr (OH) 2 · 8H 2 O was added 0.640 g, at 60 ° C. Stir for 3 hours. Thereafter, 0.960 g of acetic acid was added for neutralization, 24.4 g of chlorodimethylvinylsilane was added, and the mixture was stirred at 60 ° C. for 8 hours. The obtained product was filtered, washed with water, azeotropically dehydrated, and distilled under reduced pressure to synthesize the following branched silicone oil. An organopolysiloxane having Mw = 3,300, Vi value = 6.06 × 10 ⁻² mol / 100 g, and a = 3, b = 6, c = 3, c ′ = 3 from a ²⁹ Si-NMR spectrum. I found it.

（式中、ｃ＝９０） [Synthesis Example 3]
(A-3)
In an acetonitrile solvent, 90.1 g of trimethylsilanol, 6,660 g of hexamethylcyclotrisiloxane, and 121 g of sodium dicatecholphenylsiloxy were added, followed by stirring at 60 ° C. for 12 hours. The resulting product was filtered, methyltrimethoxysilane _{408g, Sr (OH) 2 ·} 8H 2 O was added 8.10 g, was stirred for 3 hours at 60 ° C.. Thereafter, 12.2 g of acetic acid was added for neutralization, and the obtained product was filtered, and methanol and toluene were distilled off under reduced pressure to synthesize the following one-end dialkoxyorganopolysiloxane. It was found that Mw = 6,800.

(Where c = 90)

(A-3)
(A-3) synthesized in organopolysiloxane 680 g, polydimethylsiloxane-.alpha., .omega.-diol (Mw = 280) 72.0g, Sr (OH) 2 · 8H 2 O was added 3.76 g, at 60 ° C. 18 Stirred for hours. Thereafter, 5.64 g of acetic acid was added for neutralization, 13.0 g of chlorodimethylvinylsilane was added, and the mixture was stirred at 60 ° C. for 8 hours. The obtained product was filtered, washed with water, azeotropically dehydrated, and distilled under reduced pressure to synthesize the following branched silicone oil. It has Mw = 73,000, Vi value = 2.74 × 10 ⁻³ mol / 100 g, and was found to be an organopolysiloxane having a = 10, b = 90, and c = 90 from a ²⁹ Si-NMR spectrum. .

（式中、ｃ＝１２） [Synthesis Example 4]
(A-4)
In an acetonitrile solvent, 90.1 g of trimethylsilanol, 890 g of hexamethylcyclotrisiloxane, and 121 g of sodium dicatecholphenylsiloxy were added, and the mixture was stirred at 60 ° C. for 6 hours. The resulting product was filtered, methyltrimethoxysilane _{408g, Sr (OH) 2 ·} 8H 2 O was added 8.10 g, was stirred for 3 hours at 60 ° C.. Thereafter, 12.2 g of acetic acid was added for neutralization, and the obtained product was filtered, and methanol and toluene were distilled off under reduced pressure to synthesize the following one-end dialkoxyorganopolysiloxane. It was found that Mw = 1,000.

(Where c = 12)

(A-4)
(A-4) synthesized in organopolysiloxane 1,000 g, polydimethylsiloxane-.alpha., .omega.-diol (Mw = 280) 12.0g, Sr (OH) 2 · 8H 2 O was added 5.06 g, 60 ° C. For 18 hours. Thereafter, 7.59 g of acetic acid was added for neutralization, 340 g of chlorodimethylvinylsilane was added, and the mixture was stirred at 60 ° C. for 8 hours. The obtained product was filtered, washed with water, azeotropically dehydrated, and distilled under reduced pressure to synthesize the following branched silicone oil. It has Mw = 81,000, Vi value = 2.47 × 10 ⁻³ mol / 100 g, and was found to be an organopolysiloxane having a = 80, b = 12, and c = 12 from a ²⁹ Si-NMR spectrum. .

[Comparative Example 1]
(A-1 ′)
Vinyl phenyl methyl silicone oil at both ends represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 3.81 × 10 ⁻² mol / 100 g)

[Comparative Example 2]
(A-2 ')
Vinyl dimethyl silicone oil at both ends represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 1.33 × 10 ⁻² mol / 100 g)

[Comparative Example 3]
(A-3 ')
63.7 g of 1,1-diphenyl-1,3-dimethyl-3,3-dimethoxydisiloxane, 1,200 g of polymethylphenylsiloxane-α, ω-diol (Mw = 530) and 48.8 g of dimethylvinylmethoxysilane Stir and adjust to 60 ° C. _{Thereafter, Sr (OH) 2 · 8H} 2 O was added 3.15 g, reaction was conducted for 3 hours at 60 ° C.. The catalyst was removed from the obtained product by filtration, and methanol and water were distilled off under reduced pressure to synthesize the following branched silicone oil. It had Mw = 5,700, Vi value = 3.51 × 10 ⁻² mol / 100 g, and was found to be an organopolysiloxane with n = 37 and m = 1 from a ²⁹ Si-NMR spectrum.

（Ｂ−２）下記式で表されるメチル系シリコーンレジン（信越化学工業株式会社製、Ｖｉ価＝９．１２×１０^−２ｍｏｌ／１００ｇ）

Component (B), component (C) and component (D) The components (B), (C) and (D) used in the examples are shown below.
(B-1) Phenyl-based silicone resin represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 0.147 mol / 100 g)

(B-2) Methyl silicone resin represented by the following formula (Shin-Etsu Chemical Co., Ltd., Vi value = 9.12 × 10 ⁻² mol / 100 g)

（Ｃ−２）下記式で表される、側鎖にヒドロシリル基を有するシリコーンオイル（信越化学工業株式会社製、ＳｉＨ価＝１．６３ｍｏｌ／１００ｇ）

(C-1) A silicone oil having hydrosilyl groups at both ends represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 0.600 mol / 100 g)

(C-2) A silicone oil having a hydrosilyl group in a side chain represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 1.63 mol / 100 g)

(D) Isododecane solution of divinylsiloxane complex of chloroplatinic acid (platinum content 0.5% by mass)

[Example 1]
100 parts by mass of (A-1), 300 parts by mass of (B-1), and 81 parts by mass of (C-1) were mixed, and 5 ppm of a divinylsiloxane complex of chloroplatinic acid was added as a platinum amount and mixed. Was prepared.

[Examples 2 to 4 and Comparative Examples 1 to 3]
A curable composition was prepared by repeating the same operation as in Example 1 except that the amount of each component was changed as shown in Table 1.

The following tests were performed on the curable compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3.
[Viscosity of curable composition]
The viscosity of the curable composition at 23 ° C. was measured using a B-type viscometer according to JIS Z 8803: 2011. The results are shown in Table 1.
[Hardness of cured product]
The prepared curable composition was poured into an aluminum dish having a diameter of 50 mm and a thickness of 10 mm, and was step-cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, and 150 ° C. × 4 hours to obtain a cured product. The hardness (durometer Shore A or Shore D) of the cured product was measured according to JIS K 6253-3: 2012. The results are shown in Table 1.
[Light transmittance of cured product]
After sandwiching a concave 1 mm thick Teflon (registered trademark) spacer between two 50 mm × 20 mm × 1 mm thick slide glasses and fixing them, the curable composition is poured, and the mixture is poured at 60 ° C. × 1 hour at 100 ° C. × 1. Step curing was performed for 150 hours at 150 ° C. for 4 hours to prepare a transmittance measurement sample. The light transmittance at 450 nm of the obtained sample was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 1.
[Tensile strength and elongation at break of cured product]
The curable composition prepared was poured into a concave Teflon (registered trademark) mold having a thickness of 150 mm × 200 mm × 2 mm, and step-cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, 150 ° C. × 4 hours, A sample was prepared. Using EZ TEST (EZ-L, manufactured by Shimadzu Corporation) in accordance with JIS K6251: 2010, the sample was pulled under the conditions of a test speed of 500 mm / min, a distance between grips of 80 mm, and a distance between gauge points of 40 mm. The strength and elongation at break were measured.
The results are shown in Table 1.
[Glass transition temperature of cured product]
The storage elastic modulus (MPa) of the cured product sample prepared as described in the section “Tensile strength and elongation at break” of the cured product was determined at −140 ° C. by DMA Q800 (manufactured by TA Instruments Co., Ltd.). The temperature at the peak top was measured from the range of ~ 150 ° C, and the temperature at the peak top obtained from the graph in which the value of Tanδ derived from the obtained values of the storage elastic modulus and the loss elastic modulus was plotted was taken as the glass transition temperature (Tg).
The measurement conditions were as follows: a sample of 20 mm length × 5 mm width × 1 mm thickness, a heating rate of 5 ° C./min, a multi-frequency mode, a tensile mode, and an amplitude of 15 μm. The results are shown in Table 1. 4 is a graph of the storage elastic modulus and a graph of Tan δ of the cured products of Example 1 (solid line) and Comparative Example 1 (dotted line). FIG. 1 shows a graph of the storage elastic modulus and a graph of Tan δ of the cured products of Example 1 (solid line) and Comparative Example 1 (dotted line).
[Temperature cycle test]
The curable composition is dispensed into a Tiger 3528 package (manufactured by Shin-Etsu Chemical Co., Ltd.), and step-cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, 150 ° C. × 4 hours, and the package is sealed with the cured product. Specimens were manufactured. A thermal cycle test (TCT) of 1,000 times at −50 ° C. to 140 ° C. was performed on 20 of the test pieces, and the number of test pieces having cracks in the sealed product was measured. The results are shown in Table 1.

Ｈ／Ｖｉ＝（組成物中のＳｉＨ基のｍｏｌ）／（組成物中のＶｉ基のｍｏｌ）
ＮＧの数＝封止物にクラックが生じた試験体の数

H / Vi = (mol of SiH group in composition) / (mol of Vi group in composition)
Number of NG = Number of specimens with cracks in the seal

  As shown in Table 1, the curable silicone resin composition using the branched organopolysiloxane of the present invention is different from the composition using the linear organopolysiloxane in place of the component (A) of the present invention. By comparison, a cured product having a low glass transition temperature and excellent crack resistance is provided. Further, the viscosity of the resin composition is sufficiently low, and the working efficiency is good.

  Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect. Within the technical scope of

The present invention provides an addition-curable silicone composition that provides a cured product having good low-temperature characteristics and excellent temperature change resistance, and a highly reliable semiconductor device in which a semiconductor element is sealed with a cured product of the composition. I do.

Claims (10)

(A) Formula (1) below

(Wherein, R ^{1 s} are each independently a group selected from a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. , R ² are each independently a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. Wherein each of R ¹ and R ² may be the same or different, provided that the organopolysiloxane has the alkenyl group only at both ends of the main chain, 100 integers, b is 5 to 100 integer, c is 5-100 integer, 0.03 ≦ a / (a + b) <1.0, (R 1 2 R 2 SiO 1/2) units of several / ^{(R 2} SiO _3/2 ) The number of units ≦ 2, and a, b, and c siloxanes (The arrangement of chains may be random or block.)
A branched organopolysiloxane represented by
(B) The following formula (2)
_{^{(R 2 3 SiO 1/2) r}} (R 2 2 SiO 2/2) s (R 2 SiO 3/2) t (SiO 4/2) u (2)
(Wherein, R ² is the same as defined above, at least two of R ² are alkenyl groups, r is an integer of 0 to 100, s is an integer of 0 to 300, and t is an integer of 0 to 200. , U is an integer from 0 to 200, and 1 ≦ t + u ≦ 400 and 2 ≦ r + s + t + u ≦ 800)
An amount of 5 to 900 parts by mass per 100 parts by mass of the organopolysiloxane (A) component represented by
(C) Organopolysiloxane having at least two hydrosilyl groups in the molecule The number of hydrosilyl groups in the component (C) is from 0.4 to the total number of alkenyl groups in the component (A) and the component (B). 4.0, and
(D) Hydrosilylation catalyst An addition-curable silicone resin composition for encapsulating a semiconductor element , comprising an amount sufficient to allow the hydrosilylation reaction to proceed. The addition-curable silicone resin composition for sealing a semiconductor element according to claim 1, wherein in the formula (1), 0.09 ≦ a / (a + b) ≦ 0.9. 3. The addition-curable silicone resin composition for sealing a semiconductor element according to claim 1, wherein in the formula (1), at least one of R ¹ is an aromatic hydrocarbon group having 6 to 12 carbon atoms. 4. object. In the component (A), the ratio of the number of monovalent aromatic hydrocarbon groups to the total number of substituents bonded to silicon atoms is 3% or more and 90% or less. The addition-curable silicone resin composition for semiconductor element sealing according to any one of the above. The component (C) has the following formula (3)
_{^{(R 3 3 SiO 1/2) r}} '(R 3 2 SiO 2/2) s' (R 3 SiO 3/2) t '(SiO 4/2) u' (3)
(Wherein, R ³ is independently a hydrogen atom, a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, , R ³ is a hydrogen atom, r ′ is an integer from 0 to 100, s ′ is an integer from 0 to 300, t ′ is an integer from 0 to 200, u ′ is an integer from 0 to 200, 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 800)
The addition-curable silicone resin composition for semiconductor element encapsulation according to any one of claims 1 to 4, which is represented by: A semiconductor device wherein a semiconductor element is encapsulated by a cured product of the addition-curable silicone resin composition for encapsulating a semiconductor element according to claim 1. The semiconductor device according to claim 6, wherein the semiconductor element is a light emitting element. The following equation (4)

(Wherein, R ^{1 s} are each independently a group selected from a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms. , R ² are each independently a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms , and each R ¹ , R 2 ² may be the same or different; c is an integer of 5 to 100; R ³ is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms); The following equation (5)

(Wherein, R ² and R ³ are the same as above, b ′ is 1 or more and b or less, and b is an integer of 5 to 100). Co-condensation with an organopolysiloxane having a group (silanol group), and then the following formula (6)

(Wherein, R ¹ is the same as described above, R ² is an alkenyl group having 2 to 10 carbon atoms , X is a halogen atom or a group represented by R ³ O— wherein R ³ is the same as above.) as engineering performing end-capped by a hydrolyzable group-containing silane compound represented by the a), and the reaction product produced by the process and (a),
(B) The following formula (2)
_{^{(R 2 3 SiO 1/2) r}} (R 2 2 SiO 2/2) s (R 2 SiO 3/2) t (SiO 4/2) u (2)
(Wherein, R ² is the same as defined above, at least two of R ² are alkenyl groups, r is an integer of 0 to 100, s is an integer of 0 to 300, and t is an integer of 0 to 200. , U is an integer from 0 to 200, and 1 ≦ t + u ≦ 400 and 2 ≦ r + s + t + u ≦ 800)
An amount of 5 to 900 parts by mass with respect to 100 parts by mass of the organopolysiloxane (A) component represented by
(C) Organopolysiloxane having at least two hydrosilyl groups in the molecule The number of hydrosilyl groups in the component (C) is from 0.4 to the total number of alkenyl groups in the component (A) and the component (B). 4.0, and
(D) Hydrosilylation catalyst A method for producing an addition-curable silicone resin composition for encapsulating a semiconductor element , comprising a step of mixing the hydrosilylation reaction with an amount sufficient to allow the hydrosilylation reaction to proceed. (A) In the reaction product, the ratio of the number of monovalent aromatic hydrocarbon groups to the total number of substituents bonded to silicon atoms is 3% or more and 90% or less. 3. The method for producing an addition-curable organopolysiloxane composition for encapsulating a semiconductor device according to item 1. The component (C) has the following formula (3)
_{^{(R 3 3 SiO 1/2) r}} '(R 3 2 SiO 2/2) s' (R 3 SiO 3/2) t '(SiO 4/2) u' (3)
(Wherein, R ³ is independently a hydrogen atom, a substituted or unsubstituted saturated hydrocarbon group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, , R ³ is a hydrogen atom, r ′ is an integer from 0 to 100, s ′ is an integer from 0 to 300, t ′ is an integer from 0 to 200, u ′ is an integer from 0 to 200, 2 ≦ r ′ + s ′ + t ′ + u ′ ≦ 800)
The method for producing an addition-curable silicone resin composition for encapsulating a semiconductor element according to any one of claims 8 to 9, which is represented by the following formula:

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