JP6776954B2 - Additive curable silicone resin composition - Google Patents

Description

The present invention relates to an addition curable silicone resin composition.

The addition-curing silicone resin composition has been used as a sealing material for sealing semiconductor elements such as LEDs because it is excellent in quick-curing property, heat resistance of cured product, weather resistance and the like. For example, Patent Document 1 (Japanese Unexamined Patent Publication No. 2007-2234) proposes an add-curable silicone resin composition that exhibits high adhesive strength to an LED package made of a thermoplastic resin such as PPA. Further, Patent Document 2 (Japanese Unexamined Patent Publication No. 2006-93354) proposes a method of sealing an optical semiconductor element by compression molding of an addition-curable silicone resin composition.

As described above, the addition-curable silicone resin is widely and generally used as a semiconductor encapsulating material, but its characteristics are not yet satisfactory. Methyl silicone resins are generally soft, have poor dicing properties, and are often tacky. By increasing the SiO _4/2 unit [Q unit] and RSiO _3/2 unit [T unit] components in order to improve the dicing property, a hard and tack-free cured product can be produced, but the strength is low and the resin becomes brittle. It ends up.

JP-A-2007-2234 Japanese Unexamined Patent Publication No. 2006-93354

The present invention has been made in view of the above problems, and is added to give a cured product having low viscosity and good dispensability before curing, sufficient strength after curing, good dicing property, and no tack. It is an object of the present invention to provide a curable silicone resin composition, particularly a methyl silicone resin composition.

（式（３）中、Ｒ¹は上記式（１）中のものと同じであり、ｎは３〜６の整数である。）
で示される環状ビニルシロキサン；（Ａ）及び（Ｂ）成分の合計１００質量部に対して２〜７質量部
（Ｄ）ヒドロシリル基を一分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサン；（Ａ）〜（Ｃ）成分中のアルケニル基１モルに対して（Ｄ）成分中のヒドロシリル基が０．４〜４．０モルとなる量、及び
（Ｅ）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
を含む付加硬化性シリコーン樹脂組成物が、硬化前は低粘度でディスペンス性が良く、硬化後は十分な強度を有し、ダイシング性が良好であり、タックのない硬化物を与えることを見出し、本発明をなすに至った。 As a result of diligent studies to solve the above problems, the present inventor has the following (A) to (E) components (A) and the following formula (1).
(R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u
(1)
(In the formula, R ¹ is a group independently selected from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, but at least 2 of R ¹ is used. Each is an alkenyl group. 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, where 1 ≦ t + u ≦ 400, 3 ≦. r + s + t + u ≦ 800.)
Branched organopolysiloxane (B) represented by the following formula (2)
(R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2)
In formula (2) , R ¹ is a group selected independently of each other from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms , where R ^{1 is used.} At least two of the alkenyl groups are in each of the two (R ¹ ₃ SiO _1/2 ) units, but in x (R ¹ ₂ SiO _2/2 ) units. No, x is an integer from 200 to 700.)
Linear organopolysiloxane (C) represented by the following formula (3)

(In the equation (3) , R ¹ is the same as that in the above equation (1) , and n is an integer of 3 to 6).
Cyclic vinyl siloxane represented by (A); (A) Organohydrogenpolysiloxane having at least 2 to 7 parts by mass (D) hydrosilyl group in one molecule with respect to 100 parts by mass of the components (A) and (B) in total; ) To 1 mol of the alkenyl group in the component (C) to 0.4 to 4.0 mol of the hydrosilyl group in the component (D), and (E) a hydrosilylation catalyst; the hydrosilylation reaction proceeds. The additive-curable silicone resin composition containing a sufficient amount of the silicone resin composition has low viscosity and good dispensability before curing, has sufficient strength after curing, has good dicing property, and has no tack. It was found to give, and the present invention was made.

（式（３）中、Ｒ¹は上記式（１）中のものと同じであり、ｎは３〜６の整数である。）
で示される環状ビニルシロキサン；（Ａ）及び（Ｂ）成分の合計１００質量部に対して２〜７質量部
（Ｄ）ヒドロシリル基を一分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサン；（Ａ）〜（Ｃ）成分中のアルケニル基１モルに対して（Ｄ）成分中のヒドロシリル基が０．４〜４．０モルとなる量、及び
（Ｅ）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
を含むことを特徴とする付加硬化性シリコーン樹脂組成物。
〔２〕
前記（Ａ）成分と（Ｂ）成分との配合比が、質量比で（Ａ）：（Ｂ）＝１：１〜２：１であることを特徴とする〔１〕記載の付加硬化性シリコーン樹脂組成物。
〔３〕
前記（Ｄ）成分が、下記式（４）
（Ｒ² ₃ＳｉＯ_1/2）_r'（Ｒ² ₂ＳｉＯ_2/2）_s'（Ｒ²ＳｉＯ_3/2）_t'（ＳｉＯ_4/2）_u'
（４）
（式中、Ｒ²は互いに独立に、水素原子又は炭素数１〜１２の置換もしくは非置換の一価飽和炭化水素基であり、Ｒ²の少なくとも２個は水素原子である。ｒ’は０〜１００の整数、ｓ’は０〜３００の整数、ｔ’は０〜２００の整数、ｕ’は０〜２００の整数であり、ただし、２≦ｒ’＋ｓ’＋ｔ’＋ｕ’≦８００である。）
で示されるオルガノハイドロジェンポリシロキサンである〔１〕又は〔２〕に記載の付加硬化性シリコーン樹脂組成物。
〔４〕
前記（Ｅ）成分の配合量が、（Ａ）〜（Ｄ）成分の合計質量に対して５〜２０ｐｐｍとなる量である〔１〕〜〔３〕のいずれかに記載の付加硬化性シリコーン樹脂組成物。
That is, the present invention provides the following addition-curable silicone resin composition.
[1]
The following (A) to (E) components (A) The following formula (1)
(R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u
(1)
(In the formula, R ¹ is a group independently selected from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, but at least 2 of R ¹ is used. Each is an alkenyl group, where 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, where 1 ≦ t + u ≦ 400, 3 ≦. r + s + t + u ≦ 800.)
Branched organopolysiloxane (B) represented by the following formula (2)
(R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2)
In formula (2) , R ¹ is a group selected independently of each other from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms , where R ^{1 is used.} At least two of the alkenyl groups are in each of the two (R ¹ ₃ SiO _1/2 ) units, but in x (R ¹ ₂ SiO _2/2 ) units. However , x is an integer from 200 to 700.)
Linear organopolysiloxane (C) represented by the following formula (3)

(In equation (3) , R ¹ is the same as that in equation (1) above, and n is an integer of 3 to 6.)
Cyclic vinyl siloxane represented by; (A) Organohydrogenpolysiloxane having at least 2 to 7 parts by mass (D) hydrosilyl group in one molecule with respect to 100 parts by mass of the components (A) and (B) in total; ) To 1 mol of alkenyl group in component (C) to 0.4 to 4.0 mol of hydrosilyl group in component (D), and (E) hydrosilylation catalyst; proceed with hydrosilylation reaction An addition curable silicone resin composition comprising a sufficient amount of.
[2]
The addition-curable silicone according to [1], wherein the compounding ratio of the component (A) and the component (B) is (A) :( B) = 1: 1 to 2: 1 in terms of mass ratio. Resin composition.
[3]
The component (D) is the following formula (4).
(R ² ₃ SiO _1/2 ) _r' (R ² ₂ SiO _2/2 ) _s' (R ² SiO _3/2 ) _t' (SiO _4/2 ) _u'
(4)
(In the formula, R ² is a hydrogen atom or a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms independently of each other, and at least two of R ² are hydrogen atoms. R'is 0. ~ 100, s'is 0-300, t'is 0-200, u'is 0-200, but 2 ≤ r'+ s'+ t'+ u'≤ 800. .)
The addition curable silicone resin composition according to [1] or [2], which is an organohydrogenpolysiloxane represented by.
[4]
The addition-curable silicone resin according to any one of [1] to [3], wherein the blending amount of the component (E) is 5 to 20 ppm with respect to the total mass of the components (A) to (D). Composition.

According to the present invention, by adding a sufficient amount of cyclic vinyl siloxane, a cured product having low viscosity and good dispensability before curing, sufficient strength after curing, good dicing property, and no tack. A curable silicone resin composition is obtained.

Hereinafter, each component of the present invention will be described.
[(A) Branched (resin-like) organopolysiloxane]
The component (A) of the present invention is the main component of the addition-curable silicone resin composition of the present invention, and has the following formula (1).
(R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u
(1)
(In the formula, R ¹ is a group independently selected from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, but at least 2 of R ¹ is used. Each is an alkenyl group. 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, where 1 ≦ t + u ≦ 400, 3 ≦. r + s + t + u ≦ 800.)
It is an organopolysiloxane represented by.

Here, R ¹ is a group selected from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12, preferably 1 to 6, more preferably 1 to 4, and an alkenyl group having 2 to 6 carbon atoms. is there. Examples of monovalent saturated hydrocarbon groups include, specifically, alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and carbon atoms of these groups. Part or all of the hydrogen atoms to be bonded are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, (meth) acrylicoxy groups, glycidyloxy groups, mercapto groups, amino groups and the like, for example, trifluoropropyl. Halogenized monovalent saturated hydrocarbon group such as group, chloropropyl group; cyanoalkyl group such as β-cyanoethyl group and γ-cyanopropyl group; 3-methacryloxypropyl group, 3-glycidyloxypropyl group, 3-mercaptopropyl Groups, 3-aminopropyl groups and the like are exemplified. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a hexenyl group, a styryl group and the like. Among these, a methyl group, a cyclohexyl group and the like are preferable, and a methyl group is particularly preferable. However, at least two of R ¹ are alkenyl groups, and a vinyl group is preferable as the alkenyl group.

Although the alkenyl group has at least two in one molecule, it contains 0.005 to 0.5 mol / 100 g, particularly 0.01 to 0.2 mol / 100 g, in the organopolysiloxane of the component (A). It is preferable to do so.
Further, the alkenyl group may be in R ¹ ₃ SiO _1/2 unit, in R ¹ ₂ SiO _2/2 unit, in R ¹ SiO _3/2 unit, or in a plurality of these. It is good, but it is preferable to have it in R ¹ ₃ SiO _1/2 unit.

Further, r is an integer of 0 to 100, preferably an integer of 0 to 75, more preferably an integer of 0 to 50, but more preferably r is 2 or more, particularly 2 to 50, and particularly 3 ~ 40, most preferably 3 to 35. In this case, when R ¹ ₃ SiO _1/2 unit has an alkenyl group, r of R ¹ ₃ SiO _1/2 unit having the alkenyl group is 2 to 50. Is preferable. s is an integer from 0 to 300, preferably an integer from 0 to 200, more preferably an integer from 0 to 100, and t is an integer from 0 to 200, preferably an integer from 0 to 100. , More preferably an integer of 0 to 50, u is an integer of 0 to 200, preferably an integer of 0 to 100, and even more preferably an integer of 0 to 50. However, 1 ≦ t + u ≦ 400, preferably 1 ≦ t + u ≦ 200, and more preferably 1 ≦ t + u ≦ 100. Further, 3 ≦ r + s + t + u ≦ 800, preferably 4 ≦ r + s + t + u ≦ 600. Since the organopolysiloxane requires R ¹ SiO _3/2 unit (T unit) and / or SiO _4/2 unit (Q unit), it has a branched (resin-like) structure.

[(B) Linear organopolysiloxane]
The component (B) of the present invention is also the main component of the addition-curable silicone resin composition of the present invention, and when used in combination with the branched organopolysiloxane of the component (A), the viscosity is further reduced. Plays a role of improving the strength of the cured product. The organopolysiloxane has the following formula (2).
(R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2)
(In the formula, the definition of R ¹ is the same as above, at least two of R ¹ are alkenyl groups and x is an integer from 200 to 700.)
It is an organopolysiloxane represented by. As for R ¹ , the same group as that given in the specific example of the component (A) can be exemplified, and x is an integer of 200 to 700, preferably 300 to 600. If x is less than 200, the cured product will not have sufficient strength, and if x is larger than 700, the cured product will become cloudy.

The alkenyl group has at least two in one molecule, and 10 × 10 ^-3 to 10 × 10 ^-1 mol / 100 g in the component (B), particularly 10 × 10 ^-3 to 10 × ^10-2 mol. It is preferable that it contains / 100 g.
Further, the alkenyl group may be in R ¹ ₃ SiO _1/2 unit, in R ¹ ₂ SiO _2/2 unit, or in a plurality of these, but in R ¹ ₃ SiO _1/2 unit. It is preferable to have.

The blending amount of the component (B) is 100 parts by mass when combined with the component (A), and the blending ratio of the component (A) and the component (B) is the mass ratio of (A) :( B) = 1: 1 to 2: 1 is preferable, 1.2: 1 to 2: 1 is more preferable, and 1.4: 1 to 2: 1 is even more preferable. Within this range, there is no tack on the cured product and the dicing property is good, which is preferable.

（式中、Ｒ¹は上記と同じであり、ｎは３〜６の整数である。）
で示される環状シロキサンであって、Ｒ¹については、上記（Ａ）成分における具体例に挙げた基と同じものが例示でき、メチル基、エチル基、プロピル基、ブチル基等のアルキル基が好ましく、より好ましくはメチル基である。ｎは３〜６の整数であり、好ましくは３又は４である。 [(C) Cyclic vinyl siloxane]
When the component (C) of the present invention is used together with the components (A) and (B), the crosslink density can be adjusted, and as a result, the viscosity of the composition and the hardness and strength of the cured product can be improved. The cyclic siloxane has the following formula (3).

(In the equation, R ¹ is the same as above, and n is an integer of 3 to 6.)
As for R ¹ , the same group as the group given in the specific example in the above component (A) can be exemplified, and an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group is preferable. , More preferably a methyl group. n is an integer of 3 to 6, preferably 3 or 4.

Specifically, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane.

The amount of the component (C) added is 2 to 7 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B), preferably 2 to 6 parts by mass, and more preferably 3 to 3 to 6 parts by mass. 6 parts by mass. If it is less than 2 parts by mass, the viscosity cannot be sufficiently lowered, and the obtained cured product does not have sufficient strength. Further, since cyclic vinylsiloxane is known to have an inhibitory effect on hydrosilylation, if it is added in an amount of more than 7 parts by mass, the curing time becomes long, and the crosslink density becomes too large, resulting in brittleness.

[(D) Organohydrogenpolysiloxane]
The component (D) of the present invention plays the role of a cross-linking agent that forms a cross-linked structure with the components (A) to (C) by a hydrosilylation reaction and cures the silicone resin composition.

(D) The organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule is not particularly limited, but the following formula (4)
(R ² ₃ SiO _1/2 ) _r' (R ² ₂ SiO _2/2 ) _s' (R ² SiO _3/2 ) _t' (SiO _4/2 ) _u'
(4)
(In the formula, R ² is a hydrogen atom or a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms independently of each other, and at least two of R ² are hydrogen atoms. R'is 0. ~ 100, s'is 0-300, t'is 0-200, u'is 0-200, but 2 ≤ r'+ s'+ t'+ u'≤ 800. .)
Organohydrogenpolysiloxane represented by is preferably used. Here, R ² is a hydrogen atom or a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 6, and an example of the monovalent saturated hydrocarbon group is specifically. Alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine, bromine and chlorine. Examples thereof include those substituted with a halogen atom such as cyano group and the like, but at least two of R ² are hydrogen atoms, and the other substituent is preferably a methyl group.

r'is an integer from 0 to 100, preferably an integer from 0 to 75, more preferably an integer from 0 to 50, but particularly 2 or more, and s'is an integer from 0 to 300. It is preferably an integer of 0 to 200, more preferably an integer of 0 to 100, but particularly preferably 1 or more, particularly 2 or more. t'is an integer from 0 to 200, preferably an integer from 0 to 100, more preferably an integer from 0 to 50, and u'is an integer from 0 to 200, preferably an integer from 0 to 100. It is more preferably an integer of 0 to 50, preferably in the range of 2≤r'+ s'+ t'+ u'≤800, and more preferably in the range of 3≤r'+ s'+ t'+ u'≤400. It is more preferable that the range is 4 ≦ r'+ s'+ t'+ u'≦ 200.

It should be noted that one molecule has at least two hydrogen atoms, and the component (D) preferably contains 0.1 to 10 mol / 100 g, particularly 0.5 to 5 mol / 100 g.
Further, the hydrogen atom may be in R ² ₃ SiO _1/2 unit, in R ² ₂ SiO _2/2 unit, in R ² SiO _3/2 unit, or in a plurality of these. It is good, but it is preferable to have it in R ² ₃ SiO _2/2 units.

The amount of the organohydrogenpolysiloxane having at least two hydrosilyl groups of the component (D) in one molecule is in the component (D) with respect to 1 mol of the alkenyl group contained in the components (A) to (C). The amount of the hydrosilyl group in the above is 0.4 to 4.0 mol, preferably 0.6 to 2.0 mol, and more preferably 0.8 to 1.6 mol. .. If it is less than 0.4 mol, curing will be poor due to insufficient SiH groups, and if it exceeds 4.0 mol, side reactions such as dehydrogenation due to residual SiH groups are likely to occur.

[(E) Hydrosilylation catalyst]
The component (E) is a hydrosilylation catalyst. The catalyst is not particularly limited as long as it has the ability to carry out the hydrosilylation reaction. Among them, a catalyst selected from a platinum group metal simple substance and a platinum group metal compound is preferable. Examples thereof include platinum-olefin complexes such as platinum (including platinum black), platinum chloride, platinum chloride acid, and platinum-divinylsiloxane complexes, platinum catalysts such as platinum-carbonyl complexes, palladium catalysts, and rhodium catalysts. These catalysts may be used alone or in combination of two or more. Among these, platinum-olefin complexes such as chloroplatinic acid and platinum-divinylsiloxane complex are particularly preferable.

The blending amount of the component (E) may be the amount of the catalyst. The amount of catalyst may be any amount as long as the hydrosilylation reaction can proceed, and may be appropriately adjusted according to the desired curing rate. For example, in the case of a platinum group metal catalyst, the amount is 5 to 20 ppm with respect to the total mass of the above components (A) to (D) on a mass basis converted to platinum group metal atoms from the viewpoint of reaction rate. Is preferable, and an amount of 5 to 10 ppm is more preferable.

The curable composition of the present invention may contain a fluorescent substance, an inorganic filler, an adhesion aid, a curing inhibitor and the like, if necessary, in addition to the above-mentioned components (A) to (E). Hereinafter, each component will be described.

[Fluorescent material]
The phosphor is not particularly limited, and a conventionally known phosphor may be used. For example, it is preferable that the light is absorbed from a semiconductor element, particularly a semiconductor light emitting diode having a nitride semiconductor as a light emitting layer, and converted into light having a different wavelength. Examples of such a phosphor include a nitride-based phosphor / oxynitride-based phosphor that is mainly activated by a lanthanoid-based element such as Eu and Ce, a lanthanoid-based phosphor such as Eu, and a transition metal-based such as Mn. Alkaline earth metal halogen apatite phosphors, alkaline earth metals halogen borate phosphors, alkaline earth metal aluminate phosphors, alkaline earth metal silicate phosphors, alkaline earth metals mainly activated by elements Alkaline earth metal thiogalate phosphor, alkaline earth metal silicon nitride phosphor, germanate phosphor, or rare earth aluminate phosphor, rare earth mainly activated by lanthanoid elements such as Ce. One or more selected from organic complex phosphors mainly activated by silicate phosphors or lanthanoid elements such as Eu, Ca-Al-Si-ON oxynitride glass phosphors, and the like. preferable.

The nitride-based phosphors mainly activated by lanthanoid elements such as Eu and Ce are M ₂ Si ₅ N ₈ : Eu (M is at least one selected from Sr, Ca, Ba, Mg and Zn. There 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 at least one selected from Sr, Ca, Ba, Mg, Zn). ) And so on.
As the oxynitride-based phosphor mainly activated by lanthanoid-based elements such as Eu and Ce, at least one selected from MSi ₂ O ₂ N ₂ : Eu (M is Sr, Ca, Ba, Mg, Zn). Is mentioned.).

Alkaline earth metal halogen apatite phosphors that are mainly activated by lanthanoid-based elements such as Eu and transition metal-based elements such as Mn include M ₅ (PO ₄ ) ₃ X: R (M is Sr, Ca, Ba). , Mg, Zn. X is at least one selected from F, Cl, Br, I. R is any one or more of Eu, Mn, Eu and Mn. .) Can be mentioned.

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

As the alkaline earth metal aluminate phosphor, 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 one or more of Eu, Mn, Eu and Mn).

Examples of the alkaline earth metal sulfide phosphor include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

Rare earth aluminate phosphors that are 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 (Al _0.8 Ga). _0.2 ) ₅ O ₁₂ : Ce, and (Y, Gd) ₃ (Al, Ga) YAG-based phosphor represented by the composition formula of ₅ O ₁₂ can be mentioned. Further, there are also Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which part or all of Y is replaced with Tb, Lu, or the like.

Examples of other phosphors include ZnS: Eu, Zn ₂ GeO ₄ : Mn, MGa ₂ S ₄ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) and the like. Be done.
The phosphor should contain at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni and Ti in place of Eu or in addition to Eu, if desired. Can be done.

Ca-Al-Si-ON-based oxynitride glass phosphor is expressed in mol%, CaCO ₃ is converted into CaO, 20 to 50 mol%, Al ₂ O ₃ is 0 to 30 mol%, SiO. 25 to 60 mol%, AlN to 5 to 50 mol%, rare earth oxide or transition metal oxide to be 0.1 to 20 mol%, and oxynitride glass having a total of 5 components of 100 mol% as a base material. It is a phosphor. In a phosphor made of oxynitride glass as a base material, the nitrogen content is preferably 15 mol% or less, and in addition to rare earth oxide ions, other rare earth element ions serving as sensitizers are used as rare earth oxides. It is preferable to include the content in the fluorescent glass in the range of 0.1 to 10 mol% as a coactivator.
Further, a fluorescent material other than the above-mentioned fluorescent material, which has the same performance and effect, can also be used.

When the phosphor is blended, the blending amount is preferably 0.1 to 2,000 parts by mass, more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the components (A) to (D). .. When the cured product of the present invention is used as a phosphor-containing wavelength conversion film, the blending amount of the phosphor is preferably 10 to 2,000 parts by mass. Further, the phosphor preferably has an average particle size 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 particle size distribution measurement by a laser light 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, zinc oxide and the like. These can be used alone or in combination of two or more. The amount of the inorganic filler to be blended is not particularly limited, but it should be appropriately blended in the range of 20 parts by mass or less, preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total components (A) to (D). Just do it.

[Adhesive aid]
The curable composition of the present invention may contain an adhesive aid, if necessary, in order to impart adhesiveness. Examples of the adhesion aid include an organosiloxane oligomer having at least two, 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, as the adhesion aid, an organooxysilyl-modified isocyanurate compound represented by the following general formula (5) and a hydrolyzed condensate thereof (organosiloxane-modified isocyanurate compound) can be used.

（Ｒ⁴は水素原子又は炭素数１〜６のメチル基、エチル基等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。） In the above formula (5), R ³ is an aliphatic unsaturated monovalent hydrocarbon group which may have an organic group represented by the following formula (6) or an oxygen atom independently of each other. However, at least one of R ³ is a group represented by the following formula (6).

(R ⁴ is a hydrogen atom or a monovalent hydrocarbon group such as a methyl group or an ethyl group having 1 to 6 carbon atoms, and k is an integer of 1 to 6, preferably an integer of 1 to 4.)

In the above formula (5), the monovalent aliphatic unsaturated hydrocarbon group which may have an oxygen atom of R ³ is preferably a straight chain having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Examples of the alkenyl group in the form or branch, such as vinyl group, allyl group, 1-butenyl group, 1-hexenyl group, 2-methylpropenyl group, (meth) acrylic group and the like can be mentioned.

When the adhesive aid is blended, the blending amount is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, and particularly preferably 0.1 part by mass, based on 100 parts by mass of the total of the components (A) to (D). It is 0.2 to 5 parts by mass. When the blending amount is not more than the above upper limit value, the hardness of the cured product is high and the surface tackiness can be suppressed.
In addition, when blending the adhesive aid, the ratio of the total number of hydrosilyl groups in the total composition to the total number of alkenyl groups in the total composition containing the present adhesive aid is 0.4. The amount of ~ 4 is preferable, the amount of 0.6 to 3 is more preferable, and the amount of 0.8 to 2 is even more preferable.

[Curing inhibitor]
The curable composition of the present invention may contain a curing inhibitor in order to control the reactivity and enhance the storage stability. The curing inhibitor is selected from the group consisting of triallyl isocyanurate, alkylmalate, acetylene alcohols, and silane-modified and siloxane-modified products thereof, hydroperoxide, tetramethylethylenediamine, benzotriazole, and mixtures thereof. Examples include compounds. When the curing inhibitor is blended, the blending amount is preferably 5 to 100 times, more preferably 5 to 50 times, the molar ratio of the effective amount of the catalyst in the hydrosilylation catalyst of the component (E). Is.

[Other additives]
In addition to the above components, other additives can be added to the curable composition of the present invention. Other additives include, for example, antistatic agents, radical inhibitors, flame retardants, surfactants, ozone deterioration inhibitors, light stabilizers, thickeners, plasticizers, antioxidants, heat stabilizers, and conductive. Examples thereof 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 inactivating agent, a physical property adjusting agent, 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 (A) component, (B) component, (C) component, (D) component and (E) component. A composition comprising (A) component, (B) component, (C) component, (D) component, (E) component and a fluorescent substance is preferable. In particular, in order to obtain a cured product having high transparency, it is preferable that the cured product does not contain an inorganic filler such as silica. 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 conventionally known methods may be followed. For example, the components (A), (B), (C), (D) and (E) can be mixed and prepared by any method. Alternatively, the components (A), (B), (C), (D), (E) and the phosphor, or the components (A), (B), (C), (D), (E), and optionally. The components may be mixed and prepared by any method. For example, it can be prepared by putting it in a commercially available stirrer (THINKY CONDITIONING MIXER (manufactured by Shinky Co., Ltd.) or the like) and mixing it uniformly for about 1 to 5 minutes.

The method for curing the curable composition of the present invention is not particularly limited, and conventionally known methods may be followed. 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 step curing at 60 to 180 ° C., preferably 60 to 150 ° C. In 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 defoam. The curable composition is then heat-cured at a temperature of 120-180 ° C. for 1-10 hours. By going through these steps, even if the cured product is thick, it is sufficiently cured, no bubbles are generated, and it is possible to have colorless transparency. In the present invention, the colorless and transparent cured product means a product having a light transmittance of 80% or more, preferably 85% or more, particularly preferably 90% or more at 450 nm with respect to a thickness of 1 mm. The measurement of the light transmittance is as described later.

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

In addition, the curable composition and the cured product of the present invention have characteristics such as excellent crack resistance, heat resistance, light resistance, and transparency, so that they are display materials, optical recording medium materials, optical equipment materials, and optical components. It is also useful for applications such as materials, optical fiber materials, optoelectronic / electronic functional organic materials, and semiconductor integrated circuit peripheral materials.

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 Guardcolum SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both made by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 20 μL (Sample concentration: 0.5 mass% -tetrahydrofuran solution)
Detector: Differential Refractometer (RI)

The Vi (vinyl) value (mol / 100 g) and SiH value (mol / 100 g) shown in the following examples are vinyl groups obtained by measuring a ¹ H-NMR spectrum of a compound at 400 MHz and using dimethyl sulfoxide as an internal standard. Alternatively, it is calculated from the integrated value of the hydrogen atom of the hydrosilyl group.

The component (C) used in Examples and Comparative Examples is shown below. In the following formula, Me represents a methyl group.

（Ｃ−２’）下記式で表される両末端ビニル（ジメチル）（メチルビニル）シリコーンオイル（信越化学工業株式会社製、Ｖｉ価＝１．１４モル／１００ｇ）

（Ｃ−３’）１，３，５，７−テトラメチルシクロテトラシロキサン（ＳｉＨ価＝１．１８モル／１００ｇ） (C-1) 1,3,5,7-Tetramethyl-1,3,5,7-Tetravinylcyclotetrasiloxane (Vi value = 1.16 mol / 100 g)
(C-2) 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (Vi value = 1.16 mol / 100 g)
(C-1') Both-terminal vinyl dimethyl silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 0.217 mol / 100 g)

(C-2') Bi-terminal vinyl (dimethyl) (methyl vinyl) silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 1.14 mol / 100 g)

(C-3') 1,3,5,7-Tetramethylcyclotetrasiloxane (SiH valence = 1.18 mol / 100 g)

The components (A), (B), (D) and (E) used in Examples and Comparative Examples are shown below. In the following formula, Me represents a methyl group.

（Ｂ）下記式で表される両末端ビニルジメチルシリコーンオイル（信越化学工業株式会社製、Ｖｉ価＝５．１２×１０^-3モル／１００ｇ）

（Ｄ）下記式で表されるＳｉＨ基含有直鎖状シリコーンオイル（信越化学工業株式会社製、ＳｉＨ価＝１．６３モル／１００ｇ）

（Ｅ）塩化白金酸のジビニルシロキサン錯体 (A) Methyl silicone resin represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 9.12 x ^10-2 mol / 100 g)

(B) Both-terminal vinyl dimethyl silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., Vi value = 5.12 × 10 ^-3 mol / 100 g)

(D) SiH group-containing linear silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 1.63 mol / 100 g)

(E) Divinylsiloxane complex of chloroplatinic acid

[Example 1]
(A) 53 parts by mass, (B) 36 parts by mass, (C) 4 parts by mass, (D) 7 parts by mass are mixed, and 5 ppm of (E) chloroplatinic acid divinylsiloxane complex is added as the amount of platinum and mixed. , A curable composition was prepared.

[Examples 2 to 4 and Comparative Examples 1 to 5]
A curable composition was prepared by repeating the same operation as in Example 1 except that the blending amount of each component was changed as shown in Table 1.

The tests shown below were performed on the curable compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 5.
[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 petri dish having a diameter of 50 mm and a thickness of 10 mm, and step-cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, and 150 ° C. × 4 hours to prepare a sample. The hardness of the obtained cured product (durometer ShoreA or ShoreD) was measured according to the method described in JIS K 6253-: 2012. The results are shown in Table 1.

[Light transmittance of cured product]
A concave 1 mm thick Teflon (registered trademark) spacer is sandwiched between two 50 mm × 20 mm × 1 mm thick slide glasses, fixed to each other, and then a curable composition is poured into the glass to 60 ° C. × 1 hour, 100 ° C. × 1. A sample for measuring the transmittance was prepared by step-curing in the order of time, 150 ° C. × 4 hours. The light transmittance of the obtained sample at 450 nm was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 1.

[Tensile strength of cured product and elongation at cutting]
The curable composition prepared was poured into a 150 mm × 200 mm × 2 mm thick concave Teflon (registered trademark) mold, and step-cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, and 150 ° C. × 4 hours for testing. A sample was prepared. Tensile sample tension using EZ TEST (EZ-L, manufactured by Shimadzu Corporation) in accordance with JIS K 6251: 2010 under the conditions of test speed 500 mm / min, grip distance 80 mm, and gauge point distance 40 mm. Strength and elongation at cutting were measured.
The results are shown in Table 1.

[Tackiness of cured product]
The resistance when the thumb was pressed against the surface of the cured product for 1 second and peeled off was sensorivaluated. Those who felt resistance were designated as "yes", and those who did not feel resistance were designated as "none". The results are shown in Table 1.

[Dicing property of cured product]
The curable composition prepared in a concave Teflon (registered trademark) mold is poured into a mold and step-cured in the order of 60 ° C. × 1 hour, 100 ° C. × 1 hour, 150 ° C. × 4 hours to obtain a thickness of 100 mm × 100 mm × 2 mm. A cured product sheet was prepared. The obtained sheet was evaluated by blade dicing with a blade of ZP07-SD2000-F1B333NBC-ZB1050 (Disco Corporation). The evaluation was "good" when the diced part was not dented, and "bad" when the diced part was dented. The results are shown in Table 1.

As shown in Table 1, the curable silicone resin composition using an appropriate amount of the cyclic vinyl siloxane of the present invention has sufficient strength, good dicing property, and gives a cured product without tack. .. In addition, the viscosity of the resin composition can be reduced, and improvement in work efficiency can be expected.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

Claims (4)

The following (A) to (E) components (A) The following formula (1)
(R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u
(1)
(In the formula, R ¹ is a group independently selected from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, but at least 2 of R ¹ is used. Each is an alkenyl group. 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, where 1 ≦ t + u ≦ 400, 3 ≦. r + s + t + u ≦ 800.)
Branched organopolysiloxane (B) represented by the following formula (2)
(R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x (2)
In formula (2) , R ¹ is a group selected independently of each other from a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an alkenyl group having 2 to 6 carbon atoms , where R ^{1 is used.} At least two of the alkenyl groups are in each of the two (R ¹ ₃ SiO _1/2 ) units, but in x (R ¹ ₂ SiO _2/2 ) units. No, x is an integer from 200 to 700.)
Linear organopolysiloxane (C) represented by the following formula (3)

(In equation (3) , R ¹ is the same as that in equation (1) above, and n is an integer of 3 to 6.)
Cyclic vinyl siloxane represented by (A); (A) Organohydrogenpolysiloxane having at least 2 to 7 parts by mass (D) hydrosilyl group in one molecule with respect to 100 parts by mass of the components (A) and (B) in total; ) To 1 mol of the alkenyl group in the component (C) to 0.4 to 4.0 mol of the hydrosilyl group in the component (D), and (E) a hydrosilylation catalyst; the hydrosilylation reaction proceeds. A curable silicone resin composition comprising a sufficient amount of the silicone resin composition. The addition-curable silicone according to claim 1, wherein the compounding ratio of the component (A) and the component (B) is (A) :( B) = 1: 1 to 2: 1 in terms of mass ratio. Resin composition. The component (D) is the following formula (4).
(R ² ₃ SiO _1/2 ) _r' (R ² ₂ SiO _2/2 ) _s' (R ² SiO _3/2 ) _t' (SiO _4/2 ) _u'
(4)
(In the formula, R ² is a hydrogen atom or a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms independently of each other, and at least two of R ² are hydrogen atoms. R'is 0. ~ 100, s'is 0-300, t'is 0-200, u'is 0-200, but 2 ≤ r'+ s'+ t'+ u'≤ 800. .)
The addition-curable silicone resin composition according to claim 1 or 2, which is an organohydrogenpolysiloxane represented by. The addition-curable silicone resin according to any one of claims 1 to 3, wherein the blending amount of the component (E) is 5 to 20 ppm with respect to the total mass of the components (A) to (D). Composition.