JP2018165348A - Highly heat-resistant addition-curable silicone resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition-curable silicone resin composition that gives a cured product having sufficient heat resistance, strength, and crack resistance.SOLUTION: An addition-curable silicone resin composition contains (A) alkenyl group-containing branched organopolysiloxane: 100 pts.mass, (B) cyclic vinyl siloxane represented by a formula (2): 1-7 pts.mass, (C) organohydrogenpolysiloxane: in such an amount that hydrosilyl groups in the (C) component are 0.4-4 mol relative to 1 mol of alkenyl groups in the (A) and (B) components; and (D) a hydrosilylation catalyst, and gives a cured product that shows, after curing, a hardness of 60 or more in durometer shore D, measured in accordance with the method described in JIS K 6253-3: 2012 (R's independently represent a C1-12 monovalent saturated hydrocarbon group or a C6-12 aromatic hydrocarbon group; and n is an integer of 3-6).SELECTED DRAWING: None

Description

  The present invention relates to a high heat resistance addition-curable silicone resin composition.

The addition-curable silicone resin composition has been used as a sealing material for sealing semiconductor elements such as LEDs since it has excellent fast curing properties, heat resistance of cured products, and light resistance.
However, in general, silicone resin has a low refractive index, and when a resin having a low refractive index is used as an LED sealing material, light is totally reflected due to the difference in refractive index between the LED chip and the resin, and the light is extracted. Efficiency will be reduced.

  In order to improve the refractive index, a method of introducing an aromatic substituent is known. However, as the aromatic substituent is introduced, the heat resistance of the resin cured product is lowered, so that high power with a large calorific value is generated. This LED could not be used.

  Patent Document 1 proposes a method for improving the heat resistance by adding a phenolic antioxidant, but there is a problem that the effect of the antioxidant is lowered when exposed to a high temperature for a long time. It was.

In addition, various methods for improving heat resistance have been proposed, but none of them has achieved sufficient heat resistance.
For example, Patent Documents 2 and 3 propose a resin composition having high heat resistance and excellent adhesive strength, and a phenyl silicone resin composition having high hardness at a wide range of temperatures. In order to make it low, it contains a lot of low molecular weight siloxane oligomers, and such a cured product has the disadvantage that it has poor mechanical properties such as strength and elongation, and is easily cracked.

  As described above, no phenyl silicone resin composition has been developed so far that provides a cured product having sufficient heat resistance, strength, and crack resistance that can be used for a high-power LED having a large calorific value.

JP 2005-272697 A Japanese Patent Application Laid-Open No. 2006-079320 JP 2005-162859 A

  The present invention has been made in view of the above problems, and an addition curable silicone resin composition that gives a cured product having sufficient heat resistance, strength, and crack resistance, particularly an addition curable phenyl silicone resin composition. The purpose is to provide.

As a result of intensive studies to achieve the above object, the present inventors have found that (A) an alkenyl group-containing branched organopolysiloxane having an aromatic hydrocarbon group, (B) a specific cyclic vinylsiloxane, and (C) an organohydrogen. An addition-curable silicone resin composition containing a predetermined amount of polysiloxane and containing (D) a hydrosilylation catalyst gives a high-hardness silicone resin having many branch points and cross-linking points, and the silicone resin has few cross-linking points. It has been found that there is less coloring when left for a long time at a high temperature than a low hardness silicone resin. The reason for this is thought to be that because there are many branch points and cross-linking points, the molecular chain is difficult to move, and thermal energy is not easily converted to energy that breaks the bond of the molecular chain. Moreover, it discovered that the viscosity of the resin composition before hardening can be made low by adding cyclic vinylsiloxane as a crosslinkable component, and the hardened | cured material after hardening can be made into high hardness and high intensity | strength. Furthermore, since R (SiO ₂ -bonded organo group) of the R ₂ SiO _2/2 unit of the linear organopolysiloxane is easily cut and discolored by heat, it does not contain a linear organopolysiloxane as a main component. The inventors have found that the present invention is preferable and have come to make the present invention.

（式中、Ｒ²は互いに独立に、炭素数１〜１２の一価飽和炭化水素基及び炭素数６〜１２の芳香族炭化水素基から選ばれる基であり、ｎは３〜６の整数である。）
（Ｃ）ケイ素原子に直接結合した水素原子（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）及び（Ｂ）成分中に含まれるアルケニル基１モルに対して、（Ｃ）成分中に含まれるヒドロシリル基０．４〜４モルに相当する量
（Ｄ）ヒドロシリル化触媒
を含み、硬化後のＪＩＳ Ｋ ６２５３−３：２０１２に記載の方法に準拠して測定した硬さがデュロメータショアＤで６０以上である硬化物を与える付加硬化型シリコーン樹脂組成物。
〔２〕
直鎖状のアルケニル基含有オルガノポリシロキサンを含まない〔１〕記載の付加硬化型シリコーン樹脂組成物。
〔３〕
（Ｂ）成分が、下記式（２’）

（式中、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である〔１〕又は〔２〕記載の付加硬化型シリコーン樹脂組成物。
〔４〕
（Ｃ）成分が、下記式（３）
（Ｒ³ ₃ＳｉＯ_1/2）₂（Ｒ³ ₂ＳｉＯ_2/2）_m （３）
（式中、Ｒ³は互いに独立に、水素原子、炭素数１〜１２の一価飽和炭化水素基及び炭素数６〜１２の芳香族炭化水素基から選ばれる基であり、Ｒ³の少なくとも２個は水素原子であり、ｍは１〜１００の整数である。）
で示される直鎖状オルガノハイドロジェンポリシロキサンである〔１〕〜〔３〕のいずれかに記載の付加硬化型シリコーン樹脂組成物。 Accordingly, the present invention provides the following addition-curable silicone resin composition.
[1]
(A) Branched organopolysiloxane represented by the following formula (1): 100 parts by mass (R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c ( SiO _4/2 ) _d
(1)
(In the formula, R ¹ is a group independently selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. And each R ¹ may be the same or different, provided that at least one of R ¹ is an aromatic hydrocarbon group and at least two are alkenyl groups, and a is an integer of 1 to 10 And b is an integer of 0 to 10, c is an integer of 1 to 100, and d is an integer of 0 to 100. However, 3 ≦ a + b + c + d ≦ 200.
(B) Cyclic vinylsiloxane represented by the following formula (2): 1 to 7 parts by mass

(In the formula, R ² is a group independently selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms, and n is an integer of 3 to 6). is there.)
(C) Organohydrogenpolysiloxane having at least two hydrogen atoms (hydrosilyl groups) directly bonded to silicon atoms in one molecule: with respect to 1 mol of alkenyl groups contained in (A) and (B) components, (C) An amount corresponding to 0.4 to 4 moles of hydrosilyl groups contained in component (D) Hardness measured in accordance with the method described in JIS K 6253-3: 2012 after curing, containing a hydrosilylation catalyst An addition-curable silicone resin composition that gives a cured product having a durometer shore D of 60 or more.
[2]
The addition-curable silicone resin composition according to [1], which does not contain a linear alkenyl group-containing organopolysiloxane.
[3]
(B) component is following formula (2 ')

(In the formula, n is an integer of 3 to 6.)
The addition-curable silicone resin composition according to [1] or [2], which is a cyclic vinylsiloxane represented by the formula:
[4]
(C) component is following formula (3)
(R ³ ₃ SiO _1/2 ) ₂ (R ³ ₂ SiO _2/2 ) _m (3)
(In the formula, R ³ is a group independently selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms, and at least 2 of R ³ . Each is a hydrogen atom, and m is an integer of 1 to 100.)
The addition-curable silicone resin composition according to any one of [1] to [3], which is a linear organohydrogenpolysiloxane represented by the formula:

  According to the present invention, the addition-curable silicone resin composition containing the components (A) to (D) can give a cured product having sufficient heat resistance, strength, and crack resistance.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
Hereinafter, each component will be described.

[(A) Branched organopolysiloxane]
(A) component of this invention becomes a main component of the addition-curable silicone resin composition of this invention, and following formula (1)
(R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c (SiO _4/2 ) _d
(1)
(In the formula, R ¹ is a group independently selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. And each R ¹ may be the same or different, provided that at least one of R ¹ is an aromatic hydrocarbon group and at least two are alkenyl groups, and a is an integer of 1 to 10 And b is an integer of 0 to 10, c is an integer of 1 to 100, and d is an integer of 0 to 100. However, 3 ≦ a + b + c + d ≦ 200.
It is the organopolysiloxane shown by these.

Here, R ¹ has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 monovalent saturated hydrocarbon groups, 6 to 12 aromatic hydrocarbon groups, and 2 to 2 carbon atoms. It is a group selected from 10, preferably 2 to 8 carbon atoms, more preferably 2 to 6 alkenyl groups.

  Examples of monovalent saturated hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups and other cycloalkyl groups, and hydrogen atoms bonded to carbon atoms of these groups. Are substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, a (meth) acryloxy group, a glycidyloxy group, a mercapto group, an amino group, etc., for example, trifluoropropyl group, chloropropyl Halogenated monovalent saturated hydrocarbon group such as a group; cyanoalkyl group such as β-cyanoethyl group and γ-cyanopropyl group; 3-methacryloxypropyl group, 3-glycidyloxypropyl group, 3-mercaptopropyl group, 3- An aminopropyl group etc. are illustrated. Among these, a methyl group, a cyclohexyl group and the like are preferable, and a methyl group is particularly preferable. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, and naphthyl group, and aralkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group. One or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as fluorine, bromine or chlorine or a cyano group. Examples of alkenyl groups include vinyl, allyl, propenyl, hexenyl, styryl and the like.

However, at least one of R ¹ is an aromatic hydrocarbon group and at least two are alkenyl groups. The aromatic hydrocarbon group is preferably a phenyl group or tolyl group, particularly preferably a phenyl group, Is preferably a vinyl group or an allyl group, and particularly preferably a vinyl group.

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

a is an integer of 1 to 10, preferably 2 to 10, more preferably an integer of 3 to 10. b is an integer of 0 to 10, preferably 0 to 8, more preferably an integer of 0 to 5. c is an integer of 1 to 100, preferably 1 to 50, more preferably an integer of 1 to 30. d is an integer of 0 to 100, preferably 0 to 50, more preferably an integer of 0 to 30. However, 3 ≦ a + b + c + d ≦ 200, preferably 4 ≦ a + b + c + d ≦ 150, more preferably 4 ≦ a + b + c + d ≦ 100, and particularly preferably 4 ≦ a + b + c + d ≦ 50. The organopolysiloxane has R ¹ SiO _3/2 units (T units), and therefore has a branched structure.

In addition, it is preferable that the composition of this invention does not contain a linear organopolysiloxane as a main component from a heat resistant point. As the linear organopolysiloxane, the following formula (R ¹ ₃ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _x
(In the formula, R ¹ is the same as above, except that at least two of R ¹ are alkenyl groups, and x is an integer of 100 to 700.)
The thing shown by is mentioned.

For R ¹ is, (A) can be exemplified the same ones as the groups listed in the specific example of component, x is an integer from 100 to 700, preferably 200 to 600.
The alkenyl group has at least two alkenyl groups in one molecule, and contains 10 × 10 ⁻³ to 10 × 10 ⁻¹ mol / 100 g, particularly 10 × 10 ⁻³ to 10 × 10 ⁻² mol / 100 g in one molecule. It is preferable. Further, the alkenyl group may be in the R ¹ ₃ SiO _1/2 unit, the R ¹ ₂ SiO _2/2 unit, or a plurality of these.

  In addition, when linear organopolysiloxane is included, it is preferable that it is less than 50 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 30 mass parts or less.

（式中、Ｒ²は互いに独立に、炭素数１〜１２の一価飽和炭化水素基及び炭素数６〜１２の芳香族炭化水素基から選ばれる基であり、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である。 [(B) Cyclic vinylsiloxane]
By using the component (B) of the present invention together with the component (A), the branch point and the crosslinking point 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 vinylsiloxane has the following formula (2)

(In the formula, R ² is a group independently selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms, and n is an integer of 3 to 6). is there.)
It is cyclic vinylsiloxane shown by these.

In the above formula, R ² is a group selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. is there.

（式中、ｎは３〜６の整数である。） Examples of monovalent saturated hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups and other cycloalkyl groups, and hydrogen atoms bonded to carbon atoms of these groups. Are substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, a (meth) acryloxy group, a glycidyloxy group, a mercapto group, an amino group, etc., for example, trifluoropropyl group, chloropropyl Halogenated monovalent saturated hydrocarbon group such as a group; cyanoalkyl group such as β-cyanoethyl group and γ-cyanopropyl group; 3-methacryloxypropyl group, 3-glycidyloxypropyl group, 3-mercaptopropyl group, 3- An aminopropyl group etc. are illustrated. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, and naphthyl group, and aralkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group. One or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as fluorine, bromine or chlorine or a cyano group. Among these, a methyl group, an ethyl group, and the like are preferable, and a methyl group is particularly preferable because it does not lower the reactivity of the vinyl group. Accordingly, those represented by the following formula (2 ′) are preferably used.

(In the formula, n is an integer of 3 to 6.)

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

  (B) As addition amount of a component, it is 1-7 mass parts with respect to 100 mass parts of (A) component, Preferably it is 2-6 mass parts. If it is less than 1 part by mass, the viscosity cannot be lowered sufficiently, and the resulting cured product does not have sufficient strength and heat resistance because the number of crosslinking points does not increase so much. On the other hand, adding more than 7 parts by mass does not cause too many vinyl groups, and since cyclic vinylsiloxane is known to have a hydrosilylation-inhibiting action, the curing time becomes very long, resulting in production. Efficiency will decrease. Moreover, even if all the vinyl groups have reacted, the crosslink density becomes too high, so that it becomes brittle. Even if the curing time is short, a certain degree of hardness is obtained, but it is not sufficient, and the light transmittance decreases because there are many unreacted vinyl groups.

[(C) Organohydrogenpolysiloxane]
Component (C) of the present invention is an organohydrogenpolysiloxane having at least two hydrogen atoms (hydrosilyl groups) directly bonded to silicon atoms in one molecule, and hydrosilylated with the components (A) and (B). It serves as a crosslinking agent that forms a crosslinked structure by reaction and cures the silicone resin composition.

(C) The organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule is not particularly limited, but in view of viscosity and strength, the following formula (3)
(R ³ ₃ SiO _1/2 ) ₂ (R ³ ₂ SiO _2/2 ) _m (3)
(In the formula, R ³ is a group independently selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms, and at least 2 of R ³ . Each is a hydrogen atom, and m is an integer of 1 to 100.)
A linear organohydrogenpolysiloxane represented by the formula is preferred.

In the above formula, R ³ is selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6, more preferably 1 to 4 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. Group. Examples of monovalent saturated hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups and other cycloalkyl groups, and hydrogen atoms bonded to carbon atoms of these groups. Are substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, a (meth) acryloxy group, a glycidyloxy group, a mercapto group, an amino group, etc., for example, trifluoropropyl group, chloropropyl Halogenated monovalent saturated hydrocarbon group such as a group; cyanoalkyl group such as β-cyanoethyl group and γ-cyanopropyl group; 3-methacryloxypropyl group, 3-glycidyloxypropyl group, 3-mercaptopropyl group, 3- An aminopropyl group etc. are illustrated. Among these, a methyl group, a cyclohexyl group and the like are preferable, and a methyl group is particularly preferable. 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. One or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as fluorine, bromine or chlorine or a cyano group. Among these, a phenyl group and a tolyl group are preferable, and a phenyl group is particularly preferable. However, at least two of R ³ are hydrogen atoms.

  m is an integer of 1 to 100, preferably an integer of 1 to 80, more preferably an integer of 1 to 60, and still more preferably an integer of 1 to 40.

  The addition amount of the organohydrogenpolysiloxane having at least two hydrosilyl groups in the component (C) is in the component (C) with respect to 1 mole of the alkenyl group contained in the components (A) and (B). The amount of the hydrosilyl group is from 0.4 to 4 mol, preferably from 0.6 to 2 mol, and more preferably from 0.8 to 1.6 mol. If the amount is less than 0.4 mol, the SiH group is insufficient, resulting in poor curing. If the amount exceeds 4 mol, side reactions such as dehydrogenation due to the remaining SiH group tend to occur.

[(D) Hydrosilylation catalyst]
Component (D) is a hydrosilylation catalyst. The catalyst is not particularly limited as long as it has an ability to allow the hydrosilylation reaction to proceed. Among these, a catalyst selected from a platinum group metal simple substance and a platinum group metal compound is preferable. For example, platinum (including platinum black), platinum chloride, chloroplatinic acid, platinum-olefin complexes such as platinum-divinylsiloxane complexes, platinum catalysts such as platinum-carbonyl complexes, palladium catalysts, rhodium catalysts and the like can be mentioned. These catalysts may be used alone or in combination of two or more. Of these, platinum-olefin complexes such as chloroplatinic acid and platinum-divinylsiloxane complexes are particularly preferred.

  Component (D) may be added in a catalytic amount. The catalyst amount may be an amount that allows the hydrosilylation reaction to proceed, and may be appropriately adjusted according to a desired curing rate. For example, in the case of a platinum group metal catalyst, from the viewpoint of reaction rate, an amount of 1 to 20 ppm relative to the total mass of the components (A) to (C) on a mass basis converted to a platinum group metal atom. Is more preferable, and an amount of 1 to 10 ppm is more preferable.

In addition to the components (A) to (D) described above, the curable composition of the present invention may contain a phosphor, an inorganic filler, an adhesion aid, a curing inhibitor, and the like as necessary.
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 light to light having a different wavelength. Examples of such phosphors include nitride-based phosphors / oxynitride-based phosphors mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid-based substances such as Eu, and transition metal-based substances such as Mn. Alkaline earth metal halogen apatite phosphor, alkaline earth metal borate 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, rare earth aluminate phosphor mainly activated by lanthanoid elements such as Ce, rare earth Select from organic complex phosphors mainly activated by lanthanoid elements such as silicate phosphors or Eu, Ca-Al-Si-O-N oxynitride glass phosphors, etc. Which is preferably at least one.

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

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

Examples of alkaline earth metal halogen apatite phosphors 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). X is at least one selected from F, Cl, Br and I. R is any one or more of Eu, Mn, Eu and Mn. Etc.).

As the alkaline earth metal borate 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, And at least one selected from Br and I. R is any one or more of Eu, Mn, Eu and Mn).

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, BaMgAl ₁₀ O ₁₇ : R (R is any 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.

As rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce, 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,} (Y, Gd) 3 (Al, Ga) 5 YAG -based phosphor represented by a composition formula of O ₁₂ and the like, and the like. Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc., in which a part or all of Y is substituted with Tb, Lu or the like.

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 and Zn). It is done.

  The phosphor contains at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, Ti instead of Eu or in addition to Eu as desired. Can do.

The Ca—Al—Si—O—N-based oxynitride glass phosphor is expressed in terms of mol%, CaCO ₃ is converted to CaO, 20 to 50 mol%, Al ₂ O ₃ is 0 to 30 mol%, SiO 2 25 to 60 mol% of Al, 5 to 50 mol% of AlN, 0.1 to 20 mol% of rare earth oxide or transition metal oxide, and a base material of an oxynitride glass in which the total of five components is 100 mol% This is a phosphor. In the phosphor using oxynitride glass as a base material, the nitrogen content is preferably 15 mol% or less. In addition to the rare earth oxide ion, another rare earth element ion serving as a sensitizer is added to the rare earth oxide. It is preferable to contain as a co-activator in content in the range of 0.1-10 mol% in fluorescent glass.

  Moreover, it is also possible to use a phosphor other than the above phosphors and having the same performance and effect.

  The blending amount in the case of blending the phosphor 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 (C). . When using the hardened | cured material of this invention as a fluorescent substance containing wavelength conversion film, it is preferable that the compounding quantity of fluorescent substance shall be 10-2,000 mass parts. The phosphor preferably has an average particle diameter of 10 nm or more, more preferably 10 nm to 10 μm, and still more preferably 10 nm to 1 μm. The average particle diameter is measured by particle size distribution measurement by a laser light diffraction method such as a cirrus laser measuring apparatus.

[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 individually by 1 type or in combination of 2 or more types. The blending amount in the case of blending the inorganic filler is not particularly limited, but is appropriately blended within a range of 20 parts by mass or less, preferably 0.1 to 10 parts by mass in total of 100 parts by mass of the components (A) to (C). That's fine.

[Adhesion aid]
The curable composition of the present invention may contain an adhesion assistant as necessary in order to impart adhesion. Examples of the adhesion assistant include organosiloxane oligomers having at least two, preferably three, functional groups selected from a hydrogen atom bonded to a silicon atom, an alkenyl group, an alkoxy group, and an epoxy group in one molecule. . The organosiloxane oligomer preferably has 4 to 50 silicon atoms, more preferably 4 to 20 silicon atoms. Further, as an adhesion assistant, an organooxysilyl-modified isocyanurate compound represented by the following general formula (4) and a hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) can be used.

（Ｒ⁵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 (4), R ⁴ independently of each other is an organic group represented by the following formula (5) or an aliphatic unsaturated monovalent hydrocarbon group which may have an oxygen atom. However, at least one of R ⁴ is a group represented by the following formula (5).

(R ⁵ is a hydrogen atom or a monovalent hydrocarbon group such as a methyl group or 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 (4), the monovalent aliphatic unsaturated hydrocarbon group optionally having an oxygen atom of R ⁴ is preferably a straight chain having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. And a branched or alkenyl group such as a vinyl group, an allyl group, a 1-butenyl group, a 1-hexenyl group, a 2-methylpropenyl group, and a (meth) acryl group.

  The blending amount in the case of blending the adhesion assistant is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, and particularly preferably with respect to 100 parts by mass in total of the components (A) to (C). 0.2 to 5 parts by mass. If the blending amount is less than or equal to the above upper limit value, the cured product hardness is high, and surface tackiness is also suppressed.

  Further, as a blending amount in the case of blending the adhesion assistant, the ratio of the total number of hydrosilyl groups in the whole composition to the total number of alkenyl groups in the whole composition containing the adhesion assistant is 0.4. The amount of ˜4 is preferred, the amount of 0.6˜3 is more preferred, and the amount of 0.8˜2 is even more preferred.

[Curing inhibitor]
The curable composition of the present invention may contain a curing inhibitor in order to control the reactivity and increase the storage stability. The curing inhibitor is a compound selected from the group consisting of triallyl isocyanurate, alkyl maleate, acetylene alcohols, silane-modified products and siloxane-modified products, hydroperoxide, tetramethylethylenediamine, benzotriazole, and mixtures thereof. Is mentioned. The amount of the curing inhibitor to be blended is preferably 5 to 100 times, more preferably 5 to 50 times the molar amount of the effective amount of the catalyst (D) in the hydrosilylation catalyst. It is.

[Other additives]
In addition to the above components, other additives can be added to the curable composition of the present invention. Examples of other additives include anti-aging agents, radical inhibitors, flame retardants, surfactants, ozone degradation inhibitors, light stabilizers, thickeners, plasticizers, antioxidants, thermal stabilizers, and conductivity. Examples include an imparting agent, an antistatic agent, a radiation blocking agent, a nucleating agent, a phosphorus 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 component (A), the component (B), the component (C), and the component (D). Preferably, it is a composition comprising (A) component, (B) component, (C) component, (D) component, and a phosphor. In particular, in order to obtain a cured product having high transparency, a material that does not contain an inorganic filler such as silica is preferable. 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, (A), (B), (C), and (D) component can be mixed and prepared by arbitrary methods. Alternatively, the (A), (B), (C), (D) component and the phosphor, or the (A), (B), (C), (D) component, and the optional component are mixed by any method. Can be prepared. For example, it can be prepared by putting in a commercially available stirrer (THINKY CONDITIONING MIXER (manufactured by Shinky Co., Ltd.)) 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 6 hours. In particular, it is preferable to cure by step cure at 60 to 180 ° C., preferably 60 to 150 ° C. In step cure, it is more preferable to go through the following two stages. First, the curable composition is heated at a temperature of 60 to 100 ° C. for 0.5 to 2 hours to sufficiently degas. Next, the curable composition is heated and cured at a temperature of 120 to 180 ° C. for 1 to 6 hours. By passing through these steps, even if the cured product is thick, it can be sufficiently cured, no bubbles are generated, and it can be colorless and transparent. In the present invention, the colorless and transparent cured product means that the light transmittance at 450 nm with respect to 1 mm thickness is 85% or more, preferably 90% or more, particularly preferably 95% or more. The measurement of light transmittance is as described later.

  Further, the composition of the present invention has a hardness measured according to the method described in JIS K 6253-3: 2012 for a cured product after curing, with a durometer shore D of 60 or more, preferably 63 or more, more preferably 65 or more. The upper limit is not particularly limited, but is usually 90 or less.

  The curable composition of the present invention provides a cured product having high optical transparency. Therefore, the curable composition of the present invention is useful for LED element sealing, particularly for blue LED or ultraviolet LED element sealing. The method of sealing an LED element etc. with the curable composition of this invention should just follow a conventionally well-known method. For example, it can be performed by a dispensing method, a compression molding method, or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

Each component used in the Examples and Comparative Examples is shown below. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group. Vi (vinyl) value (mole / 100 g) and SiH value (mole / 100 g) were determined by measuring a 400 MHz ¹ H-NMR spectrum of the compound, and a hydrogen atom of a vinyl group or hydrosilyl group obtained using dimethyl sulfoxide as an internal standard. Calculated from the integral value of.

（Ａ−２）下記式で表されるフェニル系シリコーンレジン（信越化学工業株式会社製、Ｖｉ価＝０．１８ｍｏｌ／１００ｇ）

(A-1) Phenyl silicone resin represented by the following formula (Shin-Etsu Chemical Co., Ltd., Vi value = 0.14 mol / 100 g)

(A-2) Phenyl silicone resin represented by the following formula (Shin-Etsu Chemical Co., Ltd., Vi value = 0.18 mol / 100 g)

（Ｂ−２’）１，３，５，７−テトラメチルシクロテトラシロキサン（ＳｉＨ価＝１．１８ｍｏｌ／１００ｇ） (B-1) 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane (Vi value = 1.16 mol / 100 g)
(B-2) 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (Vi value = 1.16 mol / 100 g)
(B-1 ′) Vinylsiloxane represented by the following formula (Shin-Etsu Chemical Co., Ltd., Vi value = 1.14 mol / 100 g)

(B-2 ′) 1,3,5,7-tetramethylcyclotetrasiloxane (SiH value = 1.18 mol / 100 g)

（Ｃ−２）下記式で表される側鎖ヒドロシリル基含有シリコーンオイル（信越化学工業株式会社製、ＳｉＨ価＝０．７５８ｍｏｌ／１００ｇ）

(C-1) Both-end hydrosilyl group-containing silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 0.39 mol / 100 g)

(C-2) Side chain hydrosilyl group-containing silicone oil represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 0.758 mol / 100 g)

(D) Divinylsiloxane complex of chloroplatinic acid

  The raw materials described in the following Examples and Comparative Examples were mixed to prepare Examples 1 to 4 and Comparative Examples 1 to 3, and the following evaluations were performed.

[Example 1]
(A) 100 parts by mass, (B) 5 parts by mass, (C) 62 parts by mass, (D) 2 ppm of a chloroplatinic acid divinylsiloxane complex was added and mixed to prepare a curable composition.

[Examples 2 to 4 and Comparative Examples 1 to 3]
Except having changed the compounding quantity of each component as described in Table 1, the same operation as Example 1 was repeated, and the curable composition was prepared.

[Viscosity of composition]
After preparing each composition, the viscosity at 23 ° C. was measured with a rotational viscometer by the method described in JIS K 7117-1: 1999. The results are shown in Table 1.

[Refractive index of composition]
Each composition was prepared, and the refractive index at a wavelength of 589 nm was measured at 25 ° C. by a method described in JIS K 0062: 1992 using a refractive index measuring device (RX-9000α manufactured by ATAGO) for a liquid sample before curing. The results are shown in Table 1.

[Hardness of cured product]
The prepared curable composition was poured into an aluminum petri dish with a diameter of 50 mm and a thickness of 10 mm, and step-cured in the order of 1 hour at 100 ° C. and 4 hours at 150 ° C. to prepare a sample. The hardness (Shore D) of the obtained cured product was measured according to the method described in JIS K 6253-3: 2012. The results are shown in Table 1.

[Tensile strength of cured product / elongation at cutting]
After preparing each composition, it heated at 100 degreeC for 1 hour and then at 150 degreeC for 4 hours, and produced the sheet-like hardened | cured material. Using the cured sheet, tensile strength and elongation at break were measured by the method described in JIS K 6249: 2003. 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 glass slides, and after fixing them, the curable composition is poured, 100 ° C. × 1 hour, 150 ° C. × 4 Step cure was performed in order of time, and a transmittance measurement sample was prepared. 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.

[Heat resistance of cured product (light transmittance)]
A concave 1 mm thick Teflon (registered trademark) spacer is sandwiched between two 50 mm × 20 mm × 1 mm thick glass slides, and after fixing them, the curable composition is poured, 100 ° C. × 1 hour, 150 ° C. × 4 After step curing in order of time, the sample was left at 200 ° C. for 1,000 hours, and the light transmittance at 450 nm was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 1.

  As shown in Table 1, the curable silicone resin composition using an appropriate amount of the cyclic vinylsiloxane of the present invention gives a cured product having sufficient heat resistance, strength, and crack resistance, and further the viscosity of the resin composition. The working efficiency can be expected to be improved.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  Since the curable composition of the present invention provides a cured product having excellent crack resistance, heat resistance, light resistance, transparency and other properties, display materials, optical recording medium materials, optical equipment materials, optical component materials It is also useful for applications such as optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials.

Claims (4)

(A) Branched organopolysiloxane represented by the following formula (1): 100 parts by mass (R ¹ ₃ SiO _1/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ SiO _3/2 ) _c ( SiO _4/2 ) _d
(1)
(In the formula, R ¹ is a group independently selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. And each R ¹ may be the same or different, provided that at least one of R ¹ is an aromatic hydrocarbon group and at least two are alkenyl groups, and a is an integer of 1 to 10 And b is an integer of 0 to 10, c is an integer of 1 to 100, and d is an integer of 0 to 100. However, 3 ≦ a + b + c + d ≦ 200.
(B) Cyclic vinylsiloxane represented by the following formula (2): 1 to 7 parts by mass

(In the formula, R ² is a group independently selected from a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms, and n is an integer of 3 to 6). is there.)
(C) Organohydrogenpolysiloxane having at least two hydrogen atoms (hydrosilyl groups) directly bonded to silicon atoms in one molecule: with respect to 1 mol of alkenyl groups contained in (A) and (B) components, (C) An amount corresponding to 0.4 to 4 moles of hydrosilyl groups contained in component (D) Hardness measured in accordance with the method described in JIS K 6253-3: 2012 after curing, containing a hydrosilylation catalyst An addition-curable silicone resin composition that gives a cured product having a durometer shore D of 60 or more.   The addition-curable silicone resin composition according to claim 1, which does not contain a linear alkenyl group-containing organopolysiloxane. (B) component is following formula (2 ')

(In the formula, n is an integer of 3 to 6.)
The addition-curable silicone resin composition according to claim 1, which is a cyclic vinylsiloxane represented by the formula: (C) component is following formula (3)
(R ³ ₃ SiO _1/2 ) ₂ (R ³ ₂ SiO _2/2 ) _m (3)
(In the formula, R ³ is a group independently selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms, and at least 2 of R ³ . Each is a hydrogen atom, and m is an integer of 1 to 100.)
The addition-curable silicone resin composition according to any one of claims 1 to 3, which is a linear organohydrogenpolysiloxane represented by formula (1).