JP2011246680A - Addition-curable silicone resin composition for light-emitting diode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition-curable silicone resin composition for LED having excellent characteristics such as excellent high transparency, high durability to thermal shock and the like.SOLUTION: This silicone resin composition includes at least (A) a branched organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in the molecule, and having a siloxane unit expressed by general formula (1): RSiO; (B) a linear organohydrogenpolysiloxane having hydrogen atoms each bonded to a silicon atom only at both terminals of the molecular chain, not containing aliphatic unsaturated bond in the molecule, and having 0.001-10 Pa s viscosity at 25°C; (C) an organohydrogenpolysiloxane having at least three hydrogen atoms each bonded to a silicon atom, at least one of them existing as a siloxane unit expressed by general formula (2): RHSiO, and having 0.001-10 Pa s viscosity at 25°C; and (D) an addition reactive catalyst in a catalytic amount. The formulation amount of the (B) component and the (C) component is such that: the total number of hydrogen atoms bonded to a silicon atom in the (B) component and the (C) component is 0.3-7 pieces per one alkenyl group bonded to a silicon atom in the (A) component; and the number of hydrogen atoms bonded to a silicon atom in the (B) component is 5-90% of the total number of hydrogen atoms bonded to a silicon atom in the (B) component and the (C) component.

Description

  The present invention relates to an addition-curable silicone resin composition for light-emitting diodes (LEDs), and in particular, the cured product is transparent and suitable as a light-emitting diode element protection, wavelength change / adjustment, or lens constituent material. The present invention relates to an addition-curable silicone resin material that can provide a cured product having good crack resistance even under conditions.

  It is known that when the LED is energized / lighted, a rapid temperature rise occurs and the LED element receives a thermal shock. Therefore, the LED element is subjected to a severe temperature cycle by repeatedly turning on and off the LED element.

  Epoxy resin is generally used as a sealing material for LED elements. However, since the elastic modulus of the epoxy resin is high, the bonding wire may be broken due to stress due to the temperature cycle, or the epoxy resin may be cracked. Moreover, due to the stress that the epoxy resin gives to the LED chip, there is a concern that the light emission efficiency is lowered due to the collapse of the crystal structure of the semiconductor material.

  As a countermeasure, a method of using room temperature curable silicone rubber as a buffer material and sealing the outside with an epoxy resin has been established as a standard method. However, in this method, since the epoxy resin does not adhere to the silicone resin, it is known that peeling occurs at the interface between the epoxy resin and the silicone rubber due to the temperature cycle, and the light extraction efficiency is extremely lowered with time. Yes.

  Therefore, it has been proposed to use a silicone resin as a material replacing the epoxy resin (see, for example, Patent Documents 1, 2, and 3). Silicone resins are superior in heat resistance, weather resistance, and discoloration resistance compared to epoxy resins, and in particular, in terms of transparency, optical properties, etc., compared to other organic materials such as epoxy resins, An example in which a blue LED and a white LED are mainly used is increasing.

  However, these silicone resins have a lower elastic modulus than epoxy resins, but they also have low mechanical properties such as bending strength, so the problem is that cracks are likely to occur due to the thermal shock that occurs when the LED is energized and lit. Have.

Japanese Patent Laid-Open No. 11-1619 JP 2002-265787 A JP 2004-186168 A JP 2004-140220 A

  The present invention has been made in view of the above circumstances, and is an addition-curable silicone for LED that has high transparency, has high resistance to thermal shock, hardly cracks even under severe temperature cycles, and does not cause peeling. It aims at providing a resin composition.

In order to solve the above problems, the present invention provides at least
(A) a branched organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having a siloxane unit represented by the following general formula (1):
RSiO _3/2 (1)
(Wherein R is a substituted or unsubstituted monovalent hydrocarbon group)
(B) a linear chain having a hydrogen atom bonded to a silicon atom only at both ends of the molecular chain, having no aliphatic unsaturated bond in the molecule, and a viscosity at 25 ° C. of 0.001 to 10 Pa · s Organohydrogenpolysiloxane,
(C) It has at least three hydrogen atoms bonded to silicon atoms in one molecule, and at least one of them is present as a siloxane unit represented by the following general formula (2), and the viscosity at 25 ° C. is 0 An organohydrogenpolysiloxane of 0.001 to 10 Pa · s,
R ¹ HSiO _2/2 (2)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond)
(D) addition reaction catalyst catalyst amount,
A silicone resin composition comprising:
The blending amount of the component (B) and the component (C) is such that the total number of hydrogen atoms bonded to the silicon atoms in the components (B) and (C) is bonded to the silicon atoms in the component (A). The number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.3 to 7 per alkenyl group and the hydrogen bonded to the silicon atoms in the component (B) and the component (C) An addition-curable silicone resin composition for light-emitting diodes, characterized in that the amount is 5 to 90% of the total number of atoms.

  Such an addition-curable silicone resin composition of the present invention has high transparency because of its excellent resistance to discoloration, and has high resistance to thermal shock. However, cracks and peeling are unlikely to occur.

In this case, the content of the siloxane unit represented by the general formula (1) of the component (A) can be 50 to 100 mol%.
Thus, it is good also considering the content of the siloxane unit represented by RSiO3 _{/ 2} of (A) component as a high ratio with 50-100 mol%.

  As described above, the addition-curable silicone resin composition of the present invention has high thermal shock resistance of the cured product, so that it is difficult for cracks and peeling to occur and is excellent in high transparency. Therefore, it is useful as a material for a light emitting diode element.

It is sectional drawing which shows typically an example of the light-emitting semiconductor device with which the addition-curable silicone resin composition of this invention is used suitably.

Hereinafter, the present invention will be described in more detail.
As described above, the conventionally used sealing materials for LED elements have the problem that cracks are likely to occur due to thermal shocks that occur particularly during energization / lighting of the LED, and severe temperature cycling is required. There has been a demand for a sealing material that does not easily crack or peel off.

Therefore, as a result of intensive studies by the present inventors, as a base polymer, at least two alkenyl groups bonded to silicon atoms are contained in one molecule, and branched organoorganisms having a siloxane unit represented by RSiO _3/2. Organohydrogenpolysiloxane using polysiloxane and having hydrogen atoms bonded to silicon atoms only at both ends of the molecular chain as a crosslinking agent, and organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule It was found that the above-mentioned problems can be achieved by combining these at a specific ratio, and an addition-curable silicone resin composition suitable as an LED element material has been completed.

That is, the addition-curable silicone resin composition for light-emitting diodes of the present invention is at least
(A) a branched organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having a siloxane unit represented by the following general formula (1):
RSiO _3/2 (1)
(Wherein R is a substituted or unsubstituted monovalent hydrocarbon group)
(B) a linear chain having a hydrogen atom bonded to a silicon atom only at both ends of the molecular chain, having no aliphatic unsaturated bond in the molecule, and a viscosity at 25 ° C. of 0.001 to 10 Pa · s Organohydrogenpolysiloxane,
(C) It has at least three hydrogen atoms bonded to silicon atoms in one molecule, and at least one of them is present as a siloxane unit represented by the following general formula (2), and the viscosity at 25 ° C. is 0 An organohydrogenpolysiloxane of 0.001 to 10 Pa · s,
R ¹ HSiO _2/2 (2)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond)
(D) addition reaction catalyst catalyst amount,
A silicone resin composition comprising:
The blending amount of the component (B) and the component (C) is such that the total number of hydrogen atoms bonded to the silicon atoms in the components (B) and (C) is bonded to the silicon atoms in the component (A). The number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.3 to 7 per alkenyl group and the hydrogen bonded to the silicon atoms in the component (B) and the component (C) The amount is 5 to 90% of the total number of atoms.

Hereinafter, each component of the present invention will be described in detail.
<(A) component>
The component (A) is a branched organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a siloxane unit represented by the following general formula (1).
RSiO _3/2 (1)
(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group.)

  In the general formula (1), the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom represented by R is usually an unsubstituted or substituted group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms. Specific examples of such hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl and heptyl groups; Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group and phenethyl group; Saturated hydrocarbon group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, and the like; Eniru group, an alkenyl group is preferred. As the alkenyl group, a vinyl group is preferable.

  The siloxane unit (T unit) represented by the general formula (1) may be at least one in the molecule, but is preferably contained in an amount of 50 to 100 mol%, particularly 60 to 100 mol%. Is preferred.

In addition to the siloxane unit represented by the general formula (1), the component (A) includes R ₃ SiO _1/2 unit (M unit), R ₂ SiO _2/2 unit (D unit), and SiO _4/2. One or two or more units selected from the unit (Q unit) may be contained (wherein R is independently a substituted or unsubstituted monovalent hydrocarbon group). The content of M units is preferably 0 to 50 mol%, particularly preferably 0 to 40 mol%, the content of D units is preferably 0 to 50 mol%, particularly preferably 0 to 40 mol%, and Q units Is preferably 0 to 20 mol%, particularly preferably 0 to 10 mol% (provided that the total of M, D, T and Q units is 100 mol%). Among these, those consisting only of T units, those consisting of M units and T units, those consisting of M units, D units and T units are preferred.

At least two of these Rs are alkenyl groups, preferably 0.1 to 30 mol%, particularly preferably 0.5 to 20 mol% are alkenyl groups.
If the alkenyl group content is too small, the curability of the composition may be lowered, and if it is too much, the cured silicone resin may be brittle.

The component (A) may be liquid or solid at room temperature, but if it is solid at room temperature, it must be soluble in a solvent or have a melting point.
As the component (A), one type may be used, or two or more types having different structures may be used in combination.

<(B) component>
The (B) component organohydrogenpolysiloxane functions as a chain extender. As a result, it has high resistance to thermal shock, and crack growth is avoided even under severe temperature cycles. This organohydrogenpolysiloxane has one hydrogen atom (that is, SiH group) bonded to a silicon atom only at both ends of the molecular chain, and a viscosity at 25 ° C. of 0.001 to 10 Pa · s, preferably It is a linear one of 0.01 to 1 Pa · s (viscosity is a value measured by a rotational viscometer).
The organohydrogenpolysiloxane of component (B) does not have an aliphatic unsaturated bond in the molecule.

The molecular structure of the linear organohydrogenpolysiloxane may be substantially linear. Here, “substantially linear” in component (B) is usually 99 to 100 mol%, preferably 99.5 to siloxane units constituting the main chain portion excluding both ends of the molecular chain. 100 mol% means R ¹ ₂ SiO _2/2 units (wherein R ¹ is each independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond) . Both ends of the molecular chain are preferably blocked with a diorganohydrogensiloxy group represented by R ¹ ₂ (H) SiO _1/2 unit (wherein R ¹ is the same as described above). .

In the above formula, the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond represented by R ¹ usually has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. Specific examples thereof include those exemplified as the organic group bonded to the silicon atom other than the alkenyl group bonded to the silicon atom in the component (A), and a methyl group and a phenyl group are preferable.

（式中、Ｒ^１は前記と同様であり、ｎは（Ｂ）成分のオルガノハイドロジェンポリシロキサンの２５℃における粘度が０．００１〜１０Ｐａ・ｓ、好ましくは０．０１〜１Ｐａ・ｓとなる整数である。） The organohydrogenpolysiloxane of component (B) is preferably represented by the following general formula (3).

(In the formula, R ¹ is the same as above, and n is the viscosity of the organohydrogenpolysiloxane of component (B) at 25 ° C. of 0.001 to 10 Pa · s, preferably 0.01 to 1 Pa · s. (It is an integer.)

(B) The compounding quantity of the organohydrogenpolysiloxane of a component is as having described in the term of the (C) component mentioned later.
The (B) component organohydrogenpolysiloxane may be used alone or in combination of two or more.

<(C) component>
The organohydrogenpolysiloxane of component (C) has at least 3, preferably 3 to 100, more preferably 3 to 50, hydrogen atoms bonded to silicon atoms (that is, SiH groups) in one molecule. And at least one of them, preferably 20 to 100%, more preferably 30 to 80% (number basis) of the SiH group, is present as an organohydrogensiloxane unit represented by the following general formula (2). The viscosity at 25 ° C. is 0.001 to 10 Pa · s, preferably 0.01 to 5 Pa · s (the viscosity is a value measured by a rotational viscometer).
R ¹ HSiO _2/2 (2)
(In the formula, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond.)
The organohydrogenpolysiloxane of component (C) also has no aliphatic unsaturated bond in the molecule.

The molecular structure of the organohydrogenpolysiloxane of component (C) is not particularly limited, and may be any of linear, cyclic, branched, three-dimensional network, etc., preferably substantially Is linear. In addition, cyclic siloxane may be bonded to the molecular chain terminal. Here, “substantially linear” in component (C) is usually a siloxane unit constituting the main chain portion excluding both ends of the molecular chain (the cyclic siloxane when a cyclic siloxane is bonded). 99-100 mol%, preferably 99.5-100 mol%, means that R ² ₂ SiO _2/2 units (wherein R ² is independently a hydrogen atom or R ¹ ). .

  The hydrogen atom bonded to the silicon atom may be located at the end of the molecular chain or at the non-end of the molecular chain in the organohydrogenpolysiloxane molecule of the component (C). Good. Moreover, when the cyclic siloxane has couple | bonded with the molecular chain terminal, you may be located in this cyclic siloxane.

In the general formula (2), the unsubstituted or substituted monovalent hydrocarbon group not having an aliphatic unsaturated bond represented by R ¹ is usually 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. . Specific examples thereof include those exemplified as the organic group bonded to the silicon atom other than the alkenyl group bonded to the silicon atom in the component (A), and a methyl group and a phenyl group are preferable.

As the unit other than the general formula (2) contained in the organohydrogenpolysiloxane of the component (C), a unit represented by the following general formula (4) is preferably exemplified.
R ¹ _e H _f SiO _{(4-ef) / 2} (4)
(Wherein R ¹ is the same as above, e is 0.7 to 2.1, f is 0.001 to 1.0, and e + f is a number from 0.8 to 2.7, preferably, e is a number from 1.0 to 2.0, f is a number from 0.01 to 1.0, and e + f is a number from 1.1 to 2.5.)

As the organohydrogenpolysiloxane of component (C), R ¹ HSiO _2/2 units are contained in the molecule, and R ¹ ₂ R ² SiO _1/2 units and / or R ¹ ₂ SiO _{2 /} Examples thereof optionally contain ₂ units (wherein R ¹ and R ² are the same as described above).

（式中、Ｒ^１は前記と同様であり、ｐ^１は３以上、ｐ^２は１以上、ｐ^３、ｑ^３は共に１以上、ｐ^４は３以上、ｑ^４は１以上の整数である。但し、ｐ^１〜ｐ^４及びｑ^３〜ｑ^４は、（Ｃ）成分のオルガノハイドロジェンポリシロキサンの２５℃における粘度が０．００１〜１０Ｐａ・ｓ、好ましくは０．０１〜５Ｐａ・ｓとなる整数である。） Specifically, for example, 1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, both ends trimethylsiloxy group-blocked methylhydrogen poly Siloxane, Trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both end dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, Trimethylsiloxy group-capped methylhydrogensiloxane / diphenyl Siloxane copolymer, trimethylsiloxy group blocked at both ends, methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, trimethylsiloxy group at both ends Chain methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane A dimethylsiloxane-methylphenylsiloxane copolymer, a copolymer comprising (CH ₃ ) (H) SiO _2/2 units, (CH ₃ ) ₃ SiO _1/2 units and SiO _4/2 units, (CH ₃ ) (H) a copolymer comprising SiO _2/2 units, (CH ₃ ) ₂ SiO _2/2 units, (CH ₃ ) ₃ SiO _1/2 units and SiO _4/2 units, (CH ₃ ) (H ) and _{SiO 2/2} units _{(CH 3)} 2 _(H) and _{SiO 1/2} units (C _{3) 3} SiO _1/2 units and _{SiO 4/2 units,} copolymers composed _of the (CH 3) _{(H) SiO 2/2} units and _{(CH 3)} 2 _{(H) SiO 1/2} units (CH ₃ ) A copolymer composed of ₂ SiO _2/2 units, (CH ₃ ) ₃ SiO _1/2 units, and SiO _4/2 units may be mentioned, and more preferably, for example, the following may be mentioned.

(In the formula, R ¹ is the same as above, p ¹ is 3 or more, p ² is 1 or more, p ³ and q ³ are both 1 or more, p ⁴ is 3 or more, and q ⁴ is an integer of 1 or more. . ^However, p 1 ~p ⁴ and ^q 3 to q ⁴ is, (C) organohydrogenpolysiloxane of the component of 25 ° C. · viscosity 0.001~10Pa in s, preferably a 0.01~5Pa · s Is an integer.)

The blending amount of the component (B) and the component (C) is such that the total number of hydrogen atoms bonded to the silicon atoms in the components (B) and (C) is bonded to the silicon atoms in the component (A). 0.3 to 7 per alkenyl group (that is, the molar ratio is 0.3 to 7), preferably 0.5 to 5 and bonded to the silicon atom in the component (B) An amount in which the number of hydrogen atoms (number of moles) is 5 to 90%, preferably 10 to 70% of the total number (number of moles) of hydrogen atoms bonded to the silicon atoms of the components (B) and (C). It is. When these numbers (blending amounts) do not satisfy such a range, the crack resistance is poor.
The organohydrogenpolysiloxane of component (C) may be used alone or in combination of two or more.

<(D) component>
The addition reaction catalyst of component (D) is a catalyst for crosslinking by addition reaction of component (A), component (B), and component (C). Examples thereof include chloroplatinic acid, chloroplatinic acid, Reactions with monohydric alcohols, olefin complexes of chloroplatinic acid, coordination compounds of chloroplatinic acid and vinylsiloxane, platinum-based catalysts such as platinum black, palladium-based catalysts, rhodium-based catalysts, etc. A platinum catalyst is usually used in terms of height. Particularly in this application, low chlorine catalysts that do not corrode metals are preferable because they are used for the production of sealed LEDs in the electronics field. Among them, divinyltetramethyldisiloxane and divinyldiphenyl that do not contain a chlorine component are preferred. Those modified with dimethyldisiloxane or the like are preferable. These addition reaction catalysts may be used alone or in combination of two or more.

  In addition, the compounding quantity of this addition reaction catalyst is an effective quantity (catalyst quantity) which acts as a catalyst, Preferably it is 1-1000 ppm with respect to the total amount of (A) component-(C) component. If it is 1 ppm or more, curing proceeds at an appropriate speed, and if it is 1000 ppm or less, the workable time does not become too short, and the cured product is not easily yellowed, which is economical. Most preferably, it is 5-100 ppm.

（式中、Ｒ^１は前記と同様であり、ｍは（Ｅ）成分のオルガノポリシロキサンの２５℃における粘度が０．００１〜１０Ｐａ・ｓ、好ましくは０．０１〜１Ｐａ・ｓとなる整数である。）
その使用量は（Ａ）成分１００質量部に対して、０〜１００質量部、好ましくは０〜５０質量部である。 <Optional component>
In the composition of the present invention, a linear reactive organopolysiloxane represented by the following general formula (5) is used as an optional component other than the components (A) to (D) and the component (E). You may add in the range which does not impair the effect of invention. The component (E) is an additive component effective for adjusting the curability of the composition and the hardness of the cured product.

(In the formula, R ¹ is the same as described above, and m is an integer at which the viscosity of the organopolysiloxane of component (E) at 25 ° C. is 0.001 to 10 Pa · s, preferably 0.01 to 1 Pa · s. is there.)
The usage-amount is 0-100 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0-50 mass parts.

  As other optional components, for example, all conventionally known control agent compounds which are compounds having a curing inhibitory effect on the addition reaction catalyst can be used. Such compounds include phosphorus-containing compounds such as triphenylphosphine, nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, sulfur-containing compounds, acetylenic compounds, compounds containing two or more alkenyl groups, hydropar Examples include oxy compounds and maleic acid derivatives. Since the degree of cure retarding effect by the control agent compound varies greatly depending on the chemical structure of the control agent compound, it is preferable to adjust the addition amount of the control agent compound to an optimum amount for each of the control agent compounds used. Is an amount in such a range that long-term storage stability at room temperature is obtained and curing is not inhibited, usually 0.5 parts by mass or less, preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of component (A). Used in an amount of 0.3 parts by weight.

  Moreover, you may contain the adhesion imparting agent for improving the adhesiveness in this composition. Examples of the adhesion-imparting agent include silane coupling agents and hydrolysis condensates thereof. As silane coupling agents, epoxy group-containing silane coupling agents, (meth) acrylic group-containing silane coupling agents, isocyanate group-containing silane coupling agents, isocyanurate group-containing silane coupling agents, amino group-containing silane coupling agents , And known ones such as a mercapto group-containing silane coupling agent are exemplified, and preferably 0.1 to 20 parts by mass, more preferably 0.3 to 100 parts by mass in total of the component (A) and the component (B). -10 parts by mass.

  Such a cured product of the composition of the present invention is excellent in high transparency and does not generate cracks or peeling even under severe temperature cycles, and is therefore useful as a sealing material for light-emitting diodes. Such a light emitting diode is useful in various fields such as a switching element, illumination, and backlight of a liquid crystal display.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example etc.
[Example 1]
(PhSiO _3/2 ) _0.8 [(CH ₂ ═CH) Me ₂ SiO _0.5 ] Branched organopolysiloxane represented by _0.2 [content of silicon atom-bonded vinyl group = 14.3 mol %, Silicon atom-bonded phenyl group content in all silicon-bonded organic groups = 57 mol%, weight average molecular weight in terms of standard styrene = 2350] 100 parts by mass, HMe ₂ SiO (Ph ₂ SiO) ₁ SiMe ₂ H 6.8 parts by mass of an organohydrogenpolysiloxane having a viscosity of 4 mPas having a structure, 30 mol% of phenyl groups based on the total of hydrogen atoms, phenyl groups and methyl groups bonded to silicon atoms, and hydrogen gas generation amount Is 19.8 parts by weight of an organohydrogenpolysiloxane having a viscosity of 20 mPas, chloroplatinic acid / 1,3-divinyltetate 0.06 parts by mass of a toluene solution containing 1% by mass of a platinum atom content of a lamethyldisiloxane complex, 0.05 parts by mass of ethynylcyclohexanol, and 3 parts by mass of γ-glycidoxypropyltrimethoxysilane were uniformly mixed. Thus, a silicone composition (a) was prepared. When this silicone composition (a) was cured by heating at 150 ° C. for 4 hours, the hardness was 69 in Shore D.

[Example 2]
24.6 parts by mass of an organohydrogenpolysiloxane having a structure of HMe ₂ SiO (Ph ₂ SiO) ₁ SiMe ₂ H and a viscosity of 4 mPas, based on the total of hydrogen atoms, phenyl groups and methyl groups bonded to silicon atoms Except for using 2.6 parts by mass of an organohydrogenpolysiloxane having a viscosity of 20 mPas with a hydrogen gas generation amount of 140 mol / g having 30 mol% of phenyl groups, and changing the ratio of the amount of component (B) used, A silicone composition (b) was prepared according to Example 1. When the silicone composition (b) was cured by heating at 150 ° C. for 4 hours, the hardness was 66 in Shore D.

[Example 3]
HMe ₂ SiO (Ph ₂ SiO) ₁ SiMe ₂ H structure, 2.7 parts by mass of an organohydrogenpolysiloxane having a viscosity of 4 mPas, based on the sum of hydrogen atoms, phenyl groups and methyl groups bonded to silicon atoms Except for using 23.8 parts by mass of an organohydrogenpolysiloxane having a viscosity of 20 mPas with a hydrogen gas generation rate of 140 ml / g having 30 mol% of phenyl groups, and changing the ratio of the amount of component (B) used, A silicone composition (c) was prepared according to Example 1. When the silicone composition (c) was cured by heating at 150 ° C. for 4 hours, the hardness was 70 in Shore D.

[Comparative Example 1]
Without using an organohydrogenpolysiloxane having a structure of HMe ₂ SiO (Ph ₂ SiO) ₁ SiMe ₂ H, 30 mol% of the phenyl group is based on the total of hydrogen atoms, phenyl groups and methyl groups bonded to silicon atoms. A silicone composition (d) was prepared according to Example 1 except that 26 parts by mass of an organohydrogenpolysiloxane having a hydrogen gas generation amount of 140 ml / g and a viscosity of 20 mPas was used. When the silicone composition (d) was cured by heating at 150 ° C. for 4 hours, the hardness was 70 in Shore D.

[Comparative Example 2]
Using 27 parts by mass of an organohydrogenpolysiloxane having a structure of HMe ₂ SiO (Ph ₂ SiO) ₁ SiMe ₂ H, 30 phenyl groups are added to the total of hydrogen atoms, phenyl groups and methyl groups bonded to silicon atoms. A silicone composition (e) was prepared according to Example 1, except that no organohydrogenpolysiloxane having a viscosity of 20 mPas and a hydrogen gas generation amount of 140% by mole was used. When this silicone composition (e) was cured by heating at 150 ° C. for 4 hours, the hardness was 65 in Shore D.

The evaluation methods in the silicone compositions (a) to (e) prepared in the above examples and comparative examples were performed as follows.
[Evaluation methods]
As the light emitting semiconductor package light emitting element, a light emitting semiconductor device as shown in FIG. 1 having a light emitting layer made of InGaN and mounting an LED chip having a main light emission peak of 470 nm was used. Here, 1 is a housing, 2 is a light emitting element, 3 and 4 are lead electrodes, 5 is a die bond material, 6 is a gold wire, and 7 is a sealing resin. The curing conditions for the sealing resin 7 are 150 ° C. and 4 hours.

Moisture resistance and infrared reflow test method 10 light-emitting semiconductor devices were placed in a constant temperature and humidity chamber at 85 ° C and 85% for 24 hours, and then passed through an infrared reflow device (260 ° C) three times to observe changes in appearance. did. The results are shown in Table 1. In addition, the thing by which the crack of resin and the peeling from an LED package were confirmed was counted as NG.

As shown in Table 1, Examples 1 to 3 in which the ratio of (B) component ((B) / (B) + (C)) (mol%) is within the range of 5 to 90% are NG numbers. Is 0, and the crack resistance is good even under high temperature / low temperature cycle conditions, it is understood that peeling does not occur and the light extraction efficiency is high. Moreover, such a silicone resin was also excellent in high transparency.
On the other hand, Comparative Example 1 containing no component (B) and 100% of component (B) and Comparative Example 2 containing no component (C) are more than half of the resin cracks and peeled off from the LED package. Has occurred. Thereby, when a conventional thing is used as a sealing material, it turns out that productivity of LED will worsen.

  From the above, since the addition-curable silicone resin composition of the present invention has high resistance to thermal shock, it is difficult to generate cracks and has high light extraction efficiency, and is subjected to severe temperature cycles. It proved to be useful for LEDs.

  The present invention is not limited to the above embodiment. The above-described 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 any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

DESCRIPTION OF SYMBOLS 1 ... Housing | casing 2 ... Light emitting element 3, 4 ... Lead electrode 5 ... Die-bonding material,
6 ... gold wire, 7 ... sealing resin.

Claims (2)

at least,
(A) a branched organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having a siloxane unit represented by the following general formula (1):
RSiO _3/2 (1)
(Wherein R is a substituted or unsubstituted monovalent hydrocarbon group)
(B) a linear chain having a hydrogen atom bonded to a silicon atom only at both ends of the molecular chain, having no aliphatic unsaturated bond in the molecule, and a viscosity at 25 ° C. of 0.001 to 10 Pa · s Organohydrogenpolysiloxane,
(C) It has at least three hydrogen atoms bonded to silicon atoms in one molecule, and at least one of them is present as a siloxane unit represented by the following general formula (2), and the viscosity at 25 ° C. is 0 An organohydrogenpolysiloxane of 0.001 to 10 Pa · s,
R ¹ HSiO _2/2 (2)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond)
(D) addition reaction catalyst catalyst amount,
A silicone resin composition comprising:
The blending amount of the component (B) and the component (C) is such that the total number of hydrogen atoms bonded to the silicon atoms in the components (B) and (C) is bonded to the silicon atoms in the component (A). The number of hydrogen atoms bonded to the silicon atom in the component (B) is 0.3 to 7 per alkenyl group and the hydrogen bonded to the silicon atoms in the component (B) and the component (C) An addition-curable silicone resin composition for light-emitting diodes, characterized in that the amount is 5 to 90% of the total number of atoms.   2. The addition-curable silicone resin composition for a light-emitting diode according to claim 1, wherein the content of the siloxane unit represented by the general formula (1) in the component (A) is 50 to 100 mol%. object.

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