KR101805925B1

KR101805925B1 - Curable organopolysiloxane composition, optical element sealing material and optical element

Info

Publication number: KR101805925B1
Application number: KR1020110135156A
Authority: KR
Inventors: 아따루 고바야시; 신지 기무라; 도시유끼 오자이; 에이이찌 다베이
Original assignee: 신에쓰 가가꾸 고교 가부시끼가이샤
Priority date: 2010-12-16
Filing date: 2011-12-15
Publication date: 2017-12-06
Also published as: TW201237106A; JP5553018B2; CN102585510B; TWI512050B; JP2012126834A; KR20120067945A; CN102585510A

Abstract

The present invention relates to a curable organopolysiloxane composition which provides a cured product which does not cause cracking of the resin or peeling off from the package even in the moisture absorption reflow test and an optical element sealing material containing the composition, Lt; / RTI >
Further, a compound having an ester bond and an alkoxysilyl group specific to a conventional curable organopolysiloxane composition is blended.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable organopolysiloxane composition, an optical element sealing material and an optical element,

TECHNICAL FIELD The present invention relates to a curable organopolysiloxane composition, an optical element sealing material and an optical element, and more particularly, to a cured organopolysiloxane composition which is capable of preventing peeling or cracking from a package in a reflow test after storage in an environment of high temperature and high humidity. An optical element sealing material comprising the composition, and an optical element which is sealed by the cured body and is highly reliable. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a curable organopolysiloxane composition.

The addition-curable organopolysiloxane composition comprises an organopolysiloxane and an organohydrogenpolysiloxane containing an aliphatic unsaturated group such as an alkenyl group, and is cured by a hydrosilylation reaction to provide a cured product. The cured product thus obtained is excellent in heat resistance, cold resistance and electrical insulation, and is transparent. Therefore, it is used in various optical applications such as LED sealing materials.

The silicon material used for optical applications, particularly LED sealing material, is subjected to a solder reflow process in the mounting of the LED device, so that it is temporarily exposed to a high temperature of about 260 캜. For this reason, resistance to cracking of the resin at the time of reflowing, peeling from the package, and the like, that is, the flowability at the bottom, is required.

In the conventional LED sealing material, it has also been proposed that the flowability is improved by adding various kinds of adhesion aids (see, for example, JP-A-2010-111811, JP-A-2010-109034, JP-A-2010-13619, JP-A-2010-13503, JP-A-2007-84766, Patent Documents 1 to 5). However, in the moisture absorption reflow test in which the resin is kept at a high temperature and a high humidity and moisture is absorbed into the resin and then the reflow is carried out, even in the case of a conventional resin, And so on, and a solution thereof has been demanded.

Japanese Patent Application Laid-Open No. 2010-111811 Japanese Patent Application Laid-Open No. 2010-109034 Japanese Patent Application Laid-Open No. 2010-13619 Japanese Patent Application Laid-Open No. 2010-13503 Japanese Patent Application Laid-Open No. 2007-84766

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a curable organopolysiloxane composition which provides a cured product which does not cause cracking of the resin or peeling from the package even in the moisture absorption reflow test, And an optical element sealed with the cured product.

As a result of intensive studies to achieve the above object, the present inventors have found that by adding a compound having a specific ester bond and an alkoxysilyl group shown below to a conventional curable organopolysiloxane composition, a silicone cured product And the present invention has been reached.

Accordingly, the present invention provides the following curable organopolysiloxane composition, optical element sealing material and optical element.

[Claim 1]

(A) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule, represented by the following average composition formula 1,

(Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon groups, R ¹ Is an aryl group, 0.1 to 40 mol% of the entire R ¹ is an alkenyl group, and a is a positive integer satisfying 1? A? 3)

(B) an organohydrogenpolysiloxane represented by the following average composition formula 2,

&Lt; Average composition formula 2 &

(Wherein, R ² is the same or is unsubstituted or substituted one heterologous to each other than an aliphatic unsaturated group hydrocarbon group, or an alkoxy group, b and c are 0.7≤b≤2.1, and 0.8≤ 0.001≤c≤1.0 b + c? 3.0)

(C) a hydrosilylation catalyst comprising a platinum group metal,

(D) a compound represented by the following formula (3)

(Wherein R ³ , R ⁴ and R ⁵ are the same or different unsubstituted or substituted monovalent hydrocarbon groups, and d is 0, 1 or 2)

&Lt; / RTI > curable organopolysiloxane composition.

[Claim 2]

The curable organopolysiloxane composition according to claim 1, wherein the component (B) has at least one silicon-bonded aryl group in one molecule.

[Claim 3]

The curable organopolysiloxane composition according to Claim 1 or 2, wherein the amount of the component (D) added is 0.1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B).

[Claim 4]

An optical element sealing material comprising the composition according to any one of claims 1 to 3.

[Claim 5]

An optical element sealed with a cured product of the sealing material according to claim 4.

The cured product of the curable organopolysiloxane composition of the present invention can be used for an optical element sealing material because of its good reliability against moisture absorption reflow.

1 is a schematic view of a package for a moisture absorption reflow test in an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

[Component (A)] [

(A) is an organopolysiloxane represented by the following average compositional formula:

(A) has an alkenyl group bonded to at least two silicon atoms in a molecule. Examples of the alkenyl group bonded to the silicon atom include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, Nyl group and the like, usually about 2 to 8, preferably about 2 to about 4, and particularly preferably a vinyl group.

The content of the alkenyl group in the component (A) is 0.1 to 40 mol% in the monovalent organic group bonded to the silicon atom (that is, unsubstituted or substituted monovalent hydrocarbon group represented by R ¹ in the above average composition formula 1) , Particularly preferably 0.2 to 20 mol%.

The component (A) has an aryl group bonded to at least one silicon atom in the molecule. As the aryl group, those having 6 to 14, preferably 6 to 10, carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group are usually used, and a phenyl group is particularly preferable.

The content of the aryl group in the component (A) is preferably at least 5 mol% of the monovalent organic group bonded to the silicon atom (i.e., the unsubstituted or substituted monovalent hydrocarbon group represented by R ¹ in the average composition formula 1) . When the aryl group is less than 5 mol% in the monovalent organic group bonded to the silicon atom, the heat resistance and low-temperature characteristics of the cured coating protective material are deteriorated and the reliability may be lowered by the thermal shock test. Therefore, Particularly, it is preferable that at least 30 mol% is an aryl group. The upper limit thereof is not specifically defined, but it is preferably 80 mol% or less, particularly preferably 70 mol% or less, of monovalent organic groups bonded to silicon atoms.

Examples of the organic group which is bonded to the silicon atom other than the alkenyl group and the aryl group of the component (A) include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group and a heptyl group; Aralkyl groups such as a benzyl group and a phenethyl group; An unsubstituted or halogen-substituted monovalent group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, such as a halogenated alkyl group such as a chloromethyl group, a 3-chloropropyl group and a 3,3,3-trifluoropropyl group, And a hydrocarbon group.

Further, a is a positive number satisfying 1 to 3, and the molecular structure of the present component may be either chain or branched, straight chain, or branched.

The viscosity measured by a rotational viscometer when the organopolysiloxane is linear is preferably in the range of about 100 to 20,000 mPa 占 퐏, particularly about 500 to 10,000 mPa 占 퐏 at 25 占 폚 in terms of workability. If the viscosity is too low, it is easy to flow, and there is a possibility that a molded protruding portion or the like may occur. If the viscosity is too high, bubbles of air mixed in necessary components may be difficult to escape. In the case of a branched phase, it is liquid or solid. In the case of a liquid, it is preferable that the viscosity at 25 ° C is in the range of about 1,000 to 5,000 mPa · s. When a solid is used, it is preferably used in combination with a straight-chain organopolysiloxane which is soluble so that the viscosity at 25 ° C is 100 to 20,000 mPa · s.

[Component (B)] [

The component (B) is an organohydrogenpolysiloxane represented by the following average compositional formula (2), which is subjected to hydrosilylation addition reaction with the component (A) to act as a crosslinking agent.

&Lt; Average composition formula 2 &

(Wherein, R ² is the same or is unsubstituted or substituted one heterologous to each other than an aliphatic unsaturated group hydrocarbon group, or an alkoxy group, b and c are 0.7≤b≤2.1, and 0.8≤ 0.001≤c≤1.0 b + c? 3.0, preferably 1.0? b? 2.0, 0.01? c? 1.0, 1.5? b + c? 2.5)

As the monovalent hydrocarbon group of the average formula 2 R ² in, for example, (A) the average formula 1 of the unsubstituted or substituted 1, other than the aliphatic unsaturated group as R ¹ specifically exemplified as the hydrocarbon group in the component An unsubstituted monovalent hydrocarbon group such as an alkyl group, an aryl group or an aralkyl group, or an unsubstituted monovalent hydrocarbon group in which some or all of the hydrogen atoms of these groups are replaced by a halogen atom (e.g., a chlorine atom, a bromine atom or a fluorine atom) , A substituted monovalent hydrocarbon group substituted with an epoxy group, a glycidyl group, and a glycidoxy group), and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and a methoxy group and an ethoxy group are preferable. R ² is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, more preferably a methyl group or a phenyl group. Further, when the substituent of the monovalent hydrocarbon group has an epoxy group-containing group or an alkoxy group, it is possible to impart adhesiveness to the cured product of the composition of the present invention.

The component (B) preferably has an aryl group bonded to a silicon atom in particular. The aryl group is preferably a phenyl group.

The content of the aryl group in the component (B) is not particularly limited so long as it is a monovalent organic group bonded to a silicon atom (that is, an unsubstituted or substituted monovalent hydrocarbon group other than the aliphatic unsaturated group represented by R ² in the average composition formula 2) At least 5 mol%. When the aryl group is contained in an amount of 5 mol% or more in the monovalent organic group bonded to the silicon atom, the cured coating protective material has better heat resistance and low-temperature characteristics, and the reliability of the thermal shock test is more excellent. Therefore, it is preferable that at least 5 mol%, especially 20 mol% or more, is an aryl group. The upper limit thereof is not particularly defined, but it is preferably 80 mol% or less, particularly preferably 60 mol% or less.

The molecular structure of the organohydrogenpolysiloxane of the component (B) is not particularly limited, and examples thereof include various types of organohydrogens such as linear, cyclic, branched, and three-dimensional mesh structures (dendritic) Polysiloxanes can be used.

It is preferable that the organohydrogenpolysiloxane has at least two SiH groups (usually about 2 to about 300) in one molecule. When the organohydrogenpolysiloxane has a straight chain structure or a branched chain structure, these SiH groups may be located only at one of the molecular chain terminal and the non-terminal molecular chain terminal, or may be located on both sides thereof.

The number of silicon atoms (degree of polymerization) in one molecule of the organohydrogenpolysiloxane is preferably 2 to 1,000, more preferably 2 to 200, and still more preferably 2 to 100. The organohydrogenpolysiloxane is preferably liquid at 25 占 폚, and the viscosity at 25 占 폚 measured by a rotational viscometer is preferably 1 to 1,000 mPa 占 퐏, more preferably 10 to 100 mPa 占 퐏 s.

Examples of the organohydrogenpolysiloxane represented by the average composition formula 2 include cyclic compounds containing at least four organohydrogensiloxane units represented by the formula: R ² HSiO, and cyclic compounds represented by the formula: R ² ₃ SiO (HR ² SiO ) _e SiR ² ₃ , a compound represented by the formula: HR ² ₂ SiO (HR ² SiO) _e SiR ² ₂ H, and a compound represented by the formula: HR ² ₂ SiO (R ² ₂ SiO) _f SiR ² ₂ H , A compound represented by the formula: HR ² ₂ SiO (HR ² SiO) _e (R ² ₂ SiO) _f SiR ² ₂ H, and the like. In the above formula, R ² is as defined above, and e and f are at least 1.

Alternatively, the organohydrogenpolysiloxane represented by the average composition formula 2 may be a siloxane unit represented by the formula: HSiO _1.5 , a siloxane unit represented by the formula: R ² HSiO and / or a siloxane unit represented by the formula: R ² ₂ HSiO _0.5 Unit. &Lt; / RTI > In addition, the organohydrogenpolysiloxane may include a monohydric siloxane unit, a diorganosiloxane unit, a triorganosiloxane unit, and / or a SiO _4/2 unit, which do not include a SiH group. R ² in the above formula is as described above.

Specific examples of the organohydrogenpolysiloxane as the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane , Methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, molecular chain double-end trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain double-ended trimethylsiloxy group blocked Dimethylsiloxane-methylhydrogensiloxane copolymer, a molecular chain double-end trimethylsiloxy-blocked diphenylsiloxane-methylhydrogensiloxane copolymer, a molecular chain double-end trimethylsiloxy group-blocked methylphenylsiloxane-methylhydrogensiloxane copolymer, Terminal trimethylsiloxy group blocked dimethylsiloxane · methylhydrogensiloxane · methylphenylsiloxane Polymer, molecular chain end trimethylsiloxy group blocked dimethylsiloxane · methylhydrogensiloxane · diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group blocked methylhydrogenpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group blocked dimethyl Polysiloxane, both ends of molecular chain dimethylhydrogensiloxy group blocked dimethylsiloxane · methylhydrogensiloxane copolymer, both ends of molecular chain dimethylhydrogensiloxy group blocked dimethylsiloxane · methylphenylsiloxane copolymer, both ends of molecular chain dimethylhydrogensiloxane blockade Dimethylsiloxane-diphenylsiloxane copolymer, molecular chain double-terminal dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, molecular chain double-terminal dimethylhydrogensiloxy group-blocked diphenylpolysiloxane, molecular chain double-terminal dimethylhydrogensiloxy group blocked di Carbonyl siloxane and methylhydrogen siloxane copolymer, those in each Example compound, a part or all of the methyl groups replaced with other alkyl groups or containing group-substituted alkyl group-epoxy group, such as an ethyl group, a propyl group organohydrogenpolysiloxane of formula: R ² ₃ SiO _0.5 , an organosiloxane copolymer comprising a siloxane unit represented by the formula: R ² ₂ HSiO _0.5 and a siloxane unit represented by the formula: SiO ₂ , an organosiloxane copolymer represented by the formula: R ² ₂ HSiO _0.5 An organosiloxane copolymer containing a siloxane unit and a siloxane unit represented by the formula: SiO ₂ , a siloxane unit represented by the formula: R ² HSiO, a siloxane unit represented by the formula: R ² SiO _1.5 and a formula: HSiO _1.5 Or an organosiloxane copolymer containing at least one of these siloxane units and an organosiloxane copolymer containing at least two of these organopolysiloxanes It may be a mixture. R ² in the above formula has the same meaning as above.

The component (B) may be used alone or in combination of two or more.

The amount of the component (B) is sufficient to cure the present composition in the presence of the hydrosilylation catalyst as the component (C), and the molar ratio of the SiH groups in the component (B) to the aliphatic unsaturated group in the component Is from 0.2 to 5, more preferably from 0.4 to 2. If the molar ratio is too small or too large, hardening may be insufficient, and characteristics such as hardness, heat resistance and crack resistance may not be satisfied.

[Component (C)] [

As the platinum group metal hydrosilylation catalyst of the component (C), any catalyst may be used as long as it facilitates the hydrosilylation addition reaction between the silicon atom-bonded aliphatic unsaturated group in the component (A) and the SiH group in the component (B). Examples of the component (C) include platinum group metals such as platinum, palladium and rhodium; compounds coordinated with chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, vinylsiloxane or acetylene compounds, Platinum) palladium, and chlorotris (triphenylphosphine) rhodium. Particularly preferred is a platinum compound.

The component (C) may be used alone or in combination of two or more.

The blending amount of the component (C) may be an effective amount as a hydrosilylation catalyst, and is preferably in the range of 0.1 to 1,000 ppm in terms of mass of the platinum group metal element relative to the total mass of the component (A) and the component (B) Preferably in the range of 1 to 500 ppm.

[Component (D)] [

The component (D) is a compound having an ester bond and an alkoxysilyl group represented by the following formula (3), and the addition of the component (D) suppresses cracking of the resin and separation from the package in the moisture absorption reflow test.

The compound having an ester bond and an alkoxysilyl group in the component (D) has at least one ester bond and at least one alkoxysilyl group in one molecule, and is a compound represented by the following formula (3).

(3)

(Wherein R ³ , R ⁴ and R ⁵ are the same or different and each is an unsubstituted or substituted monovalent hydrocarbon group and d is 0, 1 or 2, preferably 0 or 1)

Examples of the unsubstituted or substituted monovalent hydrocarbon groups represented by R ³ , R ⁴ and R ⁵ in the general formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, An alkyl group; Aryl groups such as phenyl, tolyl, xylyl and naphthyl; An unsubstituted or halogen-substituted monovalent group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as a halogenated alkyl group such as a chloromethyl group, a 3-chloropropyl group and a 3,3,3-trifluoropropyl group, And a hydrocarbon group. From among them, R ³ wherein (A) and (B) easily point to a mixture of the ingredients for a methyl group, an ethyl group are preferred, for R ⁴ in an easy point to the hydrolysis, a methyl group, and ethyl group are preferred , And R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a 2-ethylhexyl group, a 2-ethylhexyl group, -Methylhexyl group, 2-ethylhexyl group and the like.

The component (D) may be used alone or in combination of two or more.

The content of the component (D) may be an amount that does not cause tacking after curing inhibition or curing, and is preferably in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B) Preferably 0.5 to 5 parts by mass. If the amount is less than 0.1 part by mass, the effect on moisture absorption reflow may not be obtained. If the amount is more than 10 parts by mass, problems such as inhibition of curing and tack or bleeding out after curing may occur.

[Other components]

The composition of the present invention may contain, in addition to the above components (A) to (D), other optional components as long as the object of the present invention is not impaired. Specific examples thereof include the following. These other components may be used alone or in combination of two or more.

The aliphatic unsaturated group-containing compound other than the component (A)

The composition of the present invention may contain, in addition to the component (A), an aliphatically unsaturated group-containing compound which undergoes addition reaction with the component (B) for the purpose of improving the adhesiveness of the sealing material to the substrate. Such an aliphatic unsaturated group-containing compound other than the component (A) is preferably involved in the formation of a cured product, and examples thereof include organopolysiloxanes other than the component (A) having at least one aliphatic unsaturated group per molecule. The molecular structure thereof may be, for example, any of straight chain, cyclic, branched chain, and three-dimensional network. Specific examples include N-allyl-N ', N "-bis (3-trimethoxysilylpropyl) isocyanurate, N-allyl-N' And the like.

It is also possible to blend an aliphatic unsaturated group-containing organic compound other than the organopolysiloxane. Specific examples of the aliphatic unsaturated group-containing compound include monomers such as butadiene and diacrylate derived from a polyfunctional alcohol; Polyolefins such as polyethylene, polypropylene or copolymers of styrene and other ethylenically unsaturated compounds (e.g., acrylonitrile or butadiene); And oligomers or polymers derived from functional substituted organic compounds such as acrylic acid, methacrylic acid, or esters of maleic acid. The aliphatic unsaturated group-containing compound other than the component (A) may be a liquid or a solid at room temperature.

The content of the aliphatic unsaturated group-containing compound other than the above-mentioned component (A) may be such an amount as not to impair the object of the present invention, and is preferably 0.1 to 100 parts by mass relative to the total 100 parts by mass of the components (A) 10 parts by mass, and more preferably 0.5 to 5 parts by mass. If the amount is less than 0.1 part by mass, there is a fear that the effect of improvement in adhesion can not be obtained, and if it exceeds 10 parts by mass, problems such as deterioration in heat resistance of the cured product may occur.

ㆍ Additional reaction control agent

An additional reaction control agent may be incorporated into the composition of the present invention in order to secure the available time. The addition reaction control agent is not particularly limited as far as it is a compound having a curing inhibiting effect on the hydrosilylation catalyst of the component (C), and conventionally known ones can be used. Specific examples thereof include phosphorus-containing compounds such as triphenylphosphine; Nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; Sulfur-containing compounds; Acetylenic compounds such as acetylene alcohols (for example, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecin-3-ol); A compound containing two or more alkenyl groups; Hydroperoxy compounds; Maleic acid derivatives and the like.

The extent of the curing inhibition effect by the addition reaction control agent differs depending on the chemical structure of the addition reaction control agent. Therefore, it is preferable to adjust the addition amount of each of the addition reaction control agents to be used to an optimum amount, but it is usually about 0.0001 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B) . By adding an optimal amount of the addition reaction control agent, the composition is excellent in long-term storage stability and heat curing property at room temperature.

Other optional components

To inhibit the occurrence of coloration, opacity, oxidative degradation, etc. of the cured product, conventionally known antioxidants such as 2,6-di-t-butyl-4-methylphenol can be incorporated into the composition of the present invention. Further, in order to impart resistance to photo deterioration, a light stabilizer such as a hindered amine stabilizer may be incorporated into the composition of the present invention. An inorganic filler such as fumed silica may be added to the composition of the present invention in order to improve the strength within a range that does not affect the transparency of the cured product obtained from the composition of the present invention. It may also be incorporated into the inventive composition.

[Cured goods]

The curable organopolysiloxane compositions of the present invention can be cured by known curing methods under known curing conditions. Concretely, the composition can be cured by heating at 80 to 200 ° C, preferably 100 to 160 ° C. The heating time may be about 0.5 minute to 5 hours, particularly about 1 minute to 3 hours. When precision such as LED sealing is required, it is preferable to slightly increase the curing time. The form of the resulting cured product is not particularly limited and may be, for example, a gel cured product, an elastomer cured product, or a resin cured product. When the cured product is used for sealing an optical element, it is preferable to use a colorless transparent material having a high refractive index (a refractive index of 1.54 or more, particularly 1.54 to 1.65).

[Optical element sealing material]

The cured product of the composition of the present invention is excellent in heat resistance, cold resistance and electrical insulation as well as cured product of ordinary curable organopolysiloxane composition, and is also excellent in moisture absorption resistance. As the optical element sealed by the sealing material containing the composition of the present invention, for example, an LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, a CCD and the like can be given. Such an optical element can be sealed by applying a sealing material containing the composition of the present invention to the optical element and curing the applied sealing material by a known curing method under known curing conditions, specifically, as described above.

[Example]

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

In the following examples, the viscosity is a value measured at 25 캜 using a rotational viscometer. The refractive index was measured at 25 占 폚 using a digital refractometer RX-5000 manufactured by ATAGO at 589 nm and the hardness was measured according to JIS-K6249. In the following examples, parts represent parts by mass.

In the following examples, the symbol representing the average composition of the silicone oil or the silicone resin represents the following units. The number of moles of each silicone oil or each silicone resin indicates the number of moles of vinyl groups or SiH groups contained in each component.

M ^H : (CH ₃ ) ₂ HSiO _1/2

^{_{M Vi: (CH 2 = CH}} ) (CH 3) 2 SiO 1/2

^{_{M ΦVi: (CH 2 = CH}} ) (C 6 H 5) (CH 3) SiO 1/2

_{D: (CH 3) 2 SiO} 2/2

^{_{D Vi: (CH 2 = CH}} ) (CH 3) SiO 2/2

D ^Φ : (C ₆ H ₅ ) ₂ SiO _2/2

T ^Φ : (C ₆ H ₅ ) SiO _3/2

[Preparation Example 1] Preparation of platinum catalyst

The reaction product of the hexachloroplatinic acid and the sym-tetramethyl divinyl disiloxane was diluted with silicone oil having a viscosity of 0.7 Pa s and an average composition formula: M ^Vi ₂ D ₁₉ D ^Φ ₉ such that the platinum content was 1.0% by mass, A platinum catalyst (Catalyst A) used in this Example and Comparative Example was prepared.

[Preparation Example 2] the average formula: Synthesis of a silicone resin of M ^Vi ₁ T ^Φ ₃

In a 10 L flask, 4,380 g of water and 1,800 g of xylene were put, and a mixed solution of 1,903 g of trichlorophenylsilane, 361.5 g of chlorodimethylvinylsilane and 360 g of xylene was added dropwise so that the internal temperature did not exceed 60 캜, Thereafter, stirring was continued at 60 ° C to 65 ° C for 2 hours. After cooling to room temperature, the water phase was separated. The organic phase was washed with sodium sulfate and then potassium hydroxide (4.3 g) was added, and stirring was continued at 130 캜 to 140 캜 for 12 hours. After removing 700 g of xylene, the mixture was cooled to 50 to 60 DEG C, and further 21.8 g of chlorotrimethylsilane and 19.9 g of potassium acetate were added thereto, and stirring was continued at 50 DEG C to 60 DEG C for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a xylene solution of silicone resin having an average composition formula of M ^Vi ₁ T ^Φ ₃ (nonvolatile content of about 50 mass%).

[Preparation Example 3] Synthesis of silicone resin having an average composition formula: D ^Vi ₁ T ^Φ ₄

To a 10 L flask was added 4,500 g of water and 1,605 g of toluene, and a mixed solution of 1,862 g of trichlorophenylsilane, 310 g of dichloromethylvinylsilane and 384 g of toluene was added dropwise thereto at an internal temperature not exceeding 60 캜, Followed by stirring at 60 ° C to 65 ° C for 2 hours. After cooling to room temperature, the water phase was separated. The organic phase was washed with aqueous sodium bicarbonate, then 0.5 g of a 50 mass% aqueous potassium hydroxide solution was added, and stirring was continued at 100 ° C to 110 ° C for 2 hours. After cooling to 40 to 45 占 폚, 1.45 g of chlorotrimethylsilane and 5.05 g of potassium acetate were added and stirring was continued at 40 占 폚 to 45 占 폚 for 2 hours. Thereafter, toluene was removed by concentration under reduced pressure such that the nonvolatile content became about 50% by mass. After cooling to room temperature, the mixture was filtered to obtain a toluene solution of a silicone resin having an average composition formula: D ^Vi ₁ T ^Φ ₄ (nonvolatile content: about 50 mass%).

[Preparation Example 4] Synthesis of silicone oil having an average composition formula of M ^ΦVi ₂ D ^Φ _3.6

200 g of water and 117 g of toluene were placed in a 500 mL flask, and the mixture was heated to 75 DEG C, and 100 g of dichlorodiphenylsilane was dropped thereinto, and stirring was continued at 80 DEG C for 3 hours. After cooling to room temperature, the water phase was separated. The organic phase was dried over anhydrous sodium sulfate (10 g) and filtered to obtain a toluene solution of dichlorodiphenylsilane hydrolyzed oligomer. Toluene was removed by concentration under reduced pressure, and 30.6 g of dimethyldiphenyl divinyl disiloxane was added and mixed. Further, 5.0 g of concentrated sulfuric acid was added, and the condensation reaction was carried out for 5 hours under the condition of 50 캜 / 15 mmHg. 100 g of toluene and 100 g of 10 mass% sodium sulfate aqueous solution were added and mixed, followed by separation of the aqueous phase. The organic phase was washed with aqueous sodium bicarbonate and water, and then toluene was removed by concentration under reduced pressure. The resulting cloudy liquid was filtered to obtain a silicone oil having an average composition formula of M ^Φ ^Vi ₂ D ^Φ _3.6 , which was colorless and transparent and had a viscosity at 25 ° C. of about 2,000 mPa · s.

[Example 1]

22 parts of silicone oil having an average composition formula of M ^? ^Vi ₂ D ^? _3.6 , 53 parts of silicone resin having an average composition formula of M ^Vi ₁ T ^? ₃ , 22 parts of an organohydrogenpolysiloxane having an average composition formula: M ^H ₂ D ^? ₁ , and 1 part of a compound having an ester bond represented by the following formula (4) and a compound having a methoxysilyl group (additive A) was mixed with 0.0056 part of 3-methyl-1-dodecin-3-ol as a control agent and 0.05 part of the catalyst A, To obtain a polysiloxane composition. The composition was cured by heating at 100 占 폚 for 2 hours and further at 150 占 폚 for 4 hours. The hardness of the resulting elastomer (A) was 27 in Shore D. Further, the test results of the moisture absorption reflow are shown in Table 1.

[Example 2]

A composition was prepared in accordance with Example 1, except that in place of Additive A, 1 part of a compound having an ester bond and a methoxysilyl group (additive B) represented by the following general formula (5) was used. The organopolysiloxane composition was cured by heating at 100 DEG C for 2 hours and further at 150 DEG C for 4 hours. The hardness of the resulting elastomer (B) was 25 at Shore D. Further, the test results of the moisture absorption reflow are shown in Table 1.

[Comparative Example 1]

A composition was prepared according to Example 1 except that 1 part of N-allyl-N ', N "-bis (3-triethoxysilylpropyl) isocyanurate (Additive C) was used in place of Additive A. The organopolysiloxane composition was cured by heating at 100 DEG C for 2 hours and further at 150 DEG C for 4 hours. The hardness of the obtained elastomer (C) was 40 in Shore D. Further, the test results of the moisture absorption reflow are shown in Table 1 Respectively.

[Comparative Example 2]

A composition was prepared in accordance with Example 1 except that 1 part of 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.) was used instead of the additive A. The organopolysiloxane composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours. The hardness of the resulting elastomer (D) was 30 at Shore D. Further, the test results of the moisture absorption reflow are shown in Table 1.

[Comparative Example 3]

A composition was prepared in accordance with Example 1 except that 1 part of 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) was used instead of the additive A. The organopolysiloxane composition was cured by heating at 100 캜 for 2 hours and further at 150 캜 for 4 hours. The hardness of the resulting elastomer (E) was 28 in Shore D. Further, the test results of the moisture absorption reflow are shown in Table 1.

[Example 3]

55.1 parts of a silicone oil ^{having an} average composition formula of M ^? ^Vi ₂ D ^? _3.6 , 45 parts of a silicone resin having an average composition formula of D ^Vi ₁ T ^? ₄ , 28.6 parts of an organohydrogenpolysiloxane having an average composition formula of M ^H ₂ D ^? ₁ , 1 part of a compound having an ester bond represented by the general formula (4) and a compound having a methoxysilyl group (additive A) was mixed with 0.2 part of 3-methyl-1-dodecin-3-ol serving as a controlling agent and 0.3 part of the catalyst A, To obtain a polysiloxane composition. The composition was cured by heating at 100 占 폚 for 2 hours and further at 150 占 폚 for 4 hours. The hardness of the resulting elastomer (F) was 32 in Shore D. The test results of the moisture absorption reflow are shown in Table 2.

[Example 4]

A composition was prepared in accordance with Example 3 except that 1 part of the compound having an ester bond and the methoxysilyl group (additive B) shown above in the formula (5) was used instead of the additive A. The organopolysiloxane composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours. The hardness of the resulting elastomer (G) was 31 at Shore D. The test results of the moisture absorption reflow are shown in Table 2.

[Comparative Example 4]

A composition was prepared in accordance with Example 3, except that 1 part of N-allyl-N ', N "-bis (3-triethoxysilylpropyl) isocyanurate (Additive C) was used instead of Additive A. The organopolysiloxane composition was cured by heating at 100 占 폚 for 2 hours and further at 150 占 폚 for 4 hours, and the resulting elastomer (H) had a hardness of Shore D of 50. Further, the test results of the moisture absorption reflow were shown in Table 2 Respectively.

[Comparative Example 5]

A composition was prepared according to Example 3 except that 1 part of 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.) was used instead of the additive A. The organopolysiloxane composition was cured by heating at 100 占 폚 for 2 hours and further at 150 占 폚 for 4 hours. The hardness of the obtained elastomer (I) was 30 at Shore D. The test results of the moisture absorption reflow are shown in Table 2.

[Comparative Example 6]

A composition was prepared in accordance with Example 3 except that 1 part of 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) was used instead of the additive A. The organopolysiloxane composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours. The hardness of the obtained elastomer (J) was 33 at Shore D. The test results of the moisture absorption reflow are shown in Table 2.

Assessment Methods

Package for moisture absorption reflow test

As the test package for the moisture absorption reflow test, a simple package as shown in Fig. 1 without the LED chip was used. (1) In this case, (2, 3) is a lead electrode, and (4) is a sealing resin (a cured product of the organopolysiloxane composition obtained in Examples and Comparative Examples). The curing conditions of the organopolysiloxane composition are 2 hours at 100 占 폚 and 4 hours at 150 占 폚.

Test method for moisture absorption reflow

Ten test packages thus prepared were placed in a constant-temperature and constant-humidity bath at 85 ° C and 85% RH for 24 hours, and then passed through an infrared reflow apparatus (260 ° C) once to observe changes in appearance. The results are shown in Tables 1 and 2. Further, it was counted as NG when the resin was confirmed to be cracked or peeled off from the LED package.

1 case
2, and 3 lead electrodes
4 sealing resin

Claims

(A) an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and represented by the following average composition formula 1,
A mixture obtained by using a branched organopolysiloxane in combination with a straight-chain organopolysiloxane,
<Average composition formula 1>

(Wherein a one, R ¹ is the same or of different types of unsubstituted or substituted monovalent hydrocarbon group to each other, R is at least one is the aryl group of the ^1, 0.1 to 40 mol% of the R ¹ is an alkenyl group, a is 1, Lt; = a < = 3)
(B) an organohydrogenpolysiloxane represented by the following average composition formula 2,
&Lt; Average composition formula 2 &

(Wherein, R ² is the same or is unsubstituted or substituted one heterologous to each other than an aliphatic unsaturated group hydrocarbon group, or an alkoxy group, b and c are 0.7≤b≤2.1, and 0.8≤ 0.001≤c≤1.0 b + c? 3.0)
(C) a hydrosilylation catalyst comprising a platinum group metal,
(D) a compound represented by the following formula (3)
(3)

(Wherein R ³ , R ⁴ and R ⁵ are the same or different unsubstituted or substituted monovalent hydrocarbon groups, and d is 0, 1 or 2)
/ RTI >
Wherein the hardness after curing is equal to or greater than Shore D 25.

The curable organopolysiloxane composition according to claim 1, wherein the addition amount of the component (D) is 0.1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B).