KR20120067945A - Curable organopolysiloxane composition, optical element sealing material and optical element - Google Patents

Abstract

PURPOSE: A curable organopolysiloxane composition is provided to provide a cured material not generating separation from a package or crack of resin even by moisture-absorption reflow test. CONSTITUTION: A curable organopolysiloxane composition comprises: organopolysiloxane comprising at least two alkenyl group combined to a silicone atom in one molecule, in chemical formula 1: R^1_aSiO_(4-a)/2; organohydrogenpolysiloxane in chemical formula 2: R^2_bH_cSiO_(4-b-c)/2; a hydrosilylation catalyst; and a compound in chemical formula 3. In chemical formula 1, R^1 is a same or different substituted or unsubstituted monovalent hydrocarbon group, at least one of R^1 is aryl group, 0.1-40 mol% of total R^1 is alkenyl group, and a is a positive number, satisfying 1<=a<=3.

Description

Curable organopolysiloxane composition, optical element encapsulant and optical element {CURABLE ORGANOPOLYSILOXANE COMPOSITION, OPTICAL ELEMENT SEALING MATERIAL AND OPTICAL ELEMENT}

TECHNICAL FIELD The present invention relates to a curable organopolysiloxane composition, an optical element sealing material, and an optical element. Specifically, in a reflow test after storage in an environment of high temperature and high humidity, a cured product capable of preventing peeling or cracking from a package It relates to a curable organopolysiloxane composition for forming a film, an optical element sealing material comprising the composition, and an optical element sealed by the cured product and excellent in reliability.

The addition curable organopolysiloxane composition includes 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. Since the hardened | cured material obtained in this way is excellent in heat resistance, cold resistance, electrical insulation, and transparent, it is used for various optical uses, such as LED sealing material.

Silicone materials used for optical applications, in particular for LED sealing materials, are subjected to a solder reflow step in the mounting of LED elements, and thus are temporarily exposed to high temperatures of about 260 ° C. Therefore, resistance to cracking of the resin at the time of reflow, peeling from the package, or the like, that is, reflowability is required.

Also in the conventional LED sealing material, what improved reflow property is proposed by adding various adhesion | attachment adjuvant (Japanese Unexamined-Japanese-Patent No. 2010-111811, Unexamined-Japanese-Patent No. 2010-109034, Japan) Japanese Patent Laid-Open No. 2010-13619, Japanese Patent Laid-Open No. 2010-13503, Japanese Patent Laid-Open No. 2007-84766: Patent Documents 1 to 5). However, in the moisture absorption reflow test, which is stored under high temperature and high humidity, and then reflowed after absorbing moisture into the resin and the reflecting mirror, cracks of the resin and peeling from the package also exist in the resin which has no problem in the conventional reflow test. A back occurred and his solution was desired.

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

This invention is made | formed in view of the said situation, Curable organopolysiloxane composition which provides the hardened | cured material which does not generate | occur | produce a crack of resin and peeling from a package also in a moisture absorption reflow test, and the optical element sealing material containing the said composition, And It is an object to provide an optical element sealed with this cured product.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, and, as a result, adding the compound which has a specific ester bond and an alkoxysilyl group shown below to the conventional curable organopolysiloxane composition, the silicone hardened | cured material excellent in moisture absorption reflow resistance It discovered that this was obtained and reached | attained this invention.

Therefore, this invention provides the following curable organopolysiloxane composition, an optical element sealing material, and an optical element.

[Claim 1]

(A) organopolysiloxane which has at least 2 alkenyl groups couple | bonded with the silicon atom in 1 molecule represented by following average composition formula 1,

<Mean Composition 1>

Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group from each other, R ¹ At least one is an aryl group, 0.1 to 40 mol% of the total R ¹ is an alkenyl group, and a is a positive number satisfying 1 ≦ a ≦ 3)

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

<Mean Composition 2>

(Wherein R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group, or alkoxy group, other than aliphatic unsaturated group, b and c are 0.7 ≦ b ≦ 2.1, 0.001 ≦ c ≦ 1.0 and 0.8 ≦ positive to satisfy 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 , R ⁵ are the same or different unsubstituted or substituted monovalent hydrocarbon groups, respectively, and d is 0, 1 or 2)

Curable organopolysiloxane composition comprising a.

[Claim 2]

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

[Claim 3]

Curable organopolysiloxane composition of Claim 1 or 2 whose addition amount of (D) component is 0.1-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component.

[Claim 4]

The optical element sealing material containing the composition of any one of Claims 1-3.

[Claim 5]

The optical element sealed with the hardened | cured material of the sealing material of Claim 4.

Since the hardened | cured material of the curable organopolysiloxane composition of this invention has favorable reliability with respect to moisture absorption reflow, it can be used for an optical element sealing material.

1 is a schematic diagram of a package for hygroscopic reflow test in an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

[(A) component]

Component (A) is an organopolysiloxane represented by the following average composition formula (1).

<Mean Composition 1>

Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group from each other, R ¹ At least one is an aryl group, 0.1 to 40 mol% of the total R ¹ is an alkenyl group, and a is a positive number satisfying 1 ≦ a ≦ 3)

(A) Component has the alkenyl group couple | bonded with at least 2 silicon atom in 1 molecule, As an alkenyl group couple | bonded with this silicon atom, for example, a vinyl group, an allyl group, butenyl group, a pentenyl group, hexenyl group, heptene Usually, C2-C8, Preferably about 2-4 are mentioned, such as a nil group, Especially, it is preferable that it is a vinyl group.

Content of the alkenyl group in (A) component is 0.1-40 mol% in monovalent organic group couple | bonded with the silicon atom (that is, unsubstituted or substituted monovalent hydrocarbon group represented by R <^1> in said average composition formula 1). In particular, it is preferable that it is 0.2-20 mol%.

In addition, the component (A) has an aryl group bonded to at least one silicon atom in the molecule. As said aryl group, a C6-C14, Preferably 6-10 things, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, are mentioned normally, Especially, it is preferable that it is a phenyl group.

Content of the aryl group in (A) component is at least 5 mol% in the monovalent organic group couple | bonded with the silicon atom (that is, the unsubstituted or substituted monovalent hydrocarbon group represented by R <^1> in said average composition formula 1). It is preferable. When the aryl group is less than 5 mol% in the monovalent organic group bonded to the silicon atom, the heat resistance and the low temperature characteristic of the cured coating protective material deteriorate, which may cause a decrease in the reliability by the thermal shock test, so at least 5 mol%, It is especially preferable that 30 mol% or more is an aryl group. Although the upper limit is not specifically defined, It is preferable that it is 80 mol% or less, especially 70 mol% or less in the monovalent organic group couple | bonded with the silicon atom.

As an organic group couple | bonded with the silicon atom other than the alkenyl group and aryl group of (A) component, For example, 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, a heptyl group; Aralkyl groups such as benzyl and phenethyl; Unsubstituted or halogen-substituted monovalent having usually 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, such as halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group. Hydrocarbon group is mentioned.

In addition, a is a positive number satisfying 1 to 3, the molecular structure of the present component is linear or branched, and may be any of linear or branched.

It is preferable that the viscosity measured by the rotational viscometer when this organopolysiloxane is linear has a range of 100-20,000 mPa * s, especially 500-10,000 mPa * s at 25 degreeC from a viewpoint of workability. If the viscosity is too low, it is easy to flow, so that molded protrusions and the like may occur. If the viscosity is too high, bubbles of air mixed at the time of mixing of necessary components may be difficult to escape. Moreover, when it is a branched phase, it becomes a liquid or solid, and when it is a liquid, it is preferable that the viscosity in 25 degreeC is the range of about 1,000-5,000 mPa * s. When using a solid thing, it is preferable to use this together with soluble linear organopolysiloxane so that the viscosity in 25 degreeC may be 100-20,000 mPa * s.

[(B) component]

The component (B) is an organohydrogenpolysiloxane represented by the following average composition formula 2, and reacts with the component (A) with hydrosilylation to act as a crosslinking agent.

<Mean Composition 2>

(Wherein R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group, or alkoxy group, other than aliphatic unsaturated group, b and c are 0.7 ≦ b ≦ 2.1, 0.001 ≦ c ≦ 1.0 and 0.8 ≦ Positive numbers satisfying b + c ≦ 3.0, preferably 1.0 ≦ b ≦ 2.0, 0.01 ≦ c ≦ 1.0, and 1.5 ≦ b + c ≦ 2.5

As monovalent hydrocarbon group of R <^{2> in} the said average composition formula 2, it is concretely illustrated as an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group as R <^{1> in} the average composition formula 1 in (A) component, for example. Unsubstituted monovalent hydrocarbon groups such as an alkyl group, an aryl group, an aralkyl group, a part or all of the hydrogen atoms of these groups are halogen atoms (e.g., chlorine atoms, bromine atoms, fluorine atoms), epoxy group-containing groups (e.g. For example, substituted monovalent hydrocarbon group etc. which were substituted by epoxy group, glycidyl group, glycidoxy group) etc. are mentioned. Moreover, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. are illustrated as an alkoxy group, A methoxy group and an ethoxy group are preferable. R ² is preferably an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably a methyl group or a phenyl group. Moreover, when it has an epoxy group containing group or an alkoxy group as a substituent of the said monovalent hydrocarbon group, adhesiveness can be provided to the hardened | cured material of this composition.

It is especially preferable to have an aryl group couple | bonded with the silicon atom in (B) component. It is preferable that the said aryl group is a phenyl group.

Of the content of the aryl groups in component (B) is a monovalent organic group bonded to silicon atoms (that is, the group in the above average composition formula 2, is unsubstituted or substituted 1, other than the aliphatic unsaturated group represented by R ² hydrocarbon), It is preferable that it is at least 5 mol%. When 5 mol% or more of an aryl group is contained in the monovalent organic group couple | bonded with the silicon atom, the heat resistance and low temperature characteristic of the cured coating protective material will become more excellent, and also the reliability by a thermal shock test will become more excellent. Therefore, it is preferable that at least 5 mol%, especially 20 mol% or more is an aryl group. Although the upper limit is not specifically defined, It is preferable that it is 80 mol% or less, especially 60 mol% or less.

There is no restriction | limiting in particular in the molecular structure of the organohydrogenpolysiloxane of (B) component, For example, various organohydrogens conventionally manufactured, such as a linear, cyclic, branched chain, and three-dimensional mesh structure (resin phase), etc. Polysiloxanes can be used.

It is preferable that the said organohydrogen polysiloxane has at least 2 (usually about 2-300) SiH groups in 1 molecule. When the organohydrogenpolysiloxane has a straight chain structure or a branched chain structure, these SiH groups may be located at either one of the molecular chain terminal and the molecular chain non-terminal portion, or may be located at both sides thereof.

The number (polymerization degree) of silicon atoms in one molecule of the organohydrogenpolysiloxane is preferably 2 to 1,000, more preferably 2 to 200, still more preferably about 2 to 100. Moreover, it is preferable that the said organohydrogen polysiloxane is liquid at 25 degreeC, The viscosity in 25 degreeC measured with the rotational viscometer becomes like this. Preferably it is 1-1,000 mPa * s, More preferably, it is 10-100 mPa *. s or so.

As the organohydrogenpolysiloxane represented by the above average compositional formula 2, for example, a cyclic compound including at least four organohydrogensiloxane units represented by the formula: R ² HSiO, and a formula: R ² ₃ SiO (HR ² SiO ) _e Compound represented by SiR ² ₃ , chemical formula: HR ² ₂ SiO (HR ² SiO) Compound represented by _e SiR ² ₂ H, chemical formula: HR ² ₂ SiO (R ² ₂ SiO) _f SiR ² ₂ H And the compound represented by the formula: HR ² ₂ SiO (HR ² SiO) _e (R ² ₂ SiO) _f SiR ² ₂ H. In said formula, R <^2> is as above-mentioned, and e and f are at least 1.

Alternatively, the organohydrogenpolysiloxane represented by the average compositional 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 represented by the formula: R ² ₂ HSiO _0.5 . It may also include a unit. In addition, the organohydrogenpolysiloxane may include monoorganosiloxane units, diorganosiloxane units, triorganosiloxane units, and / or SiO _4/2 units that do not contain a SiH group. R ² in the 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, and tris (hydrogendimethylsiloxy) methylsilane , Tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, molecular chain both terminal trimethylsiloxy group blocking methylhydrogenpolysiloxane, molecular chain both terminal trimethylsiloxy group blocking Dimethylsiloxane, methylhydrogensiloxane copolymer, molecular chain both terminal trimethylsiloxy group blocking diphenylsiloxane, methylhydrogensiloxane copolymer, molecular chain both terminal trimethylsiloxy group blocking methylphenylsiloxane, methylhydrogensiloxane copolymer, molecular chain both Terminal trimethylsiloxy group blocking dimethylsiloxane, methylhydrogensiloxane, methylphenylsiloxane Polymer, molecular chain both terminal trimethylsiloxy group blocking dimethylsiloxane, methylhydrogensiloxane, diphenylsiloxane copolymer, molecular chain both terminal dimethylhydrogensiloxy group blocking methylhydrogenpolysiloxane, molecular chain both terminal dimethylhydrogensiloxy group blocking dimethyl Polysiloxane, molecular chain both terminal dimethylhydrogensiloxy group blocking dimethylsiloxane, methylhydrogensiloxane copolymer, molecular chain both terminal dimethylhydrogensiloxy group blocking dimethylsiloxane, methylphenylsiloxane copolymer, molecular chain both terminal dimethylhydrogensiloxy group blocking Dimethyl siloxane diphenyl siloxane copolymer, molecular chain both terminal dimethylhydrogensiloxy group blocking methylphenyl polysiloxane, molecular chain both terminal dimethylhydrogensiloxy group blocking diphenyl polysiloxane, molecular chain both terminal dimethylhydrogensiloxy group blocking 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 Organosiloxane copolymer comprising a siloxane unit represented by SiO _0.5 and a siloxane unit represented by the formula: R ² ₂ HSiO _0.5 and a siloxane unit represented by the formula: SiO ₂ , represented by the formula: R ² ₂ HSiO _0.5 Organosiloxane copolymer comprising a siloxane unit and a siloxane unit represented by the formula: SiO ₂ , a siloxane unit represented by the formula: R ² HSiO, and a siloxane unit represented by the formula: R ² SiO _1.5 and a formula: HSiO _1.5 Organosiloxane copolymer comprising any one or both of the siloxane units, and two or more kinds of these organopolysiloxanes. It may be a mixture. R <^2> in the said chemical formula has the same meaning as the above.

(B) A component may be used individually by 1 type or may use 2 or more types together.

The compounding quantity of (B) component is an amount sufficient to harden this composition in presence of the hydrosilylation catalyst of (C) component, and the molar ratio of the SiH group in (B) component to the aliphatic unsaturated group in (A) component is normally preferable. Preferably 0.2 to 5, more preferably 0.4 to 2. Even if the molar ratio is too small or too large, there may be a case where the curing is insufficient, and the properties as a sealing material such as hardness, heat resistance and crack resistance may not be satisfied.

[(C) component]

As the platinum group metal-based hydrosilylation catalyst of the component (C), any catalyst may be used as long as it promotes the hydrosilylation addition reaction of 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, platinum chloride, alcohol-modified platinum chloride, coordination compounds of chloroplatinic acid and olefins, vinylsiloxane or acetylene compounds, and tetrakis (triphenylforce). Although platinum group metal compounds, such as pin) palladium and chlorotris (triphenylphosphine) rhodium, are mentioned, Especially preferably, it is a platinum compound.

(C) A component may be used individually by 1 type or may use 2 or more types together.

The compounding quantity of (C) component can be an effective amount as a hydrosilylation catalyst, Preferably it is the range of 0.1-1,000 ppm by mass conversion of a platinum group metal element with respect to the total mass of (A) component and (B) component, More Preferably it is the range of 1-500 ppm.

[(D) component]

The component (D) is a compound having an ester bond and an alkoxysilyl group represented by the following formula (3), and the effect of suppressing cracking of the resin and peeling from the package in the hygroscopic reflow test is obtained by adding the component (D).

The compound having an ester bond and an alkoxysilyl group of 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).

<Formula 3>

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

As an unsubstituted or substituted monovalent hydrocarbon group as R <^3> , R <^4> , R <^5> in said Formula (3), For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, etc. An alkyl group; Aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; Unsubstituted or halogen-substituted monovalent having usually 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group. Hydrocarbon group is mentioned. Especially, since it is easy to mix with said (A) and (B) component about R <^3> , a methyl group and an ethyl group are preferable, and a methyl group and an ethyl group are preferable at the point which is easy to hydrolyze about R <^4> , For R ⁵ , a straight chain or branched alkyl group having 1 to 10 carbon atoms is preferable, in terms of being easily mixed with the above-mentioned (A) and (B) components, more preferably methyl, ethyl, propyl, 2 -Methylhexyl group, 2-ethylhexyl group, and the like.

(D) component may be used individually by 1 type or in combination of 2 or more types.

Content of (D) component may be the quantity of the grade which does not produce a tack after hardening inhibition or hardening, Preferably it is the range of 0.1-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and Preferably it is the range of 0.5-5 mass parts. If it is less than 0.1 part by mass, there is a possibility that the effect on hygroscopic reflow may not be obtained. If it exceeds 10 parts by mass, problems such as inhibition of curing, tack after cure and bleeding-out may occur.

[Other Ingredients]

Other arbitrary components can be mix | blended with the composition of this invention in addition to the said (A)-(D) component in the range which does not impair the objective of this invention. The following are mentioned as the specific example. These other components may be used individually by 1 type, or may use 2 or more types together.

Compounds containing aliphatic unsaturated groups other than the component (A)

In addition to (A) component, the composition of this invention can also mix | blend the aliphatic unsaturated group containing compound which add-reacts with (B) component for the purpose of improving adhesiveness with the base material of a sealing material. As such aliphatic unsaturated group containing compounds other than (A) component, it is preferable to participate in formation of hardened | cured material, and organopolysiloxane other than (A) component which has at least 1 aliphatic unsaturated group per molecule is mentioned. The molecular structure thereof may be, for example, linear, cyclic, branched, or three-dimensional mesh. Specific examples include N-allyl-N ', N "-bis (3-trimethoxysilylpropyl) isocyanurate, N-allyl-N', N" -bis (3-triethoxysilylpropyl) isocyanur The rate etc. are mentioned.

Moreover, it is possible to mix | blend aliphatic unsaturated group containing organic compounds other than the said organopolysiloxane. Specific examples of the aliphatic unsaturated group-containing compound include monomers such as butadiene and diacrylate derived from polyfunctional alcohols; Polyolefins such as copolymers of polyethylene, polypropylene or styrene with other ethylenically unsaturated compounds (for example, acrylonitrile or butadiene); Oligomers or polymers derived from functional substituted organic compounds, such as esters of acrylic acid, methacrylic acid or maleic acid. Aliphatic unsaturated group-containing compounds other than the component (A) may be liquid or solid at room temperature.

The content of the aliphatic unsaturated group-containing compound other than the component (A) may be an amount that does not impair the object of the present invention. It is preferable that it is the range of 10 mass parts, More preferably, it is the range of 0.5-5 mass parts. If it is less than 0.1 mass part, the effect of the adhesive improvement may not be acquired, and when it exceeds 10 mass parts, problems, such as the fall of the heat resistance of hardened | cured material, may arise.

ㆍ Additional reaction control agent

In order to secure a pot life, an addition reaction controlling agent can be mix | blended with this composition. An addition reaction control agent will not be specifically limited if it is a compound which has a hardening inhibitory effect with respect to the hydrosilylation catalyst of the said (C) component, A conventionally well-known thing 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; Acetylene-based compounds such as acetylene alcohols (for example, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecin-3-ol); Compounds containing two or more alkenyl groups; Hydroperoxy compounds; Maleic acid derivatives; and the like.

The extent of the hardening inhibitory effect by the addition reaction control agent depends on the chemical structure of the addition reaction control agent. Therefore, although it is preferable to adjust the addition amount to the optimal amount about each addition reaction control agent to be used, it is about 0.0001-5 mass parts normally with respect to 100 mass parts of total of (A) component and (B) component. . By adding the optimum amount of addition reaction controlling agent, the composition is excellent in long term storage stability and heat curability at room temperature.

Other optional ingredients

In order to suppress generation | occurrence | production of coloring, turbidity, and oxidation deterioration of hardened | cured material, conventionally well-known antioxidants, such as 2, 6- di-t- butyl- 4-methyl phenol, can be mix | blended with this composition. Moreover, in order to provide resistance to light deterioration, optical stabilizers, such as a hindered amine stabilizer, can also be mix | blended with this composition. Moreover, in order to improve the intensity | strength, inorganic fillers, such as fumed silica, can also be mix | blended with this invention composition in the range which does not affect transparency of the hardened | cured material obtained from this composition, and if necessary, dyes, pigments, flame retardants, etc. You may mix | blend with invention composition.

[Hardened]

The curable organopolysiloxane composition of the present invention can be cured by a known curing method under known curing conditions. Specifically, the composition can be cured by heating at usually 80 to 200 ° C, preferably 100 to 160 ° C. The heating time may be about 0.5 minutes to 5 hours, particularly about 1 minute to 3 hours, but when precision such as for LED sealing is required, it is preferable to slightly lengthen the curing time. The form of hardened | cured material obtained is not specifically limited, For example, any of a gel hardened | cured material, an elastomer hardened | cured material, and a resin hardened | cured material may be sufficient. When using the said hardened | cured material for optical element sealing, it is preferable to use colorless and high refractive index (refractive index 1.54 or more, especially 1.54-1.65).

[Optical element sealing material]

The cured product of the composition of the present invention is excellent in heat resistance, cold resistance and electrical insulation, and also excellent in moisture absorption and reflow resistance in the same manner as the cured product of a conventional curable organopolysiloxane composition. As an optical element sealed by the sealing material containing the composition of this invention, LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, CCD, etc. are mentioned, for example. Such an optical element can be sealed by apply | coating the sealing material containing the composition of this invention to this optical element, and hardening | curing the apply | coated sealing material by a well-known hardening method specifically, as mentioned above under well-known hardening conditions.

[Example]

Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example.

In addition, in the following example, a viscosity is the value measured at 25 degreeC using the rotational viscometer. The refractive index measured the refractive index of 589 nm at 25 degreeC using the Atago Digital Digital Refractometer RX-5000, and the hardness was measured according to JIS-K6249. In addition, in the following example, a part represents a mass part.

In addition, in the following example, the symbol which shows the average composition of silicone oil or a silicone resin represents the following units. In addition, the number-of-moles of each silicone oil or each silicone resin show the number-of-moles of the vinyl group or SiH group 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

Production Example 1 Preparation of Platinum Catalyst

The reaction product of chloroplatinic acid and sym-tetramethyldivinyldisiloxane was diluted with a silicone oil having a viscosity of 0.7 Pa · s, average composition formula: M ^Vi ₂ D ₁₉ D ^Φ ₉ so that the platinum content was 1.0 mass%, The platinum catalyst (catalyst A) used in the present Example and the comparative example was manufactured.

Production Example 2 Average Compositional Formula: Synthesis of 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 added, 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 ° C. Thereafter, stirring was continued at 60 ° C to 65 ° C for 2 hours. After cooling to room temperature, the aqueous phase was separated. The organic phase was washed with sodium sulfate water, and then 4.3 g of potassium hydroxide was added, followed by stirring at 130 ° C to 140 ° C for 12 hours. After removing 700 g of xylene, the mixture was cooled to 50 ° C. to 60 ° C., 21.8 g of chlorotrimethylsilane and 19.9 g of potassium acetate were further added, and stirring was continued at 50 ° C. to 60 ° C. for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a xylene solution of a colorless transparent average composition formula: M ^Vi ₁ T ^Φ ₃ silicone resin (about 50 mass% of nonvolatile matter).

Preparation Example 3 Synthesis of Silicone Resin of Average Composition Formula: D ^Vi ₁ T ^Φ ₄

4,500 g of water and 1,605 g of toluene were added to a 10 L flask, and a mixed solution of 1,862 g of trichlorophenylsilane, 310 g of dichloromethylvinylsilane, and 384 g of toluene was added dropwise so that the internal temperature did not exceed 60 ° C. After that, stirring was continued for 2 hours at 60 ° C to 65 ° C. After cooling to room temperature, the aqueous phase was separated. The organic phase was washed with sodium bicarbonate water, 0.5 g of a 50% by mass aqueous potassium hydroxide solution was then added, and stirring was continued at 100 ° C to 110 ° C for 2 hours. After cooling to 40 to 45 degreeC, 1.45 g of chlorotrimethylsilane and 5.05 g of potassium acetate were added, and stirring was continued at 40 to 45 degreeC for 2 hours. Then, toluene was removed so that a non volatile matter might be about 50 mass% by concentration under reduced pressure. After cooling to room temperature, the mixture was filtered to obtain a toluene solution of a colorless transparent average composition formula: D ^Vi ₁ T ^Φ ₄ silicone resin (about 50 mass% of nonvolatile matter).

Production Example 4 Synthesis of Silicone Oil of Average ^Composition M ^ΦVi ₂ D ^Φ _3.6

200 g of water and 117 g of toluene were put into a 500 mL flask, and it heated at 75 degreeC, 100 g of dichlorodiphenylsilanes were dripped there, and stirring was continued at 80 degreeC for 3 hours. After cooling to room temperature, the aqueous phase was separated. The organic phase was dried over 10 g of anhydrous sodium sulfate, filtered and fractionated to obtain a toluene solution of dichlorodiphenylsilane hydrolyzed oligomer. Toluene was removed by concentration under reduced pressure, and 30.6 g of dimethyldiphenyldivinyldisiloxane was added and mixed. Furthermore, 5.0 g of concentrated sulfuric acid was added, and condensation reaction was performed for 5 hours on 50 degreeC / 15 mmHg conditions. 100 g of toluene and 100 g of 10 mass% sodium sulfate water were added and mixed, and the water phase was separated. The organic phase was washed with sodium bicarbonate water and washed with water, and then toluene was removed by concentration under reduced pressure. The resulting turbid liquid was filtered, and the colorless and transparent and which has a viscosity at 25 ℃ about 2,000 mPa · s average composition formula: M ^Vi ₂ D ^{Φ Φ} _3.6 to obtain a silicone oil of.

Example 1

Average composition formula: 22 parts of silicone oil of M ^{Φ Vi} ₂ D ^Φ _3.6 , average composition formula: 53 parts of silicone resin of M ^Vi ₁ T ^Φ ₃ , average composition formula: 22 parts of organohydrogenpolysiloxane of M ^H ₂ D ^Φ ₁ , and A mixture of 1 part of a compound (additive A) having an ester bond represented by the following formula (4) and a methoxysilyl group is mixed with 0.0056 parts of 3-methyl-1-dodecine-3-ol and 0.05 parts of catalyst A as a control agent. An organopolysiloxane composition was obtained. The composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours. The resulting elastomer (A) had a hardness of 27 at Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 1.

[Example 2]

A composition was prepared according to Example 1, except that instead of the additive A, one part of a compound (additive B) having an ester bond and a methoxysilyl group represented by the following formula (5) was used. When the organopolysiloxane composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours, the resulting elastomer (B) had a hardness of 25 in Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 1.

Comparative Example 1

Instead of Additive A, 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. The organopolysiloxane composition was cured by heating at 100 ° C. for 2 hours and further at 150 ° C. for 4 hours. The resulting elastomer (C) had a hardness of 40 in Shore D. Further test results of hygroscopic reflow are shown in Table 1 below. Indicated.

Comparative Example 2

Instead of the additive A, a composition was prepared according to Example 1 except that 1 part of 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. When the organopolysiloxane composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours, the resulting elastomer (D) had a hardness of 30 in Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 1.

Comparative Example 3

Instead of the additive A, a composition was prepared according to Example 1 except that 1 part of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. When 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 (E) was 28 in Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 1.

[Example 3]

Average composition formula: 55.1 parts of silicone oil of M ^{Φ Vi} ₂ D ^Φ _3.6 , Average composition formula: 45 parts of silicone resin of D ^Vi ₁ T ^Φ ₄ , Average composition formula: 28.6 parts of organohydrogenpolysiloxane of M ^H ₂ D ^Φ ₁ , and the A mixture of an ester bond represented by the formula (4) and one part of a compound having an methoxysilyl group (additive A) is mixed with 0.2 parts of 3-methyl-1-dodecine-3-ol and 0.3 parts of catalyst A as a control agent A polysiloxane composition was obtained. When the 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 (F) was 32 in Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 2.

Example 4

A composition was prepared according to Example 3, except that instead of the additive A, 1 part of the compound (additive B) having an ester bond represented by the formula (5) and a methoxysilyl group was used. When 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 in Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 2.

[Comparative Example 4]

Instead of Additive A, a composition was prepared according to Example 3, except that 1 part of N-allyl-N ', N "-bis (3-triethoxysilylpropyl) isocyanurate (additive C) was used. The organopolysiloxane composition was cured by heating at 100 ° C. for 2 hours and further at 150 ° C. for 4 hours, and the resulting elastomer (H) had a hardness of 50 in Shore D. Further test results of hygroscopic reflow are shown in Table 2 below. Indicated.

[Comparative Example 5]

A composition was prepared according to Example 3 except that instead of Additive A, one part of 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. The organopolysiloxane composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours. The resulting elastomer (I) had a hardness of 30 in Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 2.

[Comparative Example 6]

A composition was prepared according to Example 3 except that instead of the additive A, one part of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. When the organopolysiloxane composition was cured by heating at 100 ° C for 2 hours and further at 150 ° C for 4 hours, the resulting elastomer (J) had a hardness of 33 in Shore D. In addition, the test results of the hygroscopic reflow are shown in Table 2.

Assessment Methods

Hygroscopic Reflow Test Package

As a test package for the hygroscopic reflow test, a simple package as shown in FIG. 1 without an LED chip was used. Here, (1) is a case, (2, 3) is a lead electrode, (4) is sealing resin (hardened | cured material of the organopolysiloxane composition obtained by the Example and the comparative example). Curing conditions of the organopolysiloxane composition are 2 hours at 100 ° C and 4 hours at 150 ° C.

Test method of hygroscopic reflow

After ten produced test packages were put into 85 degreeC and the constant temperature / humidity tank of 85% RH for 24 hours, the infrared reflow apparatus (260 degreeC) was let through once, and the change of an external appearance was observed. The results are shown in Tables 1 and 2. In addition, the thing which the crack of resin and peeling from the LED package were confirmed was counted as NG.

1 case
2, 3 lead electrodes
4 sealing resin

Claims (5)

(A) organopolysiloxane which has at least 2 alkenyl groups couple | bonded with the silicon atom in 1 molecule represented by following average composition formula 1,
<Mean Composition 1>

Wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group from each other, R ¹ At least one is an aryl group, 0.1 to 40 mol% of the total R ¹ is an alkenyl group, and a is a positive number satisfying 1 ≦ a ≦ 3)
(B) organohydrogenpolysiloxane represented by the following average composition formula 2,
<Mean Composition 2>

(Wherein R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group, or alkoxy group, other than aliphatic unsaturated group, b and c are 0.7 ≦ b ≦ 2.1, 0.001 ≦ c ≦ 1.0 and 0.8 ≦ positive to satisfy b + c≤3.0)
(C) a hydrosilylation catalyst comprising a platinum group metal,
(D) a compound represented by the following formula (3)
<Formula 3>

(Wherein R ³ , R ⁴ , R ⁵ are the same or different unsubstituted or substituted monovalent hydrocarbon groups, respectively, and d is 0, 1 or 2)
Curable organopolysiloxane composition comprising a. The curable organopolysiloxane composition according to claim 1, wherein the component (B) has at least one silicon atom-bonded aryl group in one molecule. Curable organopolysiloxane composition of Claim 1 whose addition amount of (D) component is 0.1-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component. The optical element sealing material containing the composition of any one of Claims 1-3. The optical element sealed with the hardened | cured material of the sealing material of Claim 4.

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