TWI798283B - Addition hardening polysiloxane composition, cured product, optical element - Google Patents

Abstract

其中，作為前述平均組成式(1)中之(R² R¹ ₂ SiO_1/2 )單元，其一分子中至少具有兩個以上由下述式(2)所表示之矽氧烷單元，

(A-2)下述式(3)所表示之直鏈狀有機聚矽氧烷：質量比(A-1)：(A-2)係為100：0～50：50之量。

(B)一分子中至少具有兩個以上由下述式(4)所表示之矽氧烷單元之有機氫聚矽氧烷：

(C)包含鉑族金屬之矽氫化觸媒。[Problem] To provide an addition-curable polysiloxane composition, which provides a cured product with high thermal discoloration resistance and high sulfuration resistance, and a highly reliable optical element sealed by the cured product. [Solution] An addition-hardening polysiloxane composition comprising: (A-1) an organopolysiloxane, which is a branched organopolysiloxane represented by the following average composition formula (1) :

Wherein, as the (R ² R ¹ ₂ SiO _1/2 ) unit in the aforementioned average composition formula (1), there are at least two siloxane units represented by the following formula (2) in one molecule,

(A-2) Linear organopolysiloxane represented by the following formula (3): The mass ratio (A-1):(A-2) is an amount of 100:0 to 50:50.

(B) Organohydrogenpolysiloxane having at least two siloxane units represented by the following formula (4) in one molecule:

(C) A hydrosilation catalyst containing a platinum group metal.

Description

Addition hardening polysiloxane composition, cured product, optical element

The present invention relates to an addition hardening polysiloxane composition, its cured product, and an optical element sealed with the cured product.

A device having a light emitting diode (LED) as an optical semiconductor element is usually configured by sealing the LED mounted on a substrate with a transparent resin sealing material. Epoxy resin has been used as this sealing material. However, in recent years, cracks or cracks have occurred on the resin due to the increase in heat generation or the shortening of the light wavelength associated with the miniaturization of semiconductor packages and the increase in brightness of LEDs. Yellowing, low reliability.

Therefore, from the viewpoint of heat resistance and heat discoloration resistance, silicone resin compositions as sealing materials have attracted attention, and addition reaction-curable silicone resin compositions can be shortened by heating. It hardens within a short period of time, so the productivity is high, and it is used as a sealing material for LEDs (Patent Document 1).

On the other hand, since polysiloxane resin has higher air permeability than epoxy resin, the silver substrate of LED may be corroded due to sulfur compounds present in the air. Use a polysiloxane composition having a main chain composed of dimethylsiloxane units and diphenylsiloxane units, or a main chain composed of methylphenylsiloxane units (Patent Document 2 In the case of ), although the thermal discoloration resistance is excellent, and the corrosion of the silver substrate can be suppressed to some extent, the sulfidation resistance is still insufficient.

On the other hand, a sealing material for optical semiconductor elements using an organically modified organopolysiloxane composition containing a polycyclic hydrocarbon skeleton-containing component has been proposed (Patent Documents 3 and 4). The sulfuration resistance of such a composition is generally better than that of a sealing material using phenyl-based polysiloxane, and it can suppress the corrosion of the silver substrate. However, it has serious discoloration when exposed to high temperature, and the heat discoloration resistance is not sufficient. Therefore, a sealing material for an optical semiconductor element that is excellent in transparency and mechanical strength and satisfies both sulfuration resistance and thermal discoloration resistance has been sought. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2004-292714 [Patent Document 2] Japanese Unexamined Patent Publication No. 2010-132795 [Patent Document 3] Japanese Patent Laid-Open No. 2008-069210 [Patent Document 4] Japanese Patent Laid-Open No. 2012-046604

[Problem to be Solved by the Invention]

The present invention is made in view of the above facts, and an object is to provide an addition-curable polysiloxane composition, which provides a hardened product with high heat discoloration resistance and high vulcanization resistance, and a product sealed by the cured product. Optical components with high reliability. [Means to solve the problem]

(式中，R¹ 為不含烯基之同種或異種之非取代或者取代之一價烴基，全R¹ 之至少10莫耳%為芳基，R² 為烯基；惟，a、b、c、d、e、f、g係各自滿足a≧0、b＞0、c≧0、d≧0、e≧0、f≧0及g≧0之數，惟，e+f+g＞0，且，滿足a+b+c+d+e+f+g=1之數)，其中，作為前述平均組成式(1)中之(R² R¹ ₂ SiO_1/2 )單元，其一分子中至少具有兩個以上由下述式(2)所表示之矽氧烷單元，

(式中，R¹ 係與前述相同。) (A-2)下述式(3)所表示之直鏈狀有機聚矽氧烷：質量比(A-1)：(A-2)係為100：0～50：50之量(惟，(A-2)成分係比0質量份多)。

(式中，R^1’ 為不含烯基之同種或異種之非取代或者取代之一價烴基，R³ 為甲基或苯基，h為0～50之整數，i為0～100之整數，各矽氧烷單元之排列順序為任意。惟，h為0時，R³ 為苯基，且，i為1～100之整數，被附加括弧之矽氧烷單元之排列可為無規亦可為嵌段。) (B)一分子中至少具有兩個以上由下述式(4)所表示之矽氧烷單元之有機氫聚矽氧烷：相對於(A-1)及(A-2)成分中之1個與矽原子鍵結之烯基，(B)成分中與矽原子鍵結之氫原子之數量為0.1～5.0個之量，

，及 (C)包含鉑族金屬之矽氫化觸媒。In order to achieve the above-mentioned problems, the present invention provides an addition-curable polysiloxane composition comprising: (A-1) organopolysiloxane, which is a branched polysiloxane represented by the following average composition formula (1): Organopolysiloxanes:

(wherein, R ¹ is a non-substituted or substituted monovalent hydrocarbon group of the same or different species that does not contain an alkenyl group, at least 10 mole percent of all R ¹ is an aryl group, and R ² is an alkenyl group; however, a, b, c, d, e, f, g are the numbers satisfying a≧0, b>0, c≧0, d≧0, e≧0, f≧0 and g≧0, but e+f+g> 0, and satisfy the number of a+b+c+d+e+f+g=1), wherein, as the (R ² R ¹ ₂ SiO _1/2 ) unit in the aforementioned average composition formula (1), its There are at least two siloxane units represented by the following formula (2) in one molecule,

(In the formula, ^R1 is the same as above.) (A-2) Linear organopolysiloxane represented by the following formula (3): mass ratio (A-1): (A-2) is 100: 0 to 50: 50 (provided that the component (A-2) is more than 0 parts by mass).

(wherein, R ^1' is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species that does not contain an alkenyl group, R ³ is a methyl group or a phenyl group, h is an integer of 0 to 50, and i is an integer of 0 to 100 , the arrangement order of each siloxane unit is arbitrary. However, when h is 0, ^R3 is a phenyl group, and i is an integer from 1 to 100, and the arrangement of the siloxane units in brackets can be random or It can be a block.) (B) An organohydrogenpolysiloxane having at least two siloxane units represented by the following formula (4) in one molecule: relative to (A-1) and (A- 2) One alkenyl group bonded to a silicon atom in the component, the number of hydrogen atoms bonded to a silicon atom in the component (B) is 0.1 to 5.0,

, and (C) a hydrosilation catalyst comprising a platinum group metal.

Such an addition-curable polysiloxane composition can provide a cured product having high thermal discoloration resistance and high vulcanization resistance.

Also, R ¹ in the aforementioned formula (2) and R ^1' in the aforementioned formula (3) are preferably phenyl or methyl.

If it satisfies such conditions, it can be used suitably as (A-1) component.

Also, the blending amount of the aforementioned (B) component is based on one alkenyl group bonded to the silicon atom in the aforementioned (A-1) and the aforementioned (A-2) components, which is bonded to the aforementioned (B) component The number of silicon atoms and hydrogen atoms is preferably 1.0 to 3.0.

Such a blending amount can impart high strength and vulcanization resistance to the cured product of the composition.

(式中，各矽氧烷單元之排列順序可為無規亦可為嵌段。)

The organohydrogenpolysiloxane of the aforementioned (B) component is preferably an organohydrogenpolysiloxane represented by the following formula (5) or (6).

(In the formula, the arrangement order of each siloxane unit can be random or block.)

If it satisfies such conditions, it can be used suitably as (B) component.

Also, the present invention provides a cured product obtained by curing the above-mentioned addition-curable polysiloxane composition.

Such a cured product has good strength characteristics, high vulcanization resistance, high thermal discoloration resistance, and a high refractive index.

In addition, the present invention provides an optical element sealed by the above cured product.

The cured product of the present invention has good strength properties, high vulcanization resistance, high heat discoloration resistance, and high refractive index. Therefore, an optical element sealed with such a cured product has high reliability. [Invention effect]

As mentioned above, the addition-curable polysiloxane composition of the present invention can provide a cured product with high transparency, high refractive index, high vulcanization resistance, and excellent thermal discoloration resistance. Therefore, such a cured product of the present invention can be suitably used as an optical element sealing material.

As mentioned above, it is required to develop an addition-curable polysiloxane composition that provides a cured product having high thermal discoloration resistance and high vulcanization resistance, and a highly reliable optical element sealed by the cured product.

The inventors of the present invention, as a result of actively examining the above-mentioned problems, found that if it is an addition-curable polysiloxane composition containing components (A-1), (A-2), (B) and (C) described later , then the above-mentioned problems can be achieved, and the present invention has been further completed.

(式中，R¹ 為不含烯基之同種或異種之非取代或者取代之一價烴基，全R¹ 之至少10莫耳%為芳基，R² 為烯基；惟，a、b、c、d、e、f、g係各自滿足a≧0、b＞0、c≧0、d≧0、e≧0、f≧0及g≧0之數，惟，e+f+g＞0，且，滿足a+b+c+d+e+f+g=1之數)，其中，作為前述平均組成式(1)中之(R² R¹ ₂ SiO_1/2 )單元，其一分子中至少具有兩個以上由下述式(2)所表示之矽氧烷單元，

(式中，R¹ 係與前述相同。) (A-2)下述式(3)所表示之直鏈狀有機聚矽氧烷：質量比(A-1)：(A-2)係為100：0～50：50之量(惟，(A-2)成分係比0質量份多)。

(式中，R^1’ 為不含烯基之同種或異種之非取代或者取代之一價烴基，R³ 為甲基或苯基，h為0～50之整數，i為0～100之整數，各矽氧烷單元之排列順序為任意。惟，h為0時，R³ 為苯基，且，i為1～100之整數，被附加括弧之矽氧烷單元之排列可為無規亦可為嵌段。) (B)一分子中至少具有兩個以上由下述式(4)所表示之矽氧烷單元之有機氫聚矽氧烷：相對於(A-1)及(A-2)成分中之1個與矽原子鍵結之烯基，(B)成分中與矽原子鍵結之氫原子之數量為0.1～5.0個之量，

，及 (C)包含鉑族金屬之矽氫化觸媒。That is, the present invention is an addition-hardening polysiloxane composition, which comprises: (A-1) organopolysiloxane, which is a branched organopolysiloxane represented by the following average composition formula (1): Oxygen:

(wherein, R ¹ is a non-substituted or substituted monovalent hydrocarbon group of the same or different species that does not contain an alkenyl group, at least 10 mole percent of all R ¹ is an aryl group, and R ² is an alkenyl group; however, a, b, c, d, e, f, g are the numbers satisfying a≧0, b>0, c≧0, d≧0, e≧0, f≧0 and g≧0, but e+f+g> 0, and satisfy the number of a+b+c+d+e+f+g=1), wherein, as the (R ² R ¹ ₂ SiO _1/2 ) unit in the aforementioned average composition formula (1), its There are at least two siloxane units represented by the following formula (2) in one molecule,

(In the formula, ^R1 is the same as above.) (A-2) Linear organopolysiloxane represented by the following formula (3): mass ratio (A-1): (A-2) is 100: 0 to 50: 50 (provided that the component (A-2) is more than 0 parts by mass).

(wherein, R ^1' is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species that does not contain an alkenyl group, R ³ is a methyl group or a phenyl group, h is an integer of 0 to 50, and i is an integer of 0 to 100 , the arrangement order of each siloxane unit is arbitrary. However, when h is 0, ^R3 is a phenyl group, and i is an integer from 1 to 100, and the arrangement of the siloxane units in brackets can be random or It can be a block.) (B) An organohydrogenpolysiloxane having at least two siloxane units represented by the following formula (4) in one molecule: relative to (A-1) and (A- 2) One alkenyl group bonded to a silicon atom in the component, the number of hydrogen atoms bonded to a silicon atom in the component (B) is 0.1 to 5.0,

, and (C) a hydrosilation catalyst comprising a platinum group metal.

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

[Addition hardening polysiloxane composition] The addition-curable polysiloxane composition of the present invention contains the following components (A-1), (A-2), (B), and (C). Hereinafter, each component is demonstrated in detail.

(式中，R¹ 為不含烯基之同種或異種之非取代或者取代之一價烴基，全R¹ 之至少10莫耳%為芳基，R² 為烯基；惟，a、b、c、d、e、f、g係各自滿足a≧0、b＞0、c≧0、d≧0、e≧0、f≧0及g≧0之數，惟，e+f+g＞0，且，滿足a+b+c+d+e+f+g=1之數)，其中，作為前述平均組成式(1)中之(R² R¹ ₂ SiO_1/2 )單元，其一分子中至少具有兩個以上由下述式(2)所表示之矽氧烷單元。

(式中，R¹ 係與前述相同。)<(A-1) Branched organopolysiloxane> Component (A-1) is a branched organopolysiloxane represented by the following average composition formula (1):

(wherein, R ¹ is a non-substituted or substituted monovalent hydrocarbon group of the same or different species that does not contain an alkenyl group, at least 10 mole percent of all R ¹ is an aryl group, and R ² is an alkenyl group; however, a, b, c, d, e, f, g are the numbers satisfying a≧0, b>0, c≧0, d≧0, e≧0, f≧0 and g≧0, but e+f+g> 0, and satisfy the number of a+b+c+d+e+f+g=1), wherein, as the (R ² R ¹ ₂ SiO _1/2 ) unit in the aforementioned average composition formula (1), its It has at least two or more siloxane units represented by the following formula (2) in one molecule.

(In the formula, R ¹ is the same as above.)

Component (A-1) is an essential component for obtaining the reinforcement of the polysiloxane composition, and contains either one or both of SiO _3/2 units and SiO _4/2 units.

(A-1) One molecule of the component has two or more siloxane units represented by the above formula (2). By having the siloxane unit represented by the above formula (2), it is possible to impart high strength, high refractive index, and high vulcanization resistance to the cured product of the polysiloxane composition.

As the above-mentioned R ¹ , it is not particularly limited as long as it does not contain an alkenyl group, and examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; cyclopentyl; Cycloalkyl groups such as phenyl, cyclohexyl, etc.; aryl groups such as phenyl, tolyl, stubble, naphthyl, etc.; aralkyl groups such as benzyl, phenethyl, etc.; chloromethyl, 3-chloropropyl, 3, Halogenated alkyl groups such as 3,3-trifluoropropyl, etc. are usually 1 to 12 carbon atoms, preferably 1 to 10, more preferably 1 to 8 unsubstituted or halogen-substituted valent hydrocarbon groups, especially Preferably methyl.

At least 10 mole % of all R ¹ are aryl. If the aryl group is less than 10 mol%, higher hardness and high vulcanization resistance cannot be imparted to the cured product. Examples of the aryl group include phenyl, tolyl, stubble, naphthyl and the like, particularly preferably phenyl.

The above-mentioned R ² is alkenyl, preferably vinyl, allyl, ethynyl and the like with 2 to 10 carbons, more preferably alkenyl with 2 to 6 carbons, particularly preferably vinyl.

In the component (A-1), the content of the siloxane unit represented by the formula (2) is preferably in the range of 0.01 to 1 mol per 100 g of the component (A-1), more preferably in the range of 0.05 to 0.5 mol. By satisfying the above range, a hardened product having high hardness and high sulfuration resistance can be obtained.

The component (A-1) is preferably a waxy or solid three-dimensional network organopolysiloxane resin at 23°C. The so-called "waxy" means a gelatinous (rubber-like) that does not show self-fluidity at 23°C above 10,000 Pa·s, especially above 100,000 Pa·s.

(A-1) The component may be used individually by 1 type, and may use 2 or more types together.

(式中，R^1’ 為不含烯基之同種或異種之非取代或者取代之一價烴基，R³ 為甲基或苯基，h為0～50之整數，i為0～100之整數，各矽氧烷單元之排列順序為任意。惟，h為0時，R³ 為苯基，且，i為1～100之整數，被附加括弧之矽氧烷單元之排列可為無規亦可為嵌段。)<(A-2) Linear organopolysiloxane> (A-2) The component is represented by the following formula (3), and the main chain is composed of repeating units with a phenyl group in the side chain, and the molecule Two organopolysiloxanes with vinyl and phenyl groups at both ends of the chain blocked by triorganosilyloxy groups.

(wherein, R ^1' is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species that does not contain an alkenyl group, R ³ is a methyl group or a phenyl group, h is an integer of 0 to 50, and i is an integer of 0 to 100 , the arrangement order of each siloxane unit is arbitrary. However, when h is 0, ^R3 is a phenyl group, and i is an integer from 1 to 100, and the arrangement of the siloxane units in brackets can be random or Can be block.)

In the component (A-2), R ^1' in the formula (3) is the same as R ¹ in the component (A-1).

h in formula (3) is an integer of 0-50, i is an integer of 0-100, when h is 0, R ³ is phenyl and i is 1-100. If h and i are outside the above ranges, high hardness and sulfidation resistance cannot be imparted to the cured product of the composition.

The viscosity of the component (A-2) at 25°C is preferably in the range of 10 to 100,000 mPa·s, more preferably in the range of 10 to 10,000 mPa·s. If the viscosity is within the above range, there is no doubt that this component will function as a soft segment more than necessary, and the target high hardness can be obtained. Also, there is no problem that the viscosity of the composition becomes significantly higher and the workability is poor.

(A-2) The two ends of the molecular chain of the component are sealed with a triorganosilyloxy group containing a vinyl group and a phenyl group. Thereby, it becomes possible to impart high strength and vulcanization resistance to the hardened product. Specific examples of component (A-2) include two-terminal methylphenylvinyl-blocked diphenylsiloxane, single-terminal methylphenylvinyl single-terminal diphenylvinyl-blocked diphenyl base siloxane, two-terminal diphenylvinyl-blocked diphenylsiloxane, two-terminal diphenylvinyl-blocked diphenylsiloxane-methylphenylsiloxane copolymer, etc. (A-2) The component may be used individually by 1 type, and may use 2 or more types together.

The ratio of the component (A-1) to the component (A-2) is also one of the important factors of the composition of the present invention. The blending amount of (A-1) component is the mass ratio (A-1): (A-2) in the amount of 100:0 ~ 50:50 (however, (A-2) component is more than 0 mass parts) , preferably (A-1):(A-2) in the amount of 80:20 to 60:40. If the compounding quantity of (A-1) component is less than the said range, it will become difficult to obtain the cured material which has high hardness and high sulfuration resistance.

＜(B) Organohydrogenpolysiloxane＞ Component (B) initiates the hydrosilylation reaction of components (A-1) and (A-2) and acts as a cross-linking agent. An organohydrogenpolysiloxane having a siloxane unit represented by the following formula (4). Owing to the presence of this component, it is possible to impart high hardness and high vulcanization resistance to the cured product of the polysiloxane composition containing (B) component.

The molecular structure of the component (B) is not particularly limited. For example, various organohydrogenpolysiloxanes such as linear, cyclic, branched, and three-dimensional network (resin) structures can be used. In addition, (B) component may be liquid or waxy or solid at 23 degreeC.

The organohydrogen polysiloxane of component (B) has at least 2, preferably 3 to 300, and particularly preferably 3 to 100 hydrogen atoms bonded to silicon atoms in one molecule (that is, silicon hydrogen group (SiH group)). When the organohydrogenpolysiloxane of the component (B) has a straight-chain structure, these SiH groups may be located only at the end of the molecular chain and any position other than the end, or at both positions.

(B) The number (degree of polymerization) of silicon atoms in one molecule of component is preferably from 2 to 300, more preferably from 3 to 200, and still more preferably from 4 to 150.

(式中，R⁴ 為不含烯基、互相為相同或異種之非取代或者取代，且碳原子數較佳為1～12、更佳為1～10、再更佳為1～8之鍵結於矽原子之一價烴基，係舉出與(A-1)成分中之R¹ 及(A-2)成分中之R^1’ 相同者。又，j及k係較佳為滿足0.7≦j≦2.1、0.001≦k≦1.0，且0.8≦j+k≦3.0之正數，更佳為滿足1.0≦j≦2.0、0.01≦k≦1.0，且1.55≦j+k≦2.5之正數。)As (B) component, for example, organohydrogenpolysiloxane represented by the following average composition formula (7) can be used.

(wherein, R ⁴ is a non-substituted or substituted non-alkenyl group, the same or different species, and the number of carbon atoms is preferably 1-12, more preferably 1-10, and more preferably 1-8 bonds A valent hydrocarbon group bonded to a silicon atom is the same as R ¹ in the component (A-1) and R ^1' in the component (A-2). Also, j and k are preferably satisfying 0.7≦ A positive number of j≦2.1, 0.001≦k≦1.0, and 0.8≦j+k≦3.0, preferably a positive number satisfying 1.0≦j≦2.0, 0.01≦k≦1.0, and 1.55≦j+k≦2.5.)

Specific examples of component (B) include, for example, both-terminal dimethylphenylsiloxy-blocked methylphenylhydrosiloxane-dimethylsiloxane cyclic copolymer, both-terminal methyl Phenylhydrosiloxy-blocked diphenyl polysiloxane, two-terminal methylphenylhydrosiloxy-blocked dimethylsiloxane・diphenylsiloxane・methylhydrogensiloxane copolymer wait.

(式中，各矽氧烷單元之排列順序可為無規亦可為嵌段。)

More specifically, as (B) component, the organohydrogenpolysiloxane represented by following formula (5) or (6) is mentioned.

(In the formula, the arrangement order of each siloxane unit can be random or block.)

The blending amount of component (B) is the amount of hydrogen atom bonded to silicon atom in component (B) relative to one alkenyl group bonded to silicon atom in components (A-1) and (A-2). The number is 0.1 to 5.0, preferably 0.5 to 3.0, more preferably 1.0 to 3.0. If the blending amount of the component (B) is outside the above-mentioned range, high hardness and sulfuration resistance cannot be imparted to the cured product of the composition.

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

＜(C) Hydrosilation catalyst containing platinum group metals＞ The hydrosilylation catalyst containing platinum group metals in component (C) acts as an addition reaction catalyst and promotes the alkenyl groups in components (A-1) and (A-2) and the bond in component (B) Addition reactions of hydrogen atoms bonded to silicon atoms. Specific examples thereof include platinum, palladium, rhodium, etc., chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid and enols, vinylsiloxanes, or acetylene compounds, Platinum group metals such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, or their compounds, but platinum group compounds are particularly preferred.

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

The blending amount of (C) component is sufficient as an effective amount as a catalyst, but with respect to the total amount of (A-1), (A-2) component and (B) component, it is converted into a catalytic metal element and expressed as The range of 1-500 ppm is preferable on a mass basis, and the range of 1-100 ppm is more preferable. If the above-mentioned range is satisfied, the reaction rate of the addition reaction becomes appropriate, and a hardened product having high strength can be obtained.

＜(D)Other ingredients＞ In addition to the above-mentioned components, in order to improve the adhesiveness of the composition of the present invention to the resin, an adhesiveness improver may also be added.

As the adhesion improving agent, from the viewpoint of imparting self-adhesiveness to the addition reaction hardening type composition of the present invention, organosilicon compounds such as silane and siloxane containing functional groups imparting adhesiveness, non-polysilicon compounds, etc. can be used. Oxygen-based organic compounds, etc.

Specific examples of functional groups that impart adhesiveness include alkenyl groups such as vinyl and allyl groups bonded to silicon atoms, and hydrogen atoms; epoxy groups bonded to silicon atoms through carbon atoms (for example, γ -glycidoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, etc.), or acryloxy (for example, γ-acryloxypropyl, etc.) or methacryloxy group (for example, γ-methacryloxypropyl group, etc.); alkoxysilyl group such as trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc.) and the like.

Organosilicon compounds containing functional groups that impart adhesion include silane coupling agents, siloxanes with alkoxysilyl groups and organic functional groups, and introduction of alkoxysilanes into organic compounds with reactive organic groups. base compounds, etc.

Moreover, examples of non-polysiloxane-based organic compounds include allyl organic acids, epoxy-based ring-opening catalysts, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds.

In order to improve the reinforcement, micro powder silicon dioxide can also be blended into the composition of the present invention. The specific surface area (BET method) of the fine powdered silicon dioxide is preferably at least 50 m ² /g, more preferably 50-400 m ² /g, particularly preferably 100-300 m ² /g. When the specific surface area is 50 m ² /g or more, sufficient reinforcement can be imparted to the cured product.

In the present invention, as such micropowder silica, conventional ones that have been used as reinforcing fillers for polysiloxane rubber can be used, for example, fume silica (dry silica), precipitated silica, etc., can be used. Silica (wet silica), etc. Micro-powder silicon dioxide can be used directly, but in order to impart good fluidity to the composition, it is better to use methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, etc. Organosilicon compounds such as dimethylpolysiloxane, hexamethyldisilazane, divinyltetramethyldisilazane, hexaorganodisilazane, etc. processor. One type of reinforcing silica may be used alone, or two or more types may be used in combination.

Moreover, in the composition of this invention, the reaction inhibitor which has hardening inhibitory effect with respect to the addition reaction catalyst of (C) component can be used. Examples of the reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene-based compounds; Hydroxy compounds; maleic acid derivatives, etc.

Since the degree of the hardening inhibitory effect of the reaction inhibitor is greatly different according to the chemical structure of the reaction inhibitor, the blending amount of the reaction inhibitor is preferably adjusted to the most appropriate amount according to the reaction inhibitor used . If the compounding amount of the reaction inhibitor is an optimum amount, there is no doubt that the long-term storage stability of the composition at room temperature cannot be obtained, or the hardening of the composition is hindered. Usually, it is preferable that it is 0.001-5 mass parts with respect to a total of 100 mass parts of organopolysiloxane of (A-1) component, (A-2) component, and (B) component.

In addition, examples of other optional components include inorganic fillers such as crystalline silica, hollow fillers, and silsesquioxanes, and combinations of these fillers with organoalkoxysilane compounds, organochlorine compounds, and the like. Silane compounds, organosilazane compounds, low molecular weight siloxane compounds and other organosilicon compounds with surface hydrophobized fillers; silicone rubber powder, silicone resin powder, etc.

[hardened object] Also, the present invention provides a cured product obtained by curing the above-mentioned addition-curable polysiloxane composition.

The curing method and conditions of the addition-curable polysiloxane composition of the present invention can adopt known curing methods and conditions. As an example, it can be cured at 100-180° C. for 10 minutes to 5 hours.

The cured product obtained by curing the addition-curable polysiloxane composition of the present invention has high strength, high refractive index, and excellent sulfuration resistance, especially because of its high light transmittance, and can be used as a sealing material for semiconductor elements and optical components. Or used as a protective coating material for electricity and electronics.

[Optical element] In addition, the present invention provides an optical element sealed by the above cured product.

As mentioned above, the hardened material of the present invention has high strength and high refractive index, excellent vulcanization resistance, and especially high light transmittance. Therefore, an optical element sealed with such a cured product has high reliability. [Example]

Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.

In addition, the viscosity in an Example is the value measured using the rotational viscometer at 25 degreeC.

[Examples 1-3, Comparative Examples 1-3] The following components were mixed in the blending ratio shown in Table 1 to prepare an addition-curable polysiloxane composition. In addition, the part in Table 1 shows a mass part.

(A-1) Composition: (CH ₂ =CH(CH ₃ )(C ₆ H ₅ )SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) _3.8 (SiO ₂ ) _4.3 Branched polymer silicone resin

(A-2) Composition: represented by (A-2-a)(CH ₂ =CH(CH ₃ )(C ₆ H ₅ )SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO) ₃ Linear polysiloxane oil with a viscosity of 2,000mPa·s (A-2-b)(CH ₂ =CH(CH ₃ )(C ₆ H ₅ )SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ (A-2-c)(CH ₂ =CH(CH ₃ ) ₂ SiO _1/2 ) ₂ ((C ₆ H ₅ ) ₂ SiO ) ₃ represents linear polysiloxane oil with a viscosity of 700mPa・s

(式中，各矽氧烷單元之排列順序為任意。)(B) Component: (Ba) organohydrogenpolysiloxane represented by the following formula (8)

(In the formula, the arrangement order of each siloxane unit is arbitrary.)

(Bb) organohydrogenpolysiloxane represented by the following formula (9)

(Bc) organohydrogenpolysiloxane represented by the following formula (10)

(式中，各矽氧烷單元之排列順序為任意。)(Bd) organohydrogenpolysiloxane represented by the following formula (11)

(In the formula, the arrangement order of each siloxane unit is arbitrary.)

(Be) organohydrogenpolysiloxane represented by the following formula (12)

(C) Ingredients Platinum catalyst: a complex compound of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane so that the platinum content becomes 1.0% by mass, and dimethylorganopolysilicon with a viscosity of 600mPas Catalyst diluted with oxane.

Other components: (D) Ethynylcyclohexanol (Ea) Adhesive imparting component represented by the following formula (13)

(Eb) Adhesive imparting component represented by the following formula (14)

The following evaluations were performed on the addition-curable polysiloxane compositions obtained in Examples 1-3 and Comparative Examples 1-3, and the results are shown in Table 2. In addition, in Comparative Example 4, SCR-1016 manufactured by Shin-Etsu Chemical Co., Ltd. was used as the organically modified polysiloxane material not having the siloxane unit represented by the above formula (2).

(hardness) The composition was poured into a mold so as to have a thickness of 2 mm, and it was hardened at 150° C. for 4 hours. The Type D hardness of the hardened product is measured based on JIS K6253. If the Type D hardness is 50 or more, it can be judged as a material with sufficiently high hardness.

(refractive index) The refractive index was measured at 25° C. using a digital refractometer RX-5000 manufactured by ATAGO at a wavelength of 589 nm. If the refractive index is 1.5 or more, it is a sufficiently high refractive material.

(Production of Optical Semiconductor Package (PKG)) Prepare LED packaging substrates [SMD5050 (I-CHIUN PRECISION INDUSTRY CO., manufactured by I-CHIUN PRECISION INDUSTRY CO.. and EV-B35A (manufactured by SemiLEDs Co., Ltd.) as an optical semiconductor element.

Using a die-bonding machine (AD-830 manufactured by ASM Corporation), quantitatively transfer the die-bonding material KER-3000-M2 manufactured by Shin-Etsu Chemical Co., Ltd. on the silver-plated first wire of the package substrate by molding. An optical semiconductor element is mounted thereon. Next, put the packaging substrate into an oven, heat and harden the die-bonding material (150° C., 2 hours), and electrically connect the lower electrode of the optical semiconductor element to the first wire. Next, using wire bonding, the LED packaging substrate on which the optical semiconductor element is mounted is electrically connected to the upper electrode of the optical semiconductor element and the second wire using a gold wire (FA 25 μm manufactured by Tanaka Denshi Kogyo Co., Ltd.) to obtain a mounting light. One packaging substrate for LEDs of semiconductor components.

(Vulcanization test) The composition is sealed in the designated PKG, and it is cured under the condition of 150°C x 4 hours. Next, 0.1 g of sulfur powder was put into a 100 g bottle, and the resin-encapsulated PKG was put in and sealed. After 70°C×48 hours, the PKG was taken out, and the color of the silver substrate was visually observed as its sulfur resistance. If the silver substrate of PKG turns black, it is marked as x, if it is not discolored, it is marked as ○, and if it is ○, it means excellent sulfuration resistance.

(oxygen transmission rate) The composition was poured into a mold to have an outer diameter of 100 mmΦ and a thickness of 1 mm, and it was hardened at 150° C. for 4 hours. The cured product was measured for oxygen transmission rate using an oxygen transmission rate measuring device 8000 series manufactured by Illinois Corporation. The lower the value, the material has excellent gas barrier properties and high sulfuration resistance. Pack

(light transmittance) The composition was poured into a mold so as to have a thickness of 2 mm, and it was hardened at 150° C. for 4 hours. Measure the transmittance of the hardened product at a wavelength of 400nm. If it is 80% or more, it is a material with sufficiently high transparency.

(heat discoloration resistance) The composition was poured into a mold so as to have a thickness of 2 mm, and it was hardened at 150° C. for 4 hours. After exposing the cured product under the condition of 180°C×100 hours, measure the transmittance at a wavelength of 400nm. The smaller the difference from the initial light transmittance, the more excellent the heat discoloration resistance was evaluated.

1)相對於(A-1)成分及(A-2)成分中之1個與矽原子鍵結之烯基，(B)成分中與矽原子鍵結之氫原子之數量

1) The number of hydrogen atoms bonded to the silicon atom in the component (B) relative to one of the alkenyl groups bonded to the silicon atom in the component (A-1) and (A-2)

As shown in Table 2, the polysiloxane cured products of Examples 1-3 have high hardness, high strength, high refractive index, and low oxygen transmission rate, so they are excellent in sulfuration resistance. In addition, there is little discoloration at high temperature, and it is a highly reliable material with both sulfur resistance and heat discoloration resistance.

On the other hand, Comparative Example 1, which does not contain the component (B) of the present invention, is weak in strength and has a high oxygen transmission rate of 250 cc. Therefore, the silver substrate in the vulcanization test turns black and is poor in vulcanization resistance. Although comparative examples 2 and 3 which do not contain the component (A) or component (B) of the present invention have high thermal discoloration resistance, they are proved to have high oxygen transmission rate and poor vulcanization resistance. In addition, Comparative Example 4 of the conventional organically modified polysiloxane has excellent vulcanization resistance, but it is known to have poor thermal discoloration resistance.

It can be confirmed from the above that, in addition to high refractive index and high strength, the addition-curable polysiloxane composition of the present invention has high resistance to corrosion compared with the conventional phenyl polysiloxane (Comparative Examples 1-3). Vulcanization, and compared with the conventional organically modified polysiloxane (Comparative Example 4), it can provide a cured product with excellent heat discoloration resistance and suitable for LED applications.

In addition, this invention is not limited by the said embodiment. The above-mentioned embodiments are only examples, but those having substantially the same structure as the technical idea described in the claims of the present invention and producing the same effects are all included in the technical scope of the present invention.

Claims (6)

An addition-hardening polysiloxane composition, which includes: (A-1) organopolysiloxane, which is a branched organopolysiloxane represented by the following average composition formula (1): (R ¹ ₃ SiO _1/2 ) _a (R ² R ¹ ₂ SiO _1/2 ) _b (R ² R ¹ SiO) _c (R ¹ ₂ SiO) _d (R ² SiO _3/2 ) _e (R ¹ SiO _3/2 ) _f (SiO _4/2 ) _g . ． ． (1) (wherein, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species without alkenyl, at least 10 mol% of all R ¹ is aryl, and R ² is alkenyl; however, a , b, c, d, e, f, g are the numbers satisfying a≧0, b>0, c≧0, d≧0, e=0, f=0 and g>0, but e+f +g>0, and satisfy the number of a+b+c+d+e+f+g=1), wherein, as (R ² R ¹ ₂ SiO _1/2 ) in the aforementioned average composition formula (1) A unit having at least two siloxane units represented by the following formula (2) in one molecule,

(In the formula, ^R1 is the same as above), (A-2) linear organopolysiloxane represented by the following formula (3): mass ratio (A-1): (A-2) is 100: 0~50: the amount of 50 (but, (A-2) component is more than 0 parts by mass),

(wherein, R ^1' is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species that does not contain an alkenyl group, R ³ is a methyl group or a phenyl group, h is an integer from 0 to 50, and i is an integer from 0 to 100 , the arrangement order of each siloxane unit is arbitrary; however, when h is 0, ^R3 is a phenyl group, and i is an integer from 1 to 100, and the arrangement of the siloxane units in brackets can be random or may be a block), (B) an organohydrogenpolysiloxane having at least two or more siloxane units represented by the following formula (4) in one molecule: relative to the aforementioned (A-1) component and ( A-2) One alkenyl group bonded to a silicon atom in the component, the number of hydrogen atoms bonded to a silicon atom in the aforementioned component (B) is 0.1 to 5.0,

, and (C) a hydrosilation catalyst comprising a platinum group metal. The addition-curable polysiloxane composition as described in Claim 1, wherein R ¹ in the aforementioned formula (2) and R ^1' in the aforementioned formula (3) are phenyl or methyl. The addition-curable polysiloxane composition as described in Claim 1 or Claim 2, wherein the compounding amount of the aforementioned (B) component is relative to one bonded to the aforementioned (A-1) and the aforementioned (A -2) For the alkenyl group of the silicon atom in the component, the number of hydrogen atoms bonded to the silicon atom in the component (B) is 1.0 to 3.0. The addition-hardening polysiloxane composition as described in Claim 1 or Claim 2, wherein the organohydrogenpolysiloxane of the aforementioned component (B) is an organic polysiloxane represented by the following formula (5) or (6). Hydrogen polysiloxane,

(In the formula, the arrangement order of each siloxane unit can be random or block)

A cured product obtained by curing the addition-curable polysiloxane composition described in any one of claim 1 to claim 4. An optical element sealed with the hardened material described in Claim 5.