JP2005076003A - Addition-curable silicone composition - Google Patents

Addition-curable silicone composition Download PDF

Info

Publication number
JP2005076003A
JP2005076003A JP2003311327A JP2003311327A JP2005076003A JP 2005076003 A JP2005076003 A JP 2005076003A JP 2003311327 A JP2003311327 A JP 2003311327A JP 2003311327 A JP2003311327 A JP 2003311327A JP 2005076003 A JP2005076003 A JP 2005076003A
Authority
JP
Japan
Prior art keywords
units
sio
mol
group
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2003311327A
Other languages
Japanese (ja)
Other versions
JP4180474B2 (en
Inventor
Koji Taiko
弘二 大皷
Nobuo Hirai
信男 平井
Kikuo Mochizuki
紀久夫 望月
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Momentive Performance Materials Japan LLC
Original Assignee
GE Toshiba Silicones Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GE Toshiba Silicones Co Ltd filed Critical GE Toshiba Silicones Co Ltd
Priority to JP2003311327A priority Critical patent/JP4180474B2/en
Publication of JP2005076003A publication Critical patent/JP2005076003A/en
Application granted granted Critical
Publication of JP4180474B2 publication Critical patent/JP4180474B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone composition having a high refractive index, having high transparency, and excellent in rubber physical properties. <P>SOLUTION: This composition is formed by mixing specified amounts of (B) a branched organopolysiloxane, (C) an organohydrogensiloxane, and (D) a hydrosilylation reaction catalyst into (A) a specified straight-chain organopolysiloxane containing phenyl groups, wherein the branched organopolysiloxane (B) is composed of ViR<SP>1</SP>SiO<SB>2/2</SB>(Vi is vinyl; and R<SP>1</SP>is a monovalent hydrocarbon residue which contains no aliphatic unsaturated group) units in an amount of 2-20 ml%, PhSiO<SB>3/2</SB>(Ph is phenyl) units in an amount of 10-80 ml%, Ph<SB>2</SB>SiO<SB>2/2</SB>units in an amount of 10-80 ml%, and R<SP>1</SP><SB>2</SB>SiO<SB>2/2</SB>units in an amount of 0-30 ml% and structured so that its residual hydroxy groups are sealed by R<SP>2</SP><SB>3</SB>SiO<SB>1/2</SB>(R<SP>2</SP>is methyl or phenyl) units, and the organohydrogensiloxane (C) is composed of R<SP>3</SP><SB>2</SB>HSiO<SB>1/2</SB>(R<SP>3</SP>is a monovalent hydrocarbon residue which contains no aliphatic unsaturated group) units and SiO<SB>2</SB>units and contains such units as to be composed of 1 to 10 SiO<SB>2</SB>units in a ratio of ≥ 70% in its molecule. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、レンズ、光ファイバのマッチング材料、光素子のコーティング材、プラスチック光ファイバのコア材などの光学用材料として有用な透明硬化物を与える付加硬化型シリコーン組成物に関するものである。   The present invention relates to an addition-curable silicone composition that provides a transparent cured product useful as an optical material such as a lens, an optical fiber matching material, an optical element coating material, and a plastic optical fiber core material.

光学用のプラスチック材料には、高い透明性および高屈折率が要求され、従来はエポキシ樹脂、ポリメチルメタクリレート、ポリカーボネートが多用されていたが、これらの材料は長期にわたる高温の環境下では変形、変色などが生じるので、耐熱性が求められる状況では光学材料として適さない。   Optical plastic materials are required to have high transparency and a high refractive index. Conventionally, epoxy resin, polymethyl methacrylate, and polycarbonate have been widely used. However, these materials are deformed and discolored under long-term high-temperature environments. Therefore, it is not suitable as an optical material in a situation where heat resistance is required.

これらの用途に用いうる材料としてシリコーン樹脂が注目されてきており、光学材料として必要な高屈折率を得るためには、オルガノポリシロキサンベースポリマーの一部または全部としてフェニル変性オルガノポリシロキサンを用いるのが一般的である。   Silicone resin has attracted attention as a material that can be used in these applications, and in order to obtain a high refractive index required as an optical material, phenyl-modified organopolysiloxane is used as a part or all of the organopolysiloxane base polymer. Is common.

ところが、このようなフェニル基変性されたシロキサンポリマーは、一般のジメチル系シロキサンポリマーに比べ非常に粘度が高く、作業性が悪いという問題がある。作業性の問題を改善するためには、ポリマーを低粘度化すればよく、ポリマーの低分子量化を図ることが考えられるが、低分子ポリマーではゴム物性の低下が問題となる。更に、ゴム物性の低下を補うためには、シリコーンレジン等の配合が必要となるが、この補強性を補う手段が透明性の低下を引き起こすという問題がある。   However, such a phenyl group-modified siloxane polymer has a problem that it has a very high viscosity and poor workability compared to a general dimethyl siloxane polymer. In order to improve the workability problem, the viscosity of the polymer may be reduced, and it is conceivable to reduce the molecular weight of the polymer. However, the low molecular weight polymer has a problem of deterioration of rubber properties. Furthermore, in order to make up for the decrease in physical properties of rubber, it is necessary to add a silicone resin or the like. However, there is a problem that means for supplementing this reinforcing property causes a decrease in transparency.

光学材料用の硬化性シリコーン組成物において、高屈折率、高透明性、ゴム物性等に優れたものを提供するため、ベースポリマーやオルガノハイドロジェンシロキサン、配合するシリコーンレジンの構造を工夫する手法が各種提案されているが（特許文献１〜３）、高屈折率、高透明性、ゴム物性の何れをも満足するものはなかった。
特開２００２−２６５７８７号公報 特許第３０５７１４３号公報 特許第３３４４２８６号公報 In order to provide a curable silicone composition for optical materials that is excellent in high refractive index, high transparency, rubber physical properties, etc., there is a technique to devise the structure of the base polymer, organohydrogensiloxane, and silicone resin to be blended. Although various proposals have been made (Patent Documents 1 to 3), none of them satisfies all of high refractive index, high transparency, and rubber physical properties.
JP 2002-265787 A Japanese Patent No. 3057143 Japanese Patent No. 3344286

本発明は、高屈折率、高透明性を有すると共にゴム物性に優れた硬化性シリコーン組成物の提供を目的とする。   An object of the present invention is to provide a curable silicone composition having a high refractive index and high transparency and excellent rubber properties.

本発明者らは上記目的を達成するために鋭意検討した結果、従来提案されているフェニル基変性オルガノポリシロキサン、オルガノハイドロジェンポリシロキサン、ヒドロシリル化反応用触媒、シリコーンレジンを含有する液状付加硬化型シリコーンゴム組成物は、フェニル基変性オルガノポリシロキサン、オルガノハイドロジェンポリシロキサン及びシリコーンレジン相互の相溶性に問題があり、それが透明性を阻害する要因であることを見出し、更に研究を進めた結果、高屈折率のフェニル基変性オルガノポリシロキサンに対し、相溶性のあるオルガノハイドロジェンポリシロキサン及びシリコーンレジンを配合することが極めて有効であることを見出し、本発明を完成するに至った。   As a result of diligent studies to achieve the above object, the present inventors have heretofore proposed a phenyl group-modified organopolysiloxane, an organohydrogenpolysiloxane, a hydrosilylation reaction catalyst, and a liquid addition-curing type containing a silicone resin. As a result of further investigations, the silicone rubber composition was found to have a problem with the compatibility of phenyl group-modified organopolysiloxane, organohydrogenpolysiloxane and silicone resin, which was a factor inhibiting transparency. The present inventors have found that it is extremely effective to add a compatible organohydrogenpolysiloxane and a silicone resin to a phenyl group-modified organopolysiloxane having a high refractive index, and have completed the present invention.

即ち本発明は、
（Ａ）１分子中に少なくとも１個のケイ素原子に結合するアルケニル基を有し、Ｐｈ２ＳｉＯ２／２単位（ただし、Ｐｈはフェニル基である）を２０〜６０モル％含有する直鎖状オルガノポリシロキサン；１００重量部
（Ｂ）ＶｉＲ１ＳｉＯ２／２単位２〜２０モル％、ＰｈＳｉＯ３／２単位１０〜８０モル％、Ｐｈ２ＳｉＯ２／２単位１０〜８０モル％およびＲ１ ２ＳｉＯ２／２単位０〜３０モル％からなり、残存水酸基をＲ２ ３ＳｉＯ１／２単位で封鎖してなる分岐状オルガノポリシロキサン；１０〜３００重量部
（式中、Ｖｉはビニル基、Ｐｈはフェニル基、Ｒ１は脂肪族不飽和基を含まない１価の炭化水素基、Ｒ２はメチル基またはフェニル基である）
（Ｃ）Ｒ３ ２ＨＳｉＯ１／２単位およびＳｉＯ２単位からなり、１分子中におけるＳｉＯ２単位数が１〜１０個の割合が７０％以上であるオルガノハイドロジェンシロキサン；（Ａ）、（Ｂ）成分中のケイ素原子結合アルケニル基１モルに対してＳｉＨ結合が０．４〜３モルとなる量
（式中、Ｒ３は脂肪族不飽和基を含まない１価の炭化水素基である）
（Ｄ）ヒドロシリル化反応用触媒
を含有してなる付加硬化型シリコーン組成物である。 That is, the present invention
(A) a straight chain having an alkenyl group bonded to at least one silicon atom in one molecule and containing 20 to 60 mol% of Ph 2 SiO 2/2 units (where Ph is a phenyl group) Organopolysiloxane: 100 parts by weight (B) ViR 1 SiO 2/2 units 2-20 mol%, PhSiO 3/2 units 10-80 mol%, Ph 2 SiO 2/2 units 10-80 mol% and R 1 2 Branched organopolysiloxane composed of 0 to 30 mol% of SiO 2/2 units and having residual hydroxyl groups blocked with R 2 3 SiO 1/2 units; 10 to 300 parts by weight (wherein Vi is a vinyl group, Ph Is a phenyl group, R 1 is a monovalent hydrocarbon group containing no aliphatic unsaturated group, and R 2 is a methyl group or a phenyl group)
(C) Organohydrogensiloxane comprising R 3 2 HSiO 1/2 units and SiO 2 units, and the ratio of 1 to 10 SiO 2 units in one molecule is 70% or more; (A), (B ) Amount that SiH bond is 0.4 to 3 moles per mole of silicon-bonded alkenyl group in component (wherein R 3 is a monovalent hydrocarbon group not containing an aliphatic unsaturated group)
(D) An addition-curable silicone composition containing a hydrosilylation reaction catalyst.

以下、本発明につき詳細に説明する。本発明において、（Ａ）成分のオルガノポリシロキサンは本発明組成物のベースポリマーとなるものであり、分子中に少なくとも１個のケイ素原子に結合するアルケニル基を有し、Ｐｈ２ＳｉＯ２／２単位（ただし、Ｐｈはフェニル基である）を３５〜６０モル％含有する直鎖状オルガノポリシロキサンである。 Hereinafter, the present invention will be described in detail. In the present invention, the organopolysiloxane of component (A) is a base polymer of the composition of the present invention, has an alkenyl group bonded to at least one silicon atom in the molecule, and has Ph 2 SiO 2/2. It is a linear organopolysiloxane containing 35 to 60 mol% of units (where Ph is a phenyl group).

Ｐｈ２ＳｉＯ２／２単位が２０〜６０モル％であることは、光学材料用として必要な高屈折率（２５℃における屈折率が１．４９以上）を得るために必要である。 A Ph 2 SiO 2/2 unit of 20 to 60 mol% is necessary to obtain a high refractive index (refractive index at 25 ° C. of 1.49 or more) necessary for an optical material.

Ｐｈ２ＳｉＯ２／２単位が２０モル％未満では、光学材料用として必要な高屈折率（２５℃における屈折率が１．４９以上）を得られないばかりか、(Ｂ)成分との相溶性が低下する。また、Ｐｈ２ＳｉＯ２／２単位が６０モル％より多いと組成物の高粘度化による作業性の悪化が生じる。 If the Ph 2 SiO 2/2 unit is less than 20 mol%, not only the high refractive index required for optical materials (refractive index at 25 ° C. of 1.49 or more) can be obtained, but also compatibility with the component (B). Decreases. Further, deterioration of the workability due to high viscosity of the composition and Ph 2 SiO 2/2 units is more than 60 mol% results.

次に本発明で用いる（Ｂ）成分は、特定の分子構造を有する分岐状オルガノポリシロキサンであり、本発明組成物の強度向上の作用を有すると共に、（Ａ）成分と相溶性の良いものである。   Next, the component (B) used in the present invention is a branched organopolysiloxane having a specific molecular structure, which has the effect of improving the strength of the composition of the present invention and is compatible with the component (A). is there.

かかる（Ｂ）成分は、ＶｉＲ１ＳｉＯ２／２単位２〜２０モル％、ＰｈＳｉＯ３／２単位１０〜８０モル％、Ｐｈ２ＳｉＯ２／２単位１０〜８０モル％およびＲ１ ２ＳｉＯ２／２単位０〜３０モル％からなり、残存水酸基をＲ２ ３ＳｉＯ１／２単位で封鎖してなる分岐状オルガノポリシロキサンである。
（式中、Ｖｉはビニル基、Ｐｈはフェニル基、Ｒ１は脂肪族不飽和基を含まない１価の炭化水素基、Ｒ２はメチル基またはフェニル基である）
ビニル基の含有量を示すＶｉＲ１ＳｉＯ２／２単位は、２モル％より少ないと反応硬化物は必要な強度が得られず、２０モル％より多いと架橋点が多すぎるため反応硬化物が脆くなってしまう。 The component (B) is composed of 2 to 20 mol% of ViR 1 SiO 2/2 units, 10 to 80 mol% of PhSiO 3/2 units, 10 to 80 mol% of Ph 2 SiO 2/2 units, and R 1 2 SiO 2 / It is a branched organopolysiloxane composed of 0 to 30 mol% of 2 units and having residual hydroxyl groups blocked with R 2 3 SiO 1/2 units.
(In the formula, Vi is a vinyl group, Ph is a phenyl group, R 1 is a monovalent hydrocarbon group not containing an aliphatic unsaturated group, and R 2 is a methyl group or a phenyl group)
If the ViR 1 SiO 2/2 unit indicating the vinyl group content is less than 2 mol%, the reaction cured product cannot obtain the required strength, and if it is more than 20 mol%, the reaction cured product has too many crosslinking points. It becomes brittle.

分岐状構造を形成させるＰｈＳｉＯ３／２単位は、１０モル％より少ないと反応硬化物は必要な強度が得られず、８０モル％より多いと組成物の高粘度化による作業性の悪化が生じる。 If the PhSiO 3/2 unit forming the branched structure is less than 10 mol%, the reaction cured product cannot obtain the required strength, and if it exceeds 80 mol%, the workability deteriorates due to the increase in the viscosity of the composition. .

フェニル基以外の含有量を示すＶｉＲ１ＳｉＯ２／２単位およびＲ１ ２ＳｉＯ２／２単位の合計量は２〜５０モル％が好ましく２モル％より少ないと反応硬化物に必要な強度が得られなかったり、組成物の高粘度化による作業性の悪化を生じたりする。また、５０モル％より多いと光学材料用として必要な高屈折率（２５℃における屈折率が１．４９以上）を得られないばかりか、(Ａ)成分との相溶性が低下する。 The total amount of ViR 1 SiO 2/2 units and R 1 2 SiO 2/2 units indicating the content other than the phenyl group is preferably 2 to 50 mol%, and if it is less than 2 mol%, the strength required for the reaction cured product is obtained. Or the workability deteriorates due to the increase in viscosity of the composition. On the other hand, if it exceeds 50 mol%, not only the high refractive index required for optical materials (refractive index at 25 ° C. of 1.49 or more) cannot be obtained, but the compatibility with the component (A) decreases.

上記単位にから調製されたオルガノポリシロキサンの残存水酸基はＲ２ ３ＳｉＯ１／２単位により封止しないと、(Ａ)成分と混合し脱溶した際に白濁が生じる。 If the residual hydroxyl groups of the organopolysiloxane prepared from the above units are not sealed with R 2 3 SiO 1/2 units, they become cloudy when mixed with the component (A) and dissolved.

（Ｂ）成分の配合量は、（Ａ）成分１００重量部に対し、１０〜３００重量部である。１０重量部より少ないと反応硬化物に必要な強度が得られなく、３００重量部より多いと組成物の高粘度化による作業性の悪化を生じる。   (B) The compounding quantity of a component is 10-300 weight part with respect to 100 weight part of (A) component. When the amount is less than 10 parts by weight, the strength required for the reaction-cured product cannot be obtained. When the amount is more than 300 parts by weight, workability is deteriorated due to increase in viscosity of the composition.

次に本発明で用いる（Ｃ）成分は、架橋成分として作用するオルガノハイドロジェンシロキサンである。   Next, the component (C) used in the present invention is an organohydrogensiloxane that acts as a crosslinking component.

本発明において用いる（Ｃ）オルガノハイドロジェンシロキサンは、（Ａ）成分と相溶性の良いことが必要であり、この点から、Ｒ３ ２ＨＳｉＯ１／２単位およびＳｉＯ２単位からなり、１分子中におけるＳｉＯ２単位数が１〜１０個の割合が７０％以上であるオルガノハイドロジェンシロキサンが選択される。
（式中、Ｒ３は脂肪族不飽和基を含まない１価の炭化水素基である）
１分子中におけるＳｉＯ２単位数が１〜１０個の割合が７０％より少ないと（Ａ）成分との相溶性が低下する。 The (C) organohydrogensiloxane used in the present invention must have good compatibility with the component (A). From this point, it is composed of R 3 2 HSiO 1/2 units and SiO 2 units, An organohydrogensiloxane having a ratio of 1 to 10 SiO 2 units of 70% or more is selected.
(Wherein R 3 is a monovalent hydrocarbon group containing no aliphatic unsaturated group)
When the ratio of 1 to 10 SiO 2 units in one molecule is less than 70%, the compatibility with the component (A) decreases.

（Ｃ）成分の配合量は、（Ａ）、（Ｂ）成分中のケイ素原子結合アルケニル基１モルに対してＳｉＨ結合が０．４〜３モルとなる量である。０．４モルに満たない量では十分な架橋が得られず、３モルを超える量では未反応のＳｉ−Ｈ結合が残存し、物性が不安定となる。   The amount of component (C) is such that SiH bonds are 0.4 to 3 moles per mole of silicon-bonded alkenyl groups in components (A) and (B). If the amount is less than 0.4 mol, sufficient crosslinking cannot be obtained, and if it exceeds 3 mol, unreacted Si-H bonds remain and the physical properties become unstable.

本発明の（Ｄ）成分は、ヒドロシリル化反応用触媒であり、白金黒、塩化第二白金、塩化白金酸、塩化白金酸と一価アルコールとの反応物、塩化白金酸とオレフィン類やビニルシロキサンとの錯体、白金ビスアセトアセテート、パラジウム系触媒、ロジウム系触媒等が例示される。   Component (D) of the present invention is a catalyst for hydrosilylation reaction, such as platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and monohydric alcohol, chloroplatinic acid and olefins, and vinyl siloxane. And complexes thereof, platinum bisacetoacetate, palladium-based catalysts, rhodium-based catalysts and the like.

好ましくは白金系触媒が用いられ、その使用量は硬化必要量であれば特に制限されず、（Ａ）〜（Ｃ）成分の種類、所望の硬化速度などに応じて適宜増減すべきであるが、一般的には、本発明の組成物の合計重量に対して０．０１〜１０００ｐｐｍの範囲とすればよい。特に１〜５００ｐｐｍであることが、硬化性、コストの面からも好ましい。   A platinum-based catalyst is preferably used, and the amount used thereof is not particularly limited as long as it is a necessary amount for curing, and should be appropriately increased or decreased depending on the types of components (A) to (C), a desired curing rate, and the like. In general, the content may be in the range of 0.01 to 1000 ppm based on the total weight of the composition of the present invention. In particular, 1 to 500 ppm is preferable from the viewpoint of curability and cost.

上記組成からなる本発明の硬化性組成物は、光学材料用としての用途から２５℃における屈折率が１．４９以上であることが望ましい。   The curable composition of the present invention having the above composition desirably has a refractive index of 1.49 or more at 25 ° C. for use as an optical material.

その他、本発明の組成物には、必要に応じて反応を制御するための反応制御剤、例えば、リン、窒素、硫黄などの化合物またはアセチレン系化合物を添加してもよい。また、接着性を付与するためにエポキシ基含有アルコキシシラン等のシランカップリング剤を添加してもよい。   In addition, a reaction control agent for controlling the reaction, for example, a compound such as phosphorus, nitrogen, sulfur, or an acetylene compound may be added to the composition of the present invention as necessary. Moreover, in order to provide adhesiveness, you may add silane coupling agents, such as an epoxy-group containing alkoxysilane.

以下、実施例と比較例を示すが、本発明は下記の実施例に制限されるものではない。なお、各例中の部はいずれも重量部である。
実施例１
（Ａ）平均組成が下記式（１）で示されるオルガノポリシロキサン１００重量部、（Ｂ）平均組成が下記式（２）で示され残存水酸基をＭｅ３ＳｉＯ１／２で封止したオルガノポリシロキサン１００重量部、（Ｃ）主成分が下記式（３）
で示され、１分子中におけるＳｉＯ２単位数が１〜１０個の割合が９０％のオルガノハイドロジェンシロキサン３０重量部、（Ｄ）塩化白金酸とビニルシロキサンの錯体(組成物の１０ｐｐｍとなる量)を加え、光学材料用硬化性組成物を調製した。
（１）Ｍｅ３ＳｉＯ−（Ｐｈ２ＳｉＯ）１２−（Ｍｅ２ＳｉＯ）８−（ＶｉＭｅＳｉＯ）４−ＳｉＭｅ３
（２）（ＶｉＭｅＳｉＯ２／２）１２（ＰｈＳｉＯ３／２）５５（Ｐｈ２ＳｉＯ２／２）３３（Ｍｅ２ＳｉＯ２／２）１
（３）（Ｍe２ＨＳｉＯ１／２）８（ＳｉＯ２）４
この組成物は透明で屈折率１．５３であった。この組成物を１５×１５×０．２ｃｍの板状金型に流し、１５０℃で１時間加熱して硬化させた。得られた硬化物は透明であり、機械的物性をＪＩＳ Ｋ−６３０１に従って測定したところ、下記の結果が得られた。
硬さ(ＪＩＳ−Ａ) ７０
引張強さ １．２ＭＰａ
伸び ４０％
実施例２
（Ａ）平均組成が下記式（４）で示されるオルガノポリシロキサン１００重量部、（Ｂ）平均組成が下記式（５）で示され残存水酸基をＭｅ３ＳｉＯ１／２で封止したオルガノポリシロキサン１００重量部、（Ｃ）実施例１で用いたものと同じオルガノハイドロジェンシロキサン１５重量部、（Ｄ）実施例１で用いたものと同じヒドロシリル化反応用触媒(組成物の１０ｐｐｍとなる量)を加え、光学材料用硬化性組成物を調製した。
（４）ＶｉＭｅ２ＳｉＯ−（Ｐｈ２ＳｉＯ）１２−（Ｍｅ２ＳｉＯ）８−ＳｉＭｅ２Ｖｉ
（５）（ＶｉＭｅＳｉＯ２／２）１０（ＰｈＳｉＯ３／２）５５（Ｐｈ２ＳｉＯ２／２）３３（Ｍｅ２ＳｉＯ２／２）２
この組成物は透明で屈折率１．５３であった。組成物を実施例１と同様にして硬化させたところ得られた硬化物は透明であり、物性は下記のように測定された。
硬さ(ＪＩＳ−Ａ) ３５
引張強さ ０．６ＭＰａ
伸び ５０％
比較例１
（Ａ）実施例２の式（４）で示されるオルガノポリシロキサン１００重量部、（Ｃ）実施例１で用いたものと同じオルガノハイドロジェンシロキサン６.５重量部、（Ｄ）実施例１で用いたものと同じヒドロシリル化反応用触媒(組成物の１０ｐｐｍとなる量)を加え、光学材料用硬化性組成物を調製した。 Hereinafter, although an Example and a comparative example are shown, this invention is not restrict | limited to the following Example. In addition, all the parts in each example are parts by weight.
Example 1
(A) 100 parts by weight of an organopolysiloxane having an average composition represented by the following formula (1), (B) an organopolysiloxane having an average composition represented by the following formula (2) and having residual hydroxyl groups sealed with Me 3 SiO 1/2 100 parts by weight of siloxane, (C) main component is the following formula (3)
30 parts by weight of an organohydrogensiloxane having a ratio of 1 to 10 SiO 2 units in one molecule of 90%, and (D) a complex of chloroplatinic acid and vinylsiloxane (amount of 10 ppm of the composition) ) Was added to prepare a curable composition for optical materials.
(1) Me 3 SiO- (Ph 2 SiO) 12 - (Me 2 SiO) 8 - (ViMeSiO) 4 -SiMe 3
(2) (ViMeSiO 2/2 ) 12 (PhSiO 3/2 ) 55 (Ph 2 SiO 2/2 ) 33 (Me 2 SiO 2/2 ) 1
(3) (Me 2 HSiO 1/2 ) 8 (SiO 2 ) 4
This composition was transparent and had a refractive index of 1.53. This composition was poured into a 15 × 15 × 0.2 cm plate mold and heated at 150 ° C. for 1 hour to be cured. The obtained cured product was transparent, and the following results were obtained when the mechanical properties were measured according to JIS K-6301.
Hardness (JIS-A) 70
Tensile strength 1.2 MPa
40% elongation
Example 2
(A) 100 parts by weight of an organopolysiloxane having an average composition represented by the following formula (4), (B) an organopolysiloxane having an average composition represented by the following formula (5) and having residual hydroxyl groups sealed with Me 3 SiO 1/2 100 parts by weight of siloxane, (C) 15 parts by weight of the same organohydrogensiloxane as used in Example 1, and (D) the same hydrosilylation reaction catalyst as used in Example 1 (amount to be 10 ppm of the composition) ) Was added to prepare a curable composition for optical materials.
(4) ViMe 2 SiO- (Ph 2 SiO) 12 - (Me 2 SiO) 8 -SiMe 2 Vi
(5) (ViMeSiO 2/2 ) 10 (PhSiO 3/2 ) 55 (Ph 2 SiO 2/2 ) 33 (Me 2 SiO 2/2 ) 2
This composition was transparent and had a refractive index of 1.53. When the composition was cured in the same manner as in Example 1, the obtained cured product was transparent, and the physical properties were measured as follows.
Hardness (JIS-A) 35
Tensile strength 0.6 MPa
50% elongation
Comparative Example 1
(A) 100 parts by weight of the organopolysiloxane represented by the formula (4) in Example 2, (C) 6.5 parts by weight of the same organohydrogensiloxane used in Example 1, and (D) in Example 1. The same hydrosilylation reaction catalyst as used (in an amount of 10 ppm of the composition) was added to prepare a curable composition for optical materials.

この組成物は透明で屈折率１．５３であった。組成物を実施例１と同様にして硬化させたところ得られた硬化物は透明であったが物性は実施例２の硬化物に比べ劣った。
硬さ(ＪＩＳ−Ａ) ２５
引張強さ 脆く測定不可能
伸び 脆く測定不可能
比較例２
（Ａ）平均組成が下記式（６）で示されるオルガノポリシロキサン１００重量部、（Ｂ）実施例２の式（５）で示されるオルガノポリシロキサン１００重量部、（Ｃ）実施例１で用いたものと同じオルガノハイドロジェンシロキサン１５重量部（Ｄ）実施例１で用いたものと同じヒドロシリル化反応用触媒(組成物の１０ｐｐｍとなる量)を加え、光学材料用硬化性組成物を調製した。得られた組成物には濁りが認められた。
（６）ＶｉＭｅ２ＳｉＯ−（Ｐｈ２ＳｉＯ）６−（Ｍｅ２ＳｉＯ）３４−ＳｉＭｅ２Ｖｉ
比較例３
（Ａ）実施例２の式（４）で示されるオルガノポリシロキサン１００重量部、（Ｂ）実施例２の式（５）で示され残存水酸基をＭｅ３ＳｉＯ１／２で封止しないオルガノポリシロキサン１００重量部（Ｃ）実施例１で用いたものと同じオルガノハイドロジェンシロキサン２０重量部、（Ｄ）実施例１で用いたものと同じヒドロシリル化反応用触媒(組成物の１０ｐｐｍとなる量)を加え、光学材料用硬化性組成物を調製した。得られた組成物には濁りが認められた。
比較例４
（Ａ）実施例２の式（４）で示されるオルガノポリシロキサン１００重量部、（Ｂ）実施例２の式（５）で示されたオルガノポリシロキサン１００重量部、（Ｃ）主成分が実施例１の式（３）で示され、１分子中におけるＳｉＯ２単位数が１〜１０個の割合が６０％のオルガノハイドロジェンシロキサン１５重量部、（Ｄ）実施例１で用いたものと同じヒドロシリル化反応用触媒(組成物の１０ｐｐｍとなる量)を加え、光学材料用硬化性組成物を調製した。得られた組成物には濁りが認められた。 This composition was transparent and had a refractive index of 1.53. When the composition was cured in the same manner as in Example 1, the resulting cured product was transparent, but the physical properties were inferior to those of Example 2.
Hardness (JIS-A) 25
Tensile strength Brittle, unmeasurable elongation Brittle, unmeasurable comparative example 2
(A) 100 parts by weight of an organopolysiloxane having an average composition represented by the following formula (6), (B) 100 parts by weight of an organopolysiloxane represented by the formula (5) in Example 2, and (C) used in Example 1. 15 parts by weight of the same organohydrogensiloxane (D) The same hydrosilylation catalyst as that used in Example 1 (amount of 10 ppm of the composition) was added to prepare a curable composition for optical materials. . Turbidity was recognized in the obtained composition.
(6) ViMe 2 SiO— (Ph 2 SiO) 6 — (Me 2 SiO) 34 —SiMe 2 Vi
Comparative Example 3
(A) 100 parts by weight of the organopolysiloxane represented by the formula (4) in Example 2 and (B) organopolysiloxane represented by the formula (5) in Example 2 in which the remaining hydroxyl group is not sealed with Me 3 SiO 1/2 100 parts by weight of siloxane (C) 20 parts by weight of the same organohydrogensiloxane as used in Example 1, (D) the same catalyst for hydrosilylation reaction as used in Example 1 (amount to be 10 ppm of the composition) Was added to prepare a curable composition for optical materials. Turbidity was recognized in the obtained composition.
Comparative Example 4
(A) 100 parts by weight of the organopolysiloxane represented by the formula (4) in Example 2; (B) 100 parts by weight of the organopolysiloxane represented by the formula (5) in Example 2; and (C) the main component. 15 parts by weight of an organohydrogensiloxane represented by the formula (3) in Example 1 and having a ratio of 1 to 10 SiO 2 units in one molecule of 60%, (D) the same as that used in Example 1 A catalyst for hydrosilylation reaction (amount to be 10 ppm of the composition) was added to prepare a curable composition for optical materials. Turbidity was recognized in the obtained composition.

Claims (1)

（Ａ）１分子中に少なくとも１個のケイ素原子に結合するアルケニル基を有し、Ｐｈ２ＳｉＯ２／２単位（ただし、Ｐｈはフェニル基である）を２０〜６０モル％含有する直鎖状オルガノポリシロキサン；１００重量部
（Ｂ）ＶｉＲ１ＳｉＯ２／２単位２〜２０モル％、ＰｈＳｉＯ３／２単位１０〜８０モル％、Ｐｈ２ＳｉＯ２／２単位１０〜８０モル％およびＲ１ ２ＳｉＯ２／２単位０〜３０モル％からなり、残存水酸基をＲ２ ３ＳｉＯ１／２単位で封鎖してなる分岐状オルガノポリシロキサン；１０〜３００重量部
（式中、Ｖｉはビニル基、Ｐｈはフェニル基、Ｒ１は脂肪族不飽和基を含まない１価の炭化水素基、Ｒ２はメチル基またはフェニル基である）
（Ｃ）Ｒ３ ２ＨＳｉＯ１／２単位およびＳｉＯ２単位からなり、１分子中におけるＳｉＯ２単位数が１〜１０個の割合が７０％以上であるオルガノハイドロジェンシロキサン；（Ａ）、（Ｂ）成分中のケイ素原子結合アルケニル基１モルに対してＳｉＨ結合が０．４〜３モルとなる量
（式中、Ｒ３は脂肪族不飽和基を含まない１価の炭化水素基である）
（Ｄ）ヒドロシリル化反応用触媒
を含有してなる付加硬化型シリコーン組成物。 (A) a straight chain having an alkenyl group bonded to at least one silicon atom in one molecule and containing 20 to 60 mol% of Ph 2 SiO 2/2 units (where Ph is a phenyl group) Organopolysiloxane: 100 parts by weight (B) ViR 1 SiO 2/2 units 2-20 mol%, PhSiO 3/2 units 10-80 mol%, Ph 2 SiO 2/2 units 10-80 mol% and R 1 2 Branched organopolysiloxane composed of 0 to 30 mol% of SiO 2/2 units and having residual hydroxyl groups blocked with R 2 3 SiO 1/2 units; 10 to 300 parts by weight (wherein Vi is a vinyl group, Ph Is a phenyl group, R 1 is a monovalent hydrocarbon group containing no aliphatic unsaturated group, and R 2 is a methyl group or a phenyl group)
(C) Organohydrogensiloxane comprising R 3 2 HSiO 1/2 units and SiO 2 units, and the ratio of 1 to 10 SiO 2 units in one molecule is 70% or more; (A), (B ) Amount that SiH bond is 0.4 to 3 moles per mole of silicon-bonded alkenyl group in component (wherein R 3 is a monovalent hydrocarbon group not containing an aliphatic unsaturated group)
(D) An addition-curable silicone composition comprising a hydrosilylation reaction catalyst.
JP2003311327A 2003-09-03 2003-09-03 Addition-curing silicone composition Expired - Fee Related JP4180474B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003311327A JP4180474B2 (en) 2003-09-03 2003-09-03 Addition-curing silicone composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2003311327A JP4180474B2 (en) 2003-09-03 2003-09-03 Addition-curing silicone composition

Publications (2)

Publication Number Publication Date
JP2005076003A true JP2005076003A (en) 2005-03-24
JP4180474B2 JP4180474B2 (en) 2008-11-12

Family

ID=34412922

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2003311327A Expired - Fee Related JP4180474B2 (en) 2003-09-03 2003-09-03 Addition-curing silicone composition

Country Status (1)

Country Link
JP (1) JP4180474B2 (en)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006335857A (en) * 2005-06-01 2006-12-14 Ge Toshiba Silicones Co Ltd Polyorganosiloxane composition which gives transparent cured product
JP2008101056A (en) * 2006-10-17 2008-05-01 Momentive Performance Materials Japan Kk Silicone rubber composition
EP1988125A2 (en) 2007-04-06 2008-11-05 Shin-Etsu Chemical Co., Ltd. Addition curable silicone resin composition and silicone lens using same
KR100902852B1 (en) 2006-04-24 2009-06-16 신에쓰 가가꾸 고교 가부시끼가이샤 Silicone Lens and Silicone Resin Composition for Molding Lens
JP2009523856A (en) * 2006-01-17 2009-06-25 ダウ・コーニング・コーポレイション Heat-stable transparent silicone resin composition, and preparation method and use thereof
US7553915B2 (en) 2005-12-06 2009-06-30 Shin-Etsu Chemical Co., Ltd. Silicone composition and cured product
EP2110401A1 (en) 2008-04-15 2009-10-21 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition and cured product thereof
JP2010013503A (en) * 2008-07-01 2010-01-21 Showa Highpolymer Co Ltd Curable resin composition and opto device
JP2010508377A (en) * 2006-08-28 2010-03-18 ダウ・コーニング・コーポレイション Optical component, silicone composition, and method for molding optical component
US7705093B2 (en) 2006-06-14 2010-04-27 Shin-Etsu Chemical Co., Ltd. Phosphor-filled curable silicone resin composition and cured product thereof
EP2199346A2 (en) 2008-12-22 2010-06-23 Nitto Denko Corporation Silicone resin composition
EP2221868A2 (en) 2009-02-24 2010-08-25 Shin-Etsu Chemical Co., Ltd. Optical semiconductor device encapsulated with silicone resin
US7807736B2 (en) 2006-07-18 2010-10-05 Shin-Etsu Chemical Co., Ltd. Semiconductor device encapsulated by silicone resin composition, and silicone resin tablet for encapsulating semiconductor device
WO2011125463A1 (en) * 2010-03-31 2011-10-13 積水化学工業株式会社 Sealant for optical semiconductors and optical semiconductor device
JP2012007136A (en) * 2010-05-21 2012-01-12 Sekisui Chem Co Ltd Sealing agent for optical semiconductor device and optical semiconductor device using the same
US8158265B2 (en) 2008-12-05 2012-04-17 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition that produces cured product having high refractive index, and optical element encapsulating material formed from the composition
US8299186B2 (en) 2008-06-18 2012-10-30 Dow Corning Toray Company, Ltd. Curable organopolysiloxane composition and semiconductor device
US20140031509A1 (en) * 2012-07-27 2014-01-30 Lg Chem, Ltd. Curable composition
KR20140079296A (en) 2012-12-18 2014-06-26 신에쓰 가가꾸 고교 가부시끼가이샤 Addition-curable silicone composition and optical element
US8791213B2 (en) 2012-07-19 2014-07-29 Shin-Etsu Chemical Co., Ltd. Curable silicone resin composition
US8846828B2 (en) 2008-06-18 2014-09-30 Dow Corning Toray Co. Ltd. Curable organopolysiloxane composition and semiconductor device
CN104518073A (en) * 2013-09-30 2015-04-15 三垦电气株式会社 Light-emitting device
JP2015522705A (en) * 2012-07-27 2015-08-06 エルジー・ケム・リミテッド Curable composition
KR20150104110A (en) 2013-01-10 2015-09-14 신에쓰 가가꾸 고교 가부시끼가이샤 Addition-cure-type silicone composition, sealing material for optical elements, and optical element
US9464211B2 (en) 2012-09-07 2016-10-11 Dow Corning Toray Co., Ltd. Curable silicone composition and optical semiconductor device
US9624374B2 (en) 2014-03-05 2017-04-18 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition and optical device
CN110272627A (en) * 2019-07-24 2019-09-24 杭州之江新材料有限公司 A kind of silicon gel of high refractive index and preparation method thereof
KR20200100547A (en) 2019-02-18 2020-08-26 신에쓰 가가꾸 고교 가부시끼가이샤 Heat-curable silicone composition and cured product thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6678388B2 (en) 2014-12-25 2020-04-08 信越化学工業株式会社 Curable silicone resin composition
JP6481647B2 (en) 2016-03-22 2019-03-13 信越化学工業株式会社 Ultraviolet curable silicone composition, cured product thereof, optical element sealing material comprising the composition, and optical element sealed with the optical element sealing material

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006335857A (en) * 2005-06-01 2006-12-14 Ge Toshiba Silicones Co Ltd Polyorganosiloxane composition which gives transparent cured product
US7553915B2 (en) 2005-12-06 2009-06-30 Shin-Etsu Chemical Co., Ltd. Silicone composition and cured product
JP2009523856A (en) * 2006-01-17 2009-06-25 ダウ・コーニング・コーポレイション Heat-stable transparent silicone resin composition, and preparation method and use thereof
KR100902852B1 (en) 2006-04-24 2009-06-16 신에쓰 가가꾸 고교 가부시끼가이샤 Silicone Lens and Silicone Resin Composition for Molding Lens
US7705093B2 (en) 2006-06-14 2010-04-27 Shin-Etsu Chemical Co., Ltd. Phosphor-filled curable silicone resin composition and cured product thereof
US7807736B2 (en) 2006-07-18 2010-10-05 Shin-Etsu Chemical Co., Ltd. Semiconductor device encapsulated by silicone resin composition, and silicone resin tablet for encapsulating semiconductor device
JP2010508377A (en) * 2006-08-28 2010-03-18 ダウ・コーニング・コーポレイション Optical component, silicone composition, and method for molding optical component
JP2012017470A (en) * 2006-08-28 2012-01-26 Dow Corning Corp Optical device and silicone composition, and process for fabricating the optical devices
KR101397616B1 (en) 2006-08-28 2014-05-26 다우 코닝 코포레이션 Optical devices and silicone compositions and processes fabricating the optical devices
JP2008101056A (en) * 2006-10-17 2008-05-01 Momentive Performance Materials Japan Kk Silicone rubber composition
EP1988125A2 (en) 2007-04-06 2008-11-05 Shin-Etsu Chemical Co., Ltd. Addition curable silicone resin composition and silicone lens using same
US7566756B2 (en) 2007-04-06 2009-07-28 Shin-Etsu Chemical Co., Ltd. Addition curable silicone resin composition and silicon lens using same
US8071707B2 (en) 2008-04-15 2011-12-06 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition and cured product thereof
EP2110401A1 (en) 2008-04-15 2009-10-21 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition and cured product thereof
US8846828B2 (en) 2008-06-18 2014-09-30 Dow Corning Toray Co. Ltd. Curable organopolysiloxane composition and semiconductor device
US8299186B2 (en) 2008-06-18 2012-10-30 Dow Corning Toray Company, Ltd. Curable organopolysiloxane composition and semiconductor device
JP2010013503A (en) * 2008-07-01 2010-01-21 Showa Highpolymer Co Ltd Curable resin composition and opto device
US8158265B2 (en) 2008-12-05 2012-04-17 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition that produces cured product having high refractive index, and optical element encapsulating material formed from the composition
US8329290B2 (en) 2008-12-22 2012-12-11 Nitto Denko Corporation Silicone resin composition
EP2199346A2 (en) 2008-12-22 2010-06-23 Nitto Denko Corporation Silicone resin composition
EP2221868A2 (en) 2009-02-24 2010-08-25 Shin-Etsu Chemical Co., Ltd. Optical semiconductor device encapsulated with silicone resin
US8164202B2 (en) 2009-02-24 2012-04-24 Shin-Etsu Chemical Co., Ltd. Optical semiconductor device encapsulated with silicone resin
CN102639643A (en) * 2010-03-31 2012-08-15 积水化学工业株式会社 Sealant for optical semiconductors and optical semiconductor device
JP5060654B2 (en) * 2010-03-31 2012-10-31 積水化学工業株式会社 Sealant for optical semiconductor device and optical semiconductor device
WO2011125463A1 (en) * 2010-03-31 2011-10-13 積水化学工業株式会社 Sealant for optical semiconductors and optical semiconductor device
JP2012007136A (en) * 2010-05-21 2012-01-12 Sekisui Chem Co Ltd Sealing agent for optical semiconductor device and optical semiconductor device using the same
US8791213B2 (en) 2012-07-19 2014-07-29 Shin-Etsu Chemical Co., Ltd. Curable silicone resin composition
JP2015522705A (en) * 2012-07-27 2015-08-06 エルジー・ケム・リミテッド Curable composition
US20140031509A1 (en) * 2012-07-27 2014-01-30 Lg Chem, Ltd. Curable composition
US9455210B2 (en) * 2012-07-27 2016-09-27 Lg Chem, Ltd. Curable composition
US9624345B2 (en) 2012-07-27 2017-04-18 Lg Chem, Ltd. Curable composition
US9464211B2 (en) 2012-09-07 2016-10-11 Dow Corning Toray Co., Ltd. Curable silicone composition and optical semiconductor device
KR20140079296A (en) 2012-12-18 2014-06-26 신에쓰 가가꾸 고교 가부시끼가이샤 Addition-curable silicone composition and optical element
US8957165B2 (en) 2012-12-18 2015-02-17 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition and optical element
KR20150104110A (en) 2013-01-10 2015-09-14 신에쓰 가가꾸 고교 가부시끼가이샤 Addition-cure-type silicone composition, sealing material for optical elements, and optical element
US9464192B2 (en) 2013-01-10 2016-10-11 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition, optical device encapsulating material and optical device
CN104518073A (en) * 2013-09-30 2015-04-15 三垦电气株式会社 Light-emitting device
US9624374B2 (en) 2014-03-05 2017-04-18 Shin-Etsu Chemical Co., Ltd. Addition-curable silicone composition and optical device
KR20200100547A (en) 2019-02-18 2020-08-26 신에쓰 가가꾸 고교 가부시끼가이샤 Heat-curable silicone composition and cured product thereof
CN110272627A (en) * 2019-07-24 2019-09-24 杭州之江新材料有限公司 A kind of silicon gel of high refractive index and preparation method thereof

Also Published As

Publication number Publication date
JP4180474B2 (en) 2008-11-12

Similar Documents

Publication Publication Date Title
JP4180474B2 (en) Addition-curing silicone composition
TWI402315B (en) Curable silicone composition
JP4071639B2 (en) Silicone resin composition for light emitting diode element
JP4801320B2 (en) Addition reaction curable organopolysiloxane resin composition
JP6678388B2 (en) Curable silicone resin composition
KR101913869B1 (en) Curable silicone resin composition
TWI447176B (en) Curable polyorganosiloxane composition
JP4771046B2 (en) Curable silicone rubber composition and method for producing composite molded body of liquid crystal polymer and silicone rubber
TWI477558B (en) And a hardened polysiloxane composition imparting a highly transparent polysiloxane
KR101565762B1 (en) Curable organopolysiloxane composition and cured product thereof
JP4954499B2 (en) Silicone resin lens for LED and manufacturing method thereof
TWI551654B (en) A hardened organopolysiloxane composition, an optical element sealing material, and an optical element
JP2006328102A (en) Silicone resin composition for molding lens and silicone lens
JP2005162859A (en) Addition reaction curing type organopolysiloxane resin composition and optical member
JP4494077B2 (en) Curable composition for sealing optical materials
JP2007039483A (en) Curable polyorganosiloxane composition
TWI579340B (en) Addition hardening type silicone oxygen composition and optical element
JP4267404B2 (en) Curable composition for optical materials
JP2005327777A (en) Silicone resin constituent for light emitting diode
JP3057143B2 (en) Optically curable silicone composition
CN108864429A (en) Die bond silicone resin component, die bond material and optical semiconductor device
WO2018061754A1 (en) Crosslinkable organopolysiloxane composition, cured product thereof, and led device
JP2009062446A (en) Curable silicone composition
JP5780204B2 (en) Silicone rubber molding material
JP6657340B2 (en) Curable silicone resin composition

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20060703

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20080821

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20080826

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20080827

R150 Certificate of patent or registration of utility model

Ref document number: 4180474

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110905

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120905

Year of fee payment: 4

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130905

Year of fee payment: 5

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees