JP3183384B2 - Optical resin composition and method for producing the same - Google Patents

Optical resin composition and method for producing the same

Info

Publication number
JP3183384B2
JP3183384B2 JP34852995A JP34852995A JP3183384B2 JP 3183384 B2 JP3183384 B2 JP 3183384B2 JP 34852995 A JP34852995 A JP 34852995A JP 34852995 A JP34852995 A JP 34852995A JP 3183384 B2 JP3183384 B2 JP 3183384B2
Authority
JP
Japan
Prior art keywords
weight
resin composition
compound
parts
optical resin
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.)
Expired - Fee Related
Application number
JP34852995A
Other languages
Japanese (ja)
Other versions
JPH09169883A (en
Inventor
純 中内
茂明 佐々木
幸則 沖本
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.)
Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Chemical Corp
Mitsubishi Rayon 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 Mitsubishi Chemical Corp, Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Chemical Corp
Priority to JP34852995A priority Critical patent/JP3183384B2/en
Publication of JPH09169883A publication Critical patent/JPH09169883A/en
Application granted granted Critical
Publication of JP3183384B2 publication Critical patent/JP3183384B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、高温下の成形にお
いても変質、熱着色が少なく、耐熱性、低吸湿性、低複
屈折性に優れた光学用樹脂組成物およびその製造法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical resin composition which is less deteriorated and less thermally colored even during molding at high temperatures, and is excellent in heat resistance, low moisture absorption and low birefringence, and a method for producing the same.

【０００２】[0002]

【従来の技術】光学式情報記録体用基板、光ファイバ
ー、カメラレンズ、ピックアップレンズ、ｆθレンズ等
の光学素子に使用される材料には、一般に耐熱性、低吸
湿性、低複屈折性が要求される。メタクリル樹脂は、透
明性、耐候性に優れ、機械的強度や成形加工などのバラ
ンスに優れた樹脂であるが、反面、ポリカーボネートや
ポリスチレン、アモルファスポリオレフィンなどの樹脂
に比べ吸湿率が高く、さらに、車両用コンパクトディス
クプレーヤーのピックアップレンズなどの高耐熱性が要
求される分野では、耐熱性が不充分であるという問題点
がある。また、メタクリル樹脂の複屈折率は、ポリカー
ボネートやポリスチレンと比較すると低いことは、知ら
れているが、近年、光ディスクの高密度化によりピック
アップレンズの高性能化が要求され、従来のメタクリル
樹脂よりさらに低い複屈折率の材料が望まれている。2. Description of the Related Art Materials used for optical elements such as substrates for optical information recording media, optical fibers, camera lenses, pickup lenses, and fθ lenses generally require heat resistance, low moisture absorption, and low birefringence. You. Methacrylic resin is a resin with excellent transparency, weather resistance, and excellent balance of mechanical strength and molding process, but has a higher moisture absorption rate than resins such as polycarbonate, polystyrene, and amorphous polyolefin. In a field where high heat resistance is required, such as a pickup lens of a compact disc player, there is a problem that heat resistance is insufficient. It is known that the birefringence of methacrylic resin is lower than that of polycarbonate or polystyrene.However, in recent years, the performance of pickup lenses has been required to be higher due to the higher density of optical discs. Materials with low birefringence are desired.

【０００３】これらの要求に対して、Ｎ−置換マレイミ
ドとメタクリル酸シクロヘキシルを共重合させたメタク
リル系樹脂が提案されている（特開昭６１−９５０１１
号公報、特開昭６１−１６２５０９号公報、特開昭６４
−６２３１４号公報、特開平１−２１５８１０号公
報）。これらの樹脂は、従来のメタクリル系樹脂と同等
の優れた透明性、機械的性質を保持するとともに、メタ
クリル樹脂では持ち得なかった耐熱性、低吸湿性、低複
屈折性を有する優れた樹脂である。To meet these requirements, a methacrylic resin obtained by copolymerizing an N-substituted maleimide and cyclohexyl methacrylate has been proposed (JP-A-61-95011).
JP, JP-A-61-162509, JP-A-64
JP-A-62314, JP-A-1-215810). These resins have excellent transparency and mechanical properties equivalent to those of conventional methacrylic resins, and have excellent heat resistance, low hygroscopicity, and low birefringence that methacrylic resins could not have. is there.

【０００４】しかしながら、Ｎ−置換マレイミドとメタ
クリル酸シクロヘキシルを含むメタクリル系樹脂は、通
常のメタクリル樹脂と比較して、２００℃以上の高温下
で、共重合体の変質が起こりやすく、射出成形などの溶
融成形時に変質物が異物となって成形品に混入する問題
がある。これは、高温下で、共重合体中のメタクリル酸
シクロヘキシルの側鎖が脱離し、ポリマー鎖間に架橋反
応が起こることが原因と推測されるため、共重合体中の
ゴミ等の異物を減量しても、成形機内で異物が造られる
ため、光学素子用の材料としては不適である。また、Ｎ
−置換マレイミドを含むメタクリル系樹脂は、射出成形
時など２００℃以上の高温にさらされた場合、着色しや
すく、ポリマーが黄変するため、光学的に好ましくな
い。However, methacrylic resins containing N-substituted maleimide and cyclohexyl methacrylate are more likely to deteriorate at 200 ° C. or higher than ordinary methacrylic resins at high temperatures of 200 ° C. or higher. There is a problem that the altered substance becomes a foreign substance and is mixed into the molded product during the melt molding. This is presumed to be due to the fact that the side chains of cyclohexyl methacrylate in the copolymer are eliminated at a high temperature and a cross-linking reaction occurs between the polymer chains, so that foreign substances such as dust in the copolymer are reduced. Even so, a foreign material is formed in the molding machine, so that it is not suitable as a material for an optical element. Also, N
-A methacrylic resin containing a substituted maleimide is optically unpreferable because when exposed to a high temperature of 200 ° C. or more, such as during injection molding, the resin tends to be colored and the polymer turns yellow.

【０００５】Ｎ−置換マレイミドを含むメタクリル系樹
脂の加熱黄変を低減させるために、リン原子を有する化
合物（ホスファイト系化合物）を含有させる方法が提案
されているが（特開平３−１６７２４５号公報、特開平
６−１１６３３１号公報）、この方法では、高温下での
ポリマーの変質を抑制する効果はない。[0005] In order to reduce the heating yellowing of a methacrylic resin containing an N-substituted maleimide, a method of containing a compound having a phosphorus atom (phosphite compound) has been proposed (Japanese Patent Application Laid-Open No. 3-167245). In this method, there is no effect of suppressing the deterioration of the polymer at high temperatures.

【０００６】一方、熱着色を抑制する目的で添加する一
般のホスファイト系抗酸化剤を、水系懸濁重合前より単
量体混合物に溶解させ、重合を行った場合、重合後期に
懸濁液の粘度が上がるにつれ、粒子同士が融着し始め、
固化に至る。そのため、一般には分散剤の仕込み量を増
やし、懸濁粒子の安定性を維持させる手段がとられる
が、分散剤はメタクリル系樹脂と相溶しないため、含有
量が増えるにつれ、共重合体中の異物が増えることにな
り、光学素子としては不適である。そのため、抗酸化剤
は、得られた共重合体にブレンドし、ペレットに賦形す
る手段がとられている。しかし、この方法では、ブレン
ドする工程が増えるだけでなく、ブレンドすることによ
って、系外のゴミを同伴させる結果となる。On the other hand, when a general phosphite-based antioxidant added for the purpose of suppressing thermal coloring is dissolved in a monomer mixture before the aqueous suspension polymerization, and the polymerization is carried out, the suspension is prepared at a later stage of the polymerization. As the viscosity increases, the particles begin to fuse together,
Leads to solidification. Therefore, generally, the amount of the dispersant is increased, and measures are taken to maintain the stability of the suspended particles.However, since the dispersant is not compatible with the methacrylic resin, the content of the dispersant increases in the copolymer. This increases the amount of foreign matter, and is not suitable as an optical element. Therefore, a means is employed in which the antioxidant is blended with the obtained copolymer and shaped into pellets. However, this method not only increases the number of steps for blending, but also results in entrainment of extraneous dust by blending.

【０００７】[0007]

【発明が解決しようとする課題】本発明は、上述の背景
になされたものであり、その目的とするところは、成形
時の高温においても樹脂の変質および熱着色が少なく、
耐熱性、低吸湿性、低複屈折性に優れた光学用樹脂組成
物およびその製造法を提供することにある。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above background, and has as its object to reduce the deterioration and thermal coloring of a resin even at a high temperature during molding.
An object of the present invention is to provide an optical resin composition having excellent heat resistance, low moisture absorption, and low birefringence, and a method for producing the same.

【０００８】[0008]

【課題を解決するための手段】本発明者等は、上記の目
的を達成するために鋭意検討を進めた結果、特定組成の
メタクリル系樹脂に、特定の抗酸化剤を特定の方法で特
定量含有させることにより、上記の目的が達成できるこ
とを見い出し、本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, a specific amount of a specific antioxidant was added to a methacrylic resin having a specific composition by a specific method. It has been found that the above-mentioned object can be achieved by the inclusion, and the present invention has been completed.

【０００９】すなわち、本発明は、メタクリル酸メチル
単位１０〜７０重量％、Ｎ−置換マレイミド単位５〜３
０重量％、メタクリル酸シクロヘキシル単位１５〜８５
重量％および他の共重合可能な単量体単位０〜３０重量
％からなる共重合体（Ａ）１００重量部に対して、下記
の一般式（Ｉ）That is, the present invention relates to a method for preparing a methacrylate unit comprising 10 to 70% by weight of a methyl methacrylate unit and 5 to 3% of an N-substituted maleimide unit.
0% by weight, cyclohexyl methacrylate unit 15 to 85
% By weight and 100 parts by weight of a copolymer (A) composed of 0 to 30% by weight of other copolymerizable monomer units, the following general formula (I)

【化５】 で表わされる化合物（Ｂ）０．０５〜０．５重量部、お
よび下記の一般式(II)Embedded image 0.05 to 0.5 parts by weight of a compound (B) represented by the following general formula (II):

【化６】 で表わされる化合物（Ｃ）０を超え０．５重量部以下、
を含有してなることを特徴とする光学用樹脂組成物にあ
る。Embedded image A compound represented by the formula (C): more than 0 and 0.5 parts by weight or less ;
And a resin composition for optical use, characterized by comprising:

【００１０】また、本発明は、メタクリル酸メチル１０
〜７０重量％、Ｎ−置換マレイミド５〜３０重量％、メ
タクリル酸シクロヘキシル１５〜８５重量％およびその
他共重合可能な単量体０〜３０重量％からなる単量体混
合物１００重量部に、下記の一般式（Ｉ）[0010] The present invention also relates to methyl methacrylate 10
To 70% by weight, 5 to 30% by weight of an N-substituted maleimide, 15 to 85% by weight of cyclohexyl methacrylate and 0 to 30% by weight of a copolymerizable monomer, 100 parts by weight of the following: General formula (I)

【化７】 で表わされる化合物（Ｂ）０．０５〜０．５重量部、お
よび下記の一般式(II)Embedded image 0.05 to 0.5 parts by weight of a compound (B) represented by the following general formula (II):

【化８】 で表わされる化合物（Ｃ）０を超え０．５重量部以下、
を溶解し、懸濁重合することを特徴とする光学用樹脂組
成物の製造法にある。Embedded image A compound represented by the formula (C): more than 0 and 0.5 parts by weight or less ;
Is dissolved and subjected to suspension polymerization to produce a resin composition for optical use.

【００１１】[0011]

【発明の実施の形態】本発明の光学用樹脂組成物を構成
する共重合体（Ａ）は、メタクリル酸メチル単位、Ｎ−
置換マレイミド単位、メタクリル酸シクロヘキシル単位
および他の共重合可能な単量体単位からなるものであ
る。BEST MODE FOR CARRYING OUT THE INVENTION The copolymer (A) constituting the optical resin composition of the present invention comprises a methyl methacrylate unit,
It comprises a substituted maleimide unit, a cyclohexyl methacrylate unit and other copolymerizable monomer units.

【００１２】本発明の共重合体（Ａ）を構成するのに用
いられるメタクリル酸メチルは、光学用樹脂組成物に透
明性、耐候性および機械的性質等を付与させる成分であ
る。共重合体（Ａ）中のメタクリル酸メチル単位の含有
量は１０〜７０重量％、好ましくは２０〜６５重量％の
範囲である。メタクリル酸メチル単位の含有量が１０重
量％未満では、得られる光学用樹脂組成物の機械的強度
が低下し、また、７０重量％を超えると光学用樹脂組成
物の低吸湿性が不充分となる。The methyl methacrylate used to constitute the copolymer (A) of the present invention is a component that imparts transparency, weather resistance, mechanical properties, and the like to the optical resin composition. The content of the methyl methacrylate unit in the copolymer (A) is in the range of 10 to 70% by weight, preferably 20 to 65% by weight. When the content of the methyl methacrylate unit is less than 10% by weight, the mechanical strength of the obtained optical resin composition decreases, and when it exceeds 70% by weight, the low hygroscopicity of the optical resin composition is insufficient. Become.

【００１３】また、本発明の共重合体（Ａ）を構成する
のに用いられるＮ−置換マレイミドは、光学用樹脂組成
物に耐熱性と低複屈折性を付与させる成分である。用い
ることのできるＮ−置換マレイミドとしては、特には限
定されないがＮ−シクロヘキシルマレイミド、Ｎ−イソ
プロピルマレイミド、Ｎ−フェニルマレイミド等が好ま
しい例として挙げられる。共重合体（Ａ）中のＮ−置換
マレイミド単位の含有量は５〜３０重量％、好ましくは
１０〜２５重量％の範囲である。Ｎ−置換マレイミド単
位の含有量が５重量％未満では、光学用樹脂組成物の耐
熱性の向上および低複屈折率化が充分に行えず、また、
３０重量％を超えると光学用樹脂組成物の複屈折率が大
きくなるとともに機械的強度が低下するようになる。The N-substituted maleimide used for constituting the copolymer (A) of the present invention is a component that imparts heat resistance and low birefringence to the optical resin composition. The N-substituted maleimide that can be used is not particularly limited, but preferred examples include N-cyclohexylmaleimide, N-isopropylmaleimide, and N-phenylmaleimide. The content of the N-substituted maleimide unit in the copolymer (A) is in the range of 5 to 30% by weight, preferably 10 to 25% by weight. When the content of the N-substituted maleimide unit is less than 5% by weight, it is not possible to sufficiently improve the heat resistance and lower the birefringence of the optical resin composition.
If it exceeds 30% by weight, the birefringence of the optical resin composition will increase and the mechanical strength will decrease.

【００１４】また、本発明の共重合体（Ａ）を構成する
のに用いられるメタクリル酸シクロヘキシルは、光学用
樹脂組成物に低吸湿性を付与させる成分である。共重合
体（Ａ）中のメタクリル酸シクロヘキシル単位の含有量
は１５〜８５重量％、好ましくは１５〜７５重量％の範
囲である。メタクリル酸シクロヘキシル単位の含有量が
１５重量％未満では、得られる光学用樹脂組成物の吸湿
性が高く、また、８５重量％を超えると光学用樹脂組成
物の機械的強度が低下するようになる。Further, cyclohexyl methacrylate used for constituting the copolymer (A) of the present invention is a component for imparting low hygroscopicity to the optical resin composition. The content of the cyclohexyl methacrylate unit in the copolymer (A) is in the range of 15 to 85% by weight, preferably 15 to 75% by weight. When the content of the cyclohexyl methacrylate unit is less than 15% by weight, the obtained optical resin composition has high hygroscopicity, and when the content exceeds 85% by weight, the mechanical strength of the optical resin composition decreases. .

【００１５】さらに、本発明の共重合体（Ａ）を構成す
るのに任意成分として用いられる他の共重合可能な単量
体としては、例えばスチレン、α−メチルスチル等の芳
香族ビニル化合物、アクリル酸メチル、アクリル酸エチ
ル、アクリル酸シクロヘキシル等のアクリル酸エステ
ル、メタクリル酸エチル、メタクリル酸イソボルニル、
メタクリル酸フェニル、メタクリル酸ジシクロペンタニ
ル等のメタクリル酸エステルなどが挙げられる。共重合
体（Ａ）中の他の共重合可能な単量体単位の含有量は、
０〜３０重量％、好ましくは０〜１５重量％の範囲であ
る。共重合体（Ａ）中の他の共重合可能な単量体単位の
含有量が３０重量％を超えると得られる光学用樹脂組成
物の機械的強度、耐熱性、透明性が低下し、また、用い
る単量体の種類によっては複屈折を大きくするようにな
る。Further, other copolymerizable monomers used as an optional component to constitute the copolymer (A) of the present invention include, for example, aromatic vinyl compounds such as styrene and α-methylstil, and acrylic monomers. Methyl acrylate, ethyl acrylate, acrylates such as cyclohexyl acrylate, ethyl methacrylate, isobornyl methacrylate,
Examples include methacrylates such as phenyl methacrylate and dicyclopentanyl methacrylate. The content of other copolymerizable monomer units in the copolymer (A) is
The range is 0 to 30% by weight, preferably 0 to 15% by weight. When the content of the other copolymerizable monomer unit in the copolymer (A) exceeds 30% by weight, the mechanical strength, heat resistance, and transparency of the obtained optical resin composition decrease, and Depending on the type of monomer used, birefringence is increased.

【００１６】本発明において使用される化合物（Ｂ）
は、上記の一般式（Ｉ）で表わされるフェノール系の抗
酸化剤である。この化合物（Ｂ）は、光学用樹脂組成物
を高温下、例えば２００℃以上の温度で成形する際の共
重合体（Ａ）の変質を少なくするために用いられるもの
である。化合物（Ｂ）の使用量は、共重合体（Ａ）１０
０重量部に対して、０．０５〜０．５重量部の範囲であ
り、０．０５重量部未満では、共重合体の高温下での変
質を防止することができず、また、０．５重量部を超え
る場合には、得られる光学用樹脂組成物の耐熱性を低下
させるとともに、高温下での共重合体の変質防止効果の
向上が認められず経済的にも不利である。Compound (B) used in the present invention
Is a phenolic antioxidant represented by the above general formula (I). The compound (B) is used to reduce the deterioration of the copolymer (A) when the optical resin composition is molded at a high temperature, for example, at a temperature of 200 ° C. or more. The amount of the compound (B) to be used depends on the copolymer (A) 10
The amount is in the range of 0.05 to 0.5 part by weight with respect to 0 part by weight, and when the amount is less than 0.05 part by weight, the deterioration of the copolymer at a high temperature cannot be prevented. If the amount exceeds 5 parts by weight, the heat resistance of the obtained optical resin composition is lowered, and no improvement in the effect of preventing deterioration of the copolymer at high temperatures is observed, which is economically disadvantageous.

【００１７】化合物（Ｂ）は共重合体（Ａ）にブレンド
し、賦形してもよいが、異物混入の点から、重合前に単
量体に溶解した後、重合を行う方が好ましい。上記の一
般式（Ｉ）以外のフェノール系の抗酸化剤で、２００℃
よりも低い温度でその効果を発揮することができるもの
があるが、２００℃以上の高温下で変質抑止効果を持つ
ものは、これまでにまだ上記の一般式（Ｉ）以外に見つ
かっていない。一般のメタクリル系樹脂の中には２００
℃以下で射出成形可能な樹脂もあるが、Ｎ−置換マレイ
ミドとメタクリル酸シクロヘキシルを含むポリマーは、
光学用途のため、出来るだけ内部歪みを低減させる目的
で高温で成形される。したがって、２００℃以上の高温
下での変質を防止することが重要となる。The compound (B) may be blended with the copolymer (A) and shaped, but it is preferable to dissolve the monomer before the polymerization and then perform the polymerization from the viewpoint of contamination. A phenolic antioxidant other than the above general formula (I),
Some of them can exert their effect at lower temperatures, but those having a deteriorating effect at high temperatures of 200 ° C. or higher have not yet been found other than the above general formula (I). Some methacrylic resins include 200
Although some resins can be injection molded below ℃, the polymer containing N-substituted maleimide and cyclohexyl methacrylate,
For optical use, it is molded at high temperature to reduce internal strain as much as possible. Therefore, it is important to prevent deterioration at a high temperature of 200 ° C. or higher.

【００１８】また、本発明において、添加される化合物
（Ｃ）は、上記の一般式(II)で表わされるリン系の抗酸
化剤である。この化合物（Ｃ）は、光学用樹脂組成物の
加熱時の着色を抑制するために添加されるものであり、
例えば半導体レーザーを光源に使用するピックアップレ
ンズなど特定の波長のみが透過すれば良いレンズには材
料の着色は影響しないため不要であるが、カメラレンズ
やプロジェクションレンズなどレンズの色が影響する用
途には必要となる。このような用途に対しての化合物
（Ｃ）の使用量は、共重合体（Ａ）１００重量部に対し
て、０を超えて０．５重量部以下の範囲であり、使用量
が０．５重量部を超えた場合には、得られる光学用樹脂
組成物の耐熱性が低下し、着色の抑制効果の向上が認め
られず経済的に不利である。[0018] Te present invention smell, added pressure the compound (C) is an antioxidant of the phosphorus system represented by the above general formula (II). The compound (C) is added to suppress coloring of the optical resin composition during heating.
For example, a lens that only needs to transmit a specific wavelength, such as a pickup lens that uses a semiconductor laser as a light source, is not necessary because the coloring of the material does not affect it. Required. The amount of the compound of for such purpose (C) is the copolymer (A) 100 parts by weight of in the range of 0.5 parts by weight or less than 0, the amount is zero. If the amount exceeds 5 parts by weight, the heat resistance of the obtained optical resin composition decreases, and no improvement in the effect of suppressing coloring is observed, which is economically disadvantageous.

【００１９】化合物（Ｃ）は、共重合体（Ａ）にブレン
ドした後、賦形してもよいが、ブレンド時に系外からの
異物を混入させる可能性があるため、重合前に単量体に
溶解させた後、重合を行う方が好ましい。上記の一般式
(II)で表わされる化合物以外のホスファイト系化合物
で、単量体に溶解させ、重合を行った場合、懸濁重合中
に固化せずに用いることができるものはまだ見つかって
いない。The compound (C) may be shaped after blending with the copolymer (A). However, there is a possibility that foreign matter from outside the system may be mixed during the blending. It is more preferable to carry out polymerization after dissolving in water. General formula above
When a phosphite-based compound other than the compound represented by the formula (II) is dissolved in a monomer and polymerized, it can be used without being solidified during suspension polymerization.

【００２０】本発明の光学用樹脂組成物の製造方法は、
塊状重合法、懸濁重合法、乳化重合法などの公知の方法
が可能であるが、取扱いの容易さから懸濁重合法が好ま
しい。The method for producing the optical resin composition of the present invention comprises:
Known methods such as a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method are possible, but the suspension polymerization method is preferable because of easy handling.

【００２１】本発明の光学用樹脂組成物を懸濁重合法に
より製造する場合には、まず、前記のメタクリル酸メチ
ル、Ｎ−置換マレイミド、メタクリル酸シクロヘキシル
および必要に応じて用いられる他の共重合可能な単量体
からなる単量体混合物に、上記の一般式（Ｉ）で表わさ
れる化合物、上記の一般式(II)で表わされる化合物、重
合開始剤および連鎖移動剤を溶解させる。When the optical resin composition of the present invention is produced by a suspension polymerization method, first, the above-mentioned methyl methacrylate, N-substituted maleimide, cyclohexyl methacrylate and other copolymers used if necessary a monomer mixture consisting of monomers capable of a compound represented by the above general formula (I), a compound represented by the above general formula Symbol (II), dissolving the polymerization initiator and chain transfer agent.

【００２２】次いで、その得られた均一混合液を分散安
定剤を存在させた水媒体に懸濁した後、所定の重合温度
で一時間保持して重合を完結させ、その得られた懸濁重
合物を濾過し、水洗、乾燥することにより本発明の光学
用樹脂組成物を得ることができる。Next, the obtained homogeneous mixture is suspended in an aqueous medium in which a dispersion stabilizer is present, and the suspension is maintained at a predetermined polymerization temperature for 1 hour to complete the polymerization. The optical resin composition of the present invention can be obtained by filtering, washing, and drying the substance.

【００２３】懸濁重合の際に使用される重合開始剤とし
ては、例えば２，２′−アゾビスイソブチロニトリル、
２，２′−アゾビス−２，４−ジメチルバレロニトリル
等のアゾ系開始剤、ベンゾイルパーオキサイド、ｔ−ブ
チルパーオキシ２−エチルヘキサノエート、１，１−ジ
−ｔ−ブチルパーオキシ−２−メチルシクロヘキサン等
の過酸化物系開始剤などを挙げることができる。これら
の重合開始剤の使用量は、上記単量体混合物１００重量
部に対して０．００１〜３重量部の範囲である。Examples of the polymerization initiator used in the suspension polymerization include, for example, 2,2'-azobisisobutyronitrile,
An azo initiator such as 2,2'-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, 1,1-di-t-butylperoxy-2 Peroxide initiators such as -methylcyclohexane. The amount of these polymerization initiators used is in the range of 0.001 to 3 parts by weight based on 100 parts by weight of the monomer mixture.

【００２４】また、懸濁重合において使用される連鎖移
動剤としては、例えばｔ−ブチルメルカプタン、ｎ−ブ
チルメルカプタン、ｎ−オクチルメルカプタン、ｎ−ド
デシルメルカプタン等が挙げられる。これらの連鎖移動
剤の使用量は、上記単量体混合物１００重量部に対して
０〜３重量部の範囲である。Examples of the chain transfer agent used in suspension polymerization include, for example, t-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and the like. The amount of these chain transfer agents used is in the range of 0 to 3 parts by weight based on 100 parts by weight of the monomer mixture.

【００２５】懸濁重合において使用される分散安定剤と
しては、ポリビニルアルコール、（メタ）アクリル酸の
単独重合体あるいは共重合体のアルカリ金属塩、メタク
リル酸メチルとメタクリル酸２−スルホエチルのナトリ
ウム塩の共重合体、カルボキシルセルロース、ゼラチ
ン、デンプン、硫酸バリウム、硫酸カルシウム、炭酸カ
ルシウム、炭酸マグネシウム、燐酸カルシウム等が挙げ
られる。これら分散剤は、水１００重量部に対して、
０．０１〜５重量部の範囲で使用することが好ましい。
また、必要に応じて、これら分散剤とともに、塩化ナト
リウム、塩化カリウム、硫酸ナトリウム、硫酸カリウ
ム、硫酸マンガン等の分散助剤を併用することもでき
る。Examples of the dispersion stabilizer used in the suspension polymerization include polyvinyl alcohol, an alkali metal salt of a homopolymer or copolymer of (meth) acrylic acid, and a sodium salt of methyl methacrylate and 2-sulfoethyl methacrylate. Copolymers, carboxycellulose, gelatin, starch, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, calcium phosphate and the like can be mentioned. These dispersants are based on 100 parts by weight of water.
It is preferable to use it in the range of 0.01 to 5 parts by weight.
If necessary, a dispersing aid such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and manganese sulfate can be used together with these dispersants.

【００２６】懸濁重合における単量体に対する水の量
は、特には限定されないが、単量体／水の割合が重量比
で１／１〜１／１０となる範囲が好ましく、より好まし
くは１／２〜１／４の範囲である。The amount of water with respect to the monomer in the suspension polymerization is not particularly limited, but is preferably in a range where the ratio of monomer / water is 1/1 to 1/10 by weight, more preferably 1 to 10. / 2 to ４.

【００２７】さらに、懸濁重合の重合温度は、特には限
定されないが５０〜１５０℃、好ましくは５０〜１３０
℃の範囲である。Further, the polymerization temperature of the suspension polymerization is not particularly limited, but is 50 to 150 ° C., preferably 50 to 130 ° C.
It is in the range of ° C.

【００２８】本発明の光学用樹脂組成物には、目的に応
じて、公知の添加剤、例えば染料、顔料等の着色剤、可
塑剤、離型剤、紫外線吸収剤などの光安定剤等添加する
ことが出来る。To the optical resin composition of the present invention, known additives such as coloring agents such as dyes and pigments, plasticizers, release agents, and light stabilizers such as ultraviolet absorbers may be added according to the purpose. You can do it.

【００２９】[0029]

【実施例】以下、実施例により本発明を具体的に説明す
る。なお、実施例および比較例における物性の評価は次
に示す方法を用いて行った。The present invention will be described below in detail with reference to examples. The evaluation of the physical properties in Examples and Comparative Examples was performed using the following methods.

【００３０】（１）熱変形温度（ＨＤＴ） 樹脂ペレットを加圧成形して（２００℃，２０ｋｇ／ｃ
ｍ2 ）、１２７ｍｍ×６．４ｍｍ×１３ｍｍ（厚さ）の
試片を作製し、ＡＳＴＭ−Ｄ６４８に準拠して荷重１８
２０ＫＰａで測定した。(1) Heat Deformation Temperature (HDT) Resin pellets are molded under pressure (200 ° C., 20 kg / c).
m 2 ), a sample of 127 mm × 6.4 mm × 13 mm (thickness) was prepared, and a load of 18 was measured in accordance with ASTM-D648.
It was measured at 20 KPa.

【００３１】（２）着色試験 樹脂ペレットを用いて、１００ｍｍ×５０ｍｍ×２ｍｍ
（厚さ）の平板を２３０℃、２７０℃の各温度におい
て、下記の成形条件で射出成形により作製し、着色の差
を下記の基準で評価した。 ○：２３０℃成形品と２７０℃成形品との間に差が認め
られない。 △：２７０℃成形品の方が２３０℃成形品に比べて若干
黄変している。 ×：２７０℃成形品の方が２３０℃成形品に比べて著し
く黄変している。(2) Coloring test 100 mm × 50 mm × 2 mm using resin pellets
(Thickness) flat plates were produced by injection molding at 230 ° C. and 270 ° C. under the following molding conditions, and the difference in coloring was evaluated according to the following criteria. ：: No difference is observed between the molded product at 230 ° C. and the molded product at 270 ° C. Δ: The 270 ° C molded product slightly yellowed compared to the 230 ° C molded product. ×: The 270 ° C molded product is significantly yellowed compared to the 230 ° C molded product.

【００３２】成形条件 成形機：日精樹脂（株）製、射出成形機 ＰＳ−６０Ｅ シリンダー設定温度：２３０℃、２７０℃ 金型設定温度：７０℃ 射出設定圧力：６００〜１０００ｋｇ／ｃｍ2 射出設定速度：５０％ 射出時間：１８秒 冷却時間：２３秒Molding conditions Molding machine: Nissei Plastics Co., Ltd., injection molding machine PS-60E Cylinder set temperature: 230 ° C., 270 ° C. Die set temperature: 70 ° C. Injection set pressure: 600 to 1000 kg / cm 2 Injection set speed : 50% Injection time: 18 seconds Cooling time: 23 seconds

【００３３】（３）変質試験 樹脂ペレット１ｇをオーブン中で２３０℃、２５０℃、
２７０℃の各温度で１時間加熱した後、各々を２５ｍｌ
のアセトン中に入れ、アセトン不溶分の有無を調べ、下
記の基準で判定した。加熱により共重合体が変質した場
合、溶剤に対し不溶となる。 ○：不溶分がない。 △：若干、不溶分がある。 ×：かなり不溶分がある。(3) Alteration test 1 g of resin pellets were placed in an oven at 230 ° C. and 250 ° C.
After heating at each temperature of 270 ° C. for 1 hour, each was 25 ml
In acetone, and the presence or absence of acetone-insoluble components was examined. When the copolymer is deteriorated by heating, it becomes insoluble in a solvent. ：: No insoluble content. Δ: Some insolubles were found. ×: There are considerable insolubles.

【００３４】なお、表１中の略記号は以下の化合物を表
わす。 ＭＭＡ ：メタクリル酸メチル ＣＨＭＩ：Ｎ−シクロヘキシルマレイミド ＰｈＭＩ：Ｎ−フェニルマレイミド ＣＨＭＡ：メタクリル酸シクロヘキシル 化合物（Ｉ）：上記一般式（Ｉ）で表わされる化合物
（旭電化工業（株）製、アデカスタブＡＯ−６０） 化合物(II)：上記一般式 (II) で表わされる化合物（旭
電化工業（株）製、アデカスタブ１５００） 化合物(III) ：下記の一般式 (III)で表わされる化合物The abbreviations in Table 1 represent the following compounds. MMA: methyl methacrylate CHMI: N-cyclohexylmaleimide PhMI: N-phenylmaleimide CHMA: cyclohexyl methacrylate Compound (I): Compound represented by the above general formula (I) (Adeka Stab AO-60 manufactured by Asahi Denka Kogyo KK) Compound (II): Compound represented by the above general formula (II) (Adeka Stab 1500, manufactured by Asahi Denka Kogyo KK) Compound (III): Compound represented by the following general formula (III)

【化９】 （旭電化工業（株）製、アデカスタブＡＯ−５０） 化合物(IV)：下記の一般式 (IV) で示される化合物Embedded image (ADK STAB AO-50, manufactured by Asahi Denka Kogyo KK) Compound (IV): a compound represented by the following general formula (IV)

【化１０】 （旭電化工業（株）製、アデカスタブ２１１２）Embedded image (Adeka Stub 2112, manufactured by Asahi Denka Kogyo Co., Ltd.)

【００３５】［実施例１］ メタクリル酸メチル６０重量％、Ｎ−シクロヘキシルマ
レイミド２２重量％、メタクリル酸シクロヘキシル１８
重量％の割合で混合した単量体混合物１００重量部に、
連鎖移動剤としてｎ−オクチルメルカプタン０．１５重
量部、重合開始剤として１，１−ジ−ｔ−ブチルパーオ
キシ−２−メチルシクロヘキサン０．３重量部、離型剤
としてステアリルアルコール０．２重量部、抗酸化剤と
して上記の一般式（Ｉ）で表わされる化合物（旭電化工
業（株）製、アデカスタブＡＯ−６０）０．１重量部お
よび上記の一般式（ＩＩ）で表わされる化合物（旭電化
工業（株）製、アデカスタブ１５００）０．１重量部を
加えて溶解し、均一混合液を調製した。Example 1 Methyl methacrylate 60% by weight, N-cyclohexylma
22% by weight of reimide , cyclohexyl methacrylate 18
100 parts by weight of the monomer mixture mixed in a ratio of
0.15 part by weight of n-octyl mercaptan as a chain transfer agent, 0.3 part by weight of 1,1-di-t-butylperoxy-2-methylcyclohexane as a polymerization initiator, 0.2 part by weight of stearyl alcohol as a release agent Parts, 0.1 parts by weight of a compound represented by the above general formula (I) (Adeka Stab AO-60, manufactured by Asahi Denka Kogyo KK) as an antioxidant and a compound represented by the above general formula (II) (Asahi Denka Kogyo Co., Ltd.) 0.1 parts by weight of Denka Kogyo Co., Ltd., Adekastab 1500) was added and dissolved to prepare a uniform mixed solution.

【００３６】次いで、この均一混合液を、分散安定剤と
してメタクリル酸とメタクリル酸２−スルホエチルのナ
トリウム塩の共重合体０．０２重量部、分散助剤として
硫酸ナトリウム０．１５重量部および分散媒として純水
２００重量部を入れてなる撹拌機付の５０リットルの重
合反応用圧力容器に入れ、窒素置換しながら２００ｒｐ
ｍで１５分撹拌した。その後、窒素雰囲気中で８５℃に
加温して重合を開始させ、重合発熱ピーク後、１２０℃
で、１時間加熱した。その後、冷却、濾過、水洗、乾燥
し、ビーズ状樹脂組成物を得た。得られたビーズ状の樹
脂組成物を二軸押出機（（株）池貝製、ＰＣＭ−３０）
にて２５０℃で混練し、ペレット化した。この樹脂ペレ
ットを用いて各種物性の評価を行った。得られた結果を
表１に示す。Then, 0.02 parts by weight of a copolymer of methacrylic acid and sodium salt of 2-sulfoethyl methacrylate as a dispersion stabilizer, 0.15 parts by weight of sodium sulfate as a dispersing aid, and a dispersion medium Into a 50 liter polymerization reaction pressure vessel equipped with a stirrer and containing 200 parts by weight of pure water,
and stirred for 15 minutes. Thereafter, the mixture was heated to 85 ° C. in a nitrogen atmosphere to start polymerization, and after the peak of the exothermic polymerization, 120 ° C.
For 1 hour. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a beaded resin composition. The obtained beaded resin composition is twin-screw extruder (PCM-30, manufactured by Ikegai Corporation).
At 250 ° C. and pelletized. Various physical properties were evaluated using the resin pellets. Table 1 shows the obtained results.

【００３７】［実施例２、比較例１〜６］ 単量体仕込み組成、抗酸化剤の種類および量を表１に示
したように変更した以外は、実施例１と同様にて各種の
樹脂組成物を製造した。表１にその得られた樹脂組成物
の物性の評価結果を示す。Example 2 , Comparative Examples 1 to 6 Various resins were prepared in the same manner as in Example 1 except that the monomer charge composition and the type and amount of the antioxidant were changed as shown in Table 1. A composition was prepared. Table 1 shows the evaluation results of the physical properties of the obtained resin composition.

【００３８】[0038]

【表１】 [Table 1]

【００３９】[0039]

【発明の効果】本発明の光学用樹脂組成物は、高温下の
成形においても変質および熱着色が少なく、耐熱性、低
吸湿性、低複屈折性に優れているために、各種の光学用
途、例えば光学式情報記録体基板、光ファイバー、カメ
ラレンズ、ピックアップレンズ、ｆθレンズ等の光学素
子材料として有用である。The optical resin composition of the present invention has little deterioration and thermal coloring even in molding at high temperature, and is excellent in heat resistance, low moisture absorption and low birefringence. For example, it is useful as an optical element material such as an optical information recording substrate, an optical fiber, a camera lens, a pickup lens, and an fθ lens.

フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０９Ｋ 15/32 Ｃ０９Ｋ 15/32 Ｃ Ｇ０２Ｂ 6/00 ３９１ Ｇ０２Ｂ 6/00 ３９１ (56)参考文献 特開 昭63−304045（ＪＰ，Ａ) 特開 平５−209102（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 33/08 - 33/12 C08K 5/103 C08K 5/524 C09K 15/08 C09K 15/32 G02B 6/00 391 Continuation of the front page (51) Int.Cl. 7 Identification symbol FI C09K 15/32 C09K 15/32 C G02B 6/00 391 G02B 6/00 391 (56) References JP-A-63-304045 (JP, A) JP-A-5-209102 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08L 33/08-33/12 C08K 5/103 C08K 5/524 C09K 15/08 C09K 15 / 32 G02B 6/00 391

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 メタクリル酸メチル単位１０〜７０重量
％、Ｎ−置換マレイミド単位５〜３０重量％、メタクリ
ル酸シクロヘキシル単位１５〜８５重量％および他の共
重合可能な単量体単位０〜３０重量％からなる共重合体
（Ａ）１００重量部に対して、下記の一般式（Ｉ） 【化１】 で表わされる化合物（Ｂ）０．０５〜０．５重量部、お
よび下記の一般式(II) 【化２】 で表わされる化合物（Ｃ）０を超え０．５重量部以下、
を含有してなることを特徴とする光学用樹脂組成物。1. 10 to 70% by weight of methyl methacrylate units, 5 to 30% by weight of N-substituted maleimide units, 15 to 85% by weight of cyclohexyl methacrylate units and 0 to 30% of other copolymerizable monomer units. % Of the copolymer (A) of the following general formula (I): 0.05 to 0.5 parts by weight of a compound (B) represented by the following formula (II): A compound represented by the formula (C): more than 0 and 0.5 parts by weight or less ;
An optical resin composition comprising: 【請求項２】 一般式(II)で表わされる化合物（Ｃ）の
含有量が０．１〜０．５重量部である請求項１に記載の
光学用樹脂組成物。 2. The optical resin composition according to claim 1, wherein the content of the compound (C) represented by the general formula (II) is 0.1 to 0.5 part by weight. 【請求項３】 メタクリル酸メチル１０〜７０重量％、
Ｎ−置換マレイミド５〜３０重量％、メタクリル酸シク
ロヘキシル１５〜８５重量％およびその他共重合可能な
単量体０〜３０重量％からなる単量体混合物１００重量
部に、下記の一般式（Ｉ） 【化３】 で表わされる化合物（Ｂ）０．０５〜０．５重量部、お
よび下記の一般式(II) 【化４】 で表わされる化合物（Ｃ）０を超え０．５重量部以下、
を溶解し、懸濁重合することを特徴とする光学用樹脂組
成物の製造法。3. 10 to 70% by weight of methyl methacrylate,
To 100 parts by weight of a monomer mixture comprising 5 to 30% by weight of an N-substituted maleimide, 15 to 85% by weight of cyclohexyl methacrylate and 0 to 30% by weight of other copolymerizable monomers, the following general formula (I) Embedded image And 0.05 to 0.5 parts by weight of a compound (B) represented by the following general formula (II): A compound represented by the formula (C): more than 0 and 0.5 parts by weight or less ;
A method for producing an optical resin composition, comprising: 【請求項４】 一般式(II)で表わされる化合物（Ｃ）
０．１〜０．５重量部を溶解する請求項３に記載の光学
用樹脂組成物の製造法。 4. A compound (C) represented by the general formula (II)
The method for producing an optical resin composition according to claim 3, wherein 0.1 to 0.5 part by weight is dissolved.
JP34852995A 1995-12-20 1995-12-20 Optical resin composition and method for producing the same Expired - Fee Related JP3183384B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP34852995A JP3183384B2 (en) 1995-12-20 1995-12-20 Optical resin composition and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP34852995A JP3183384B2 (en) 1995-12-20 1995-12-20 Optical resin composition and method for producing the same

Publications (2)

Publication Number Publication Date
JPH09169883A JPH09169883A (en) 1997-06-30
JP3183384B2 true JP3183384B2 (en) 2001-07-09

Family

ID=18397629

Family Applications (1)

Application Number Title Priority Date Filing Date
JP34852995A Expired - Fee Related JP3183384B2 (en) 1995-12-20 1995-12-20 Optical resin composition and method for producing the same

Country Status (1)

Country Link
JP (1) JP3183384B2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277938B1 (en) * 1996-07-30 2001-08-21 Hitachi Chemical Co., Ltd. Process for the preparation of non-birefringent optical resin and optical elements made by using the resin prepared by the process
WO2013157529A1 (en) 2012-04-17 2013-10-24 三菱瓦斯化学株式会社 Thermoplastic resin
US20150148508A1 (en) 2012-04-27 2015-05-28 Kuraray Co., Ltd. (meth) acrylic resin composition

Also Published As

Publication number Publication date
JPH09169883A (en) 1997-06-30

Similar Documents

Publication Publication Date Title
JP3183384B2 (en) Optical resin composition and method for producing the same
JPH0546368B2 (en)
JP3870670B2 (en) Non-birefringent pickup lens resin composition and pickup lens using the same
WO2006025360A1 (en) Optical copolymer and molded product comprising the same
JP2007154072A (en) Copolymer for optical use and molded-article therefrom
JP2856794B2 (en) Methacrylic resin for optical
JPH03153715A (en) Optical methacrylic resin
JP2659773B2 (en) Methacrylic copolymer
JP3870715B2 (en) Non-birefringent pickup lens resin composition and pickup lens using the same
JP3623891B2 (en) Method for producing polymer
JP3202884B2 (en) Optical element
JPH0625359A (en) Molding material having low birefringence
JPH0643461B2 (en) Method for producing optical resin composition
JPS60115605A (en) Lowly moisture-absorptive methacrylate resin
JPH11302492A (en) Resin composition for optical element and its preparation
JP4058287B2 (en) Molded body of poly (meth) acrylic copolymer
JP2515294B2 (en) Resin composition for optical element
JP2001181351A (en) Copolymer and optical transparent member
JPH04106113A (en) Heat-resistant methacrylic resin
JP2004139839A (en) Component for vehicle
JP3657113B2 (en) Low birefringence copolymer, process for producing the same, and pickup lens
JP3118282B2 (en) Method for producing methacrylic resin for optical element
JPS61247705A (en) Dispersant for suspension polymerization
JPH0768311B2 (en) Methacrylic resin for optical elements
JP2004204018A (en) Optical resin composition and optical element using the same

Legal Events

Date Code Title Description
FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20080427

Year of fee payment: 7

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

Free format text: PAYMENT UNTIL: 20090427

Year of fee payment: 8

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

Free format text: PAYMENT UNTIL: 20090427

Year of fee payment: 8

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

Free format text: PAYMENT UNTIL: 20100427

Year of fee payment: 9

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

Free format text: PAYMENT UNTIL: 20110427

Year of fee payment: 10

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

Free format text: PAYMENT UNTIL: 20110427

Year of fee payment: 10

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

Free format text: PAYMENT UNTIL: 20120427

Year of fee payment: 11

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

Free format text: PAYMENT UNTIL: 20120427

Year of fee payment: 11

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

Free format text: PAYMENT UNTIL: 20120427

Year of fee payment: 11

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

Free format text: PAYMENT UNTIL: 20130427

Year of fee payment: 12

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

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

Free format text: PAYMENT UNTIL: 20130427

Year of fee payment: 12

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

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

Free format text: PAYMENT UNTIL: 20130427

Year of fee payment: 12

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

Free format text: PAYMENT UNTIL: 20140427

Year of fee payment: 13

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees