JPH05155997A - Polycarbonate molding material for metallized product - Google Patents
Polycarbonate molding material for metallized productInfo
- Publication number
- JPH05155997A JPH05155997A JP34857791A JP34857791A JPH05155997A JP H05155997 A JPH05155997 A JP H05155997A JP 34857791 A JP34857791 A JP 34857791A JP 34857791 A JP34857791 A JP 34857791A JP H05155997 A JPH05155997 A JP H05155997A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate
- solvent
- solution
- organic solvent
- methylene chloride
- 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
Links
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 56
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 56
- 239000012778 molding material Substances 0.000 title claims description 7
- 239000002904 solvent Substances 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 66
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- -1 butyl acetate Chemical compound 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は真空蒸着、スパッタリン
グ、イオンプレーティング等の所謂乾式メタライジング
用製品を製造するに適したポリカーボネート成形材料に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate molding material suitable for producing so-called dry metallizing products such as vacuum deposition, sputtering and ion plating.
【０００２】[0002]
【従来の技術】従来、界面縮合反応で得られたポリカー
ボネートの有機溶媒溶液からポリカーボネートパウダー
を得る方法として、攪拌下の温水中又はポリカーボネー
トパウダーの温水スラリー中にポリカーボネートの有機
溶媒溶液を投入して有機溶媒を除去してパウダー化する
方法が知られている。しかしながら、この方法で得られ
るパウダーには、充分に乾燥してもなお有機溶媒が相当
量残留する。有機溶媒としては低沸点のハロゲン系炭化
水素特に塩化メチレンが広く使用されており、かかる塩
化メチレンが相当量残留するポリカーボネートをメタラ
イジング用製品の製造に用いると、ヒートサイクルテス
トにおいて蒸着膜に膨れ、剥離等の密着不良、割れ等が
発生したり、湿熱処理による腐食テストにおいては膜の
腐食、ピンホール、膨れ、剥離等が発生し易い。更にメ
タライジングの際、所定真空度到達時間が長くなり、生
産効率が悪くなる欠点もある。2. Description of the Related Art Conventionally, as a method for obtaining a polycarbonate powder from an organic solvent solution of a polycarbonate obtained by an interfacial condensation reaction, the organic solvent solution of the polycarbonate is put into an organic solvent solution by stirring in warm water or a slurry of warm water of the polycarbonate powder. A method is known in which a solvent is removed to form a powder. However, the powder obtained by this method still retains a considerable amount of organic solvent even after being sufficiently dried. Low boiling point halogenated hydrocarbons, especially methylene chloride, are widely used as the organic solvent, and when this methylene chloride is used in the production of a metallizing product in a polycarbonate, a vapor-deposited film swells in a heat cycle test, Adhesion failure such as peeling, cracking, and the like are likely to occur, and film corrosion, pinholes, swelling, and peeling are likely to occur in a corrosion test by wet heat treatment. Further, there is a drawback in that, during metallizing, the time required to reach a predetermined degree of vacuum is lengthened, and the production efficiency is deteriorated.
【０００３】有機溶媒残留量の少ないポリカーボネート
パウダーの製造法として、攪拌下の温水中又は温水スラ
リー中にポリカーボネートの有機溶媒溶液と共に非溶媒
又は貧溶媒を投入し、有機溶媒を除去してパウダー化
し、得られたパウダーを乾燥する方法が知られている。
この方法によれば、有機溶媒残留量を著しく減少させる
ことができる。しかしながら、この方法で得られたポリ
カーボネートを用いてもなおメタライジング製品の密着
性は不充分である。As a method for producing a polycarbonate powder having a small residual amount of an organic solvent, a non-solvent or a poor solvent is put together with an organic solvent solution of polycarbonate in hot water or a slurry of hot water under stirring, and the organic solvent is removed to form a powder. A method of drying the obtained powder is known.
According to this method, the residual amount of the organic solvent can be significantly reduced. However, even if the polycarbonate obtained by this method is used, the adhesion of the metallized product is still insufficient.
【０００４】[0004]
【発明が解決しようとする課題】本発明は密着性、耐久
性、作業性に優れたメタライジング用製品を製造するに
適したポリカーボネート成形材料を提供することを目的
とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polycarbonate molding material suitable for producing a metallizing product having excellent adhesion, durability and workability.
【０００５】本発明者は、非溶媒又は貧溶媒添加法で得
られる低沸点ハロゲン系有機溶媒含量の低減されたポリ
カーボネートを用いて上記目的を達成せんとして鋭意検
討した結果、非溶媒又は貧溶媒は沸点が比較的高いため
樹脂中に残留し易いこと、及びこの残留した非溶媒又は
貧溶媒がメタライズポリカーボネート製品の密着性、耐
久性等の性能を低下させることを見出し、更に検討を重
ねて本発明に到達したものである。The present inventor has made earnest studies as to achieve the above object by using a polycarbonate having a low boiling point halogenated organic solvent content obtained by a non-solvent or poor solvent addition method, and as a result, the non-solvent or poor solvent was found to be It was found that the boiling point is relatively high in the resin because it is relatively high, and that the residual non-solvent or poor solvent reduces the adhesion, durability, and other performances of the metallized polycarbonate product, and the present invention was further studied. Has reached.
【０００６】[0006]
【課題を解決するための手段】本発明は、ポリカーボネ
ートの有機溶媒溶液から非溶媒及び／又は貧溶媒を用い
て得られるポリカーボネートであって、該ポリカーボネ
ート中に残留する非溶媒及び／又は貧溶媒量が５０ppm
以下であることを特徴とするメタライジング製品用ポリ
カーボネート成形材料に係るものである。The present invention relates to a polycarbonate obtained by using a nonsolvent and / or a poor solvent from a solution of a polycarbonate in an organic solvent, and the amount of the nonsolvent and / or the poor solvent remaining in the polycarbonate. Is 50ppm
The present invention relates to a polycarbonate molding material for metallizing products characterized by the following.
【０００７】本発明でいうポリカーボネートは、二価フ
ェノールのアルカリ水溶液とホスゲンを有機溶媒の存在
下反応させて製造されるものであり、これにジカルボン
酸成分を共重合させたポリエステルカーボネートであっ
てもよい。ポリカーボネートの重合度は特に限定する必
要はなく、粘度平均分子量で通常１２０００〜５０００
０であり、特に１４０００〜３５０００が好ましい。更
に、二種以上の分子量水準のポリカーボネートの混合
物、例えば粘度平均分子量が８００００以上の超高重合
度のポリカーボネートと通常の分子量のポリカーボネー
トとの混合物であってもよい。The polycarbonate referred to in the present invention is produced by reacting an alkaline aqueous solution of a dihydric phenol with phosgene in the presence of an organic solvent, and even a polyester carbonate obtained by copolymerizing this with a dicarboxylic acid component. Good. The degree of polymerization of polycarbonate is not particularly limited, and is usually 12,000 to 5,000 in terms of viscosity average molecular weight.
0, particularly preferably 14000 to 35000. Further, it may be a mixture of two or more types of polycarbonate having a molecular weight level, for example, a mixture of a polycarbonate having an ultrahigh degree of polymerization having a viscosity average molecular weight of 80,000 or more and a polycarbonate having a normal molecular weight.
【０００８】ここで用いる二価フェノールとしては２，
２−ビス（４−ヒドロキシフエニル）プロパン［通称ビ
スフェノールＡ］が主として用いられるが、その一部又
は全部を他の二価フェノールで置換えてもよい。他の二
価フェノールとしては、例えばビス（４−ヒドロキシフ
エニル）メタン、１，１−ビス（４−ヒドロキシフェニ
ル）エタン、１，１−ビス（４−ヒドロキシフェニル）
シクロヘキサン、２，２−ビス（４−ヒドロキシ−３−
メチルフェニル）プロパン、２，２−ビス（４−ヒドロ
キシフェニル）ブタン、ビス（４−ヒドロキシフェニ
ル）スルホン、ビス（４−ヒドロキシフェニル）エーテ
ル、ビス（４−ヒドロキシフェニル）ケトン、４，４′
−ジヒドロキシジフェニル、ハイドロキノン、２，６−
ジヒドロキシナフタレン等があげられる。またフェニル
基に低級アルキル基又はハロゲン原子が置換された二価
フェノールであってもよい。また例えば三官能以上の多
官能性芳香族化合物を二価フェノール及びホスゲンと反
応させた分岐ポリカーボネートであってもよい。The dihydric phenol used here is 2,
2-Bis (4-hydroxyphenyl) propane [commonly called bisphenol A] is mainly used, but part or all of it may be replaced with other dihydric phenol. Other dihydric phenols include, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl).
Cyclohexane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, 4,4 ′
-Dihydroxydiphenyl, hydroquinone, 2,6-
Examples thereof include dihydroxynaphthalene. Further, it may be a divalent phenol in which a lower alkyl group or a halogen atom is substituted on the phenyl group. Further, for example, a branched polycarbonate obtained by reacting a trifunctional or higher polyfunctional aromatic compound with a dihydric phenol and phosgene may be used.
【０００９】二価フェノールのアルカリ水溶液に用いる
アルカリとしては、例えば水酸化ナトリウム、水酸化カ
リウム等の強塩基性水酸化物が好ましい。これらの塩基
性水酸化物は通常水溶液として用いられ、その濃度は通
常５〜１０重量％である。また塩基性水酸化物の使用量
は、二価フェノールに対する理論量である２倍モルより
やや過剰になる量が好ましく、二価フェノールに対して
２．２〜３．０倍モルが好ましい。As the alkali used in the alkali aqueous solution of dihydric phenol, for example, a strongly basic hydroxide such as sodium hydroxide or potassium hydroxide is preferable. These basic hydroxides are usually used as an aqueous solution, and the concentration thereof is usually 5 to 10% by weight. Further, the amount of the basic hydroxide used is preferably an amount that is slightly in excess of the theoretical amount of 2 times the molar amount of the dihydric phenol, and preferably 2.2 to 3.0 times the molar amount of the dihydric phenol.
【００１０】有機溶媒としては、例えば塩化メチレン、
クロロホルム、１，２−ジクロロエタン、１，１，２−
トリクロロエタン、テトラクロロエタン等のハロゲン化
脂肪族炭化水素があげられるが、工業的には塩化メチレ
ンが好ましく使用される。また末端停止剤として、例え
ばフェノール、p-tert−ブチルフェノール、２，４，６
−トリブロモフェノールの如き一価フェノール等を用い
てもよい。Examples of the organic solvent include methylene chloride,
Chloroform, 1,2-dichloroethane, 1,1,2-
Halogenated aliphatic hydrocarbons such as trichloroethane and tetrachloroethane can be mentioned, but methylene chloride is preferably used industrially. Further, as a terminal stopper, for example, phenol, p-tert-butylphenol, 2,4,6
-Monohydric phenols such as tribromophenol may be used.
【００１１】本発明の成形材料は、二価フェノールのア
ルカリ水溶液とホスゲンを有機溶媒の存在下反応させて
得られるポリカーボネートの有機溶媒溶液から、有機溶
媒を除去してポリカーボネートパウダーを得る際に、非
溶媒及び／又は貧溶媒を用いて有機溶媒含有量を著しく
減少させたポリカーボネートであって且つ非溶媒及び／
又は貧溶媒の含有量が５０ppm 以下のものである。The molding material of the present invention is prepared by removing an organic solvent from a polycarbonate organic solvent solution obtained by reacting an aqueous alkaline solution of a dihydric phenol with phosgene in the presence of an organic solvent to obtain a polycarbonate powder. A polycarbonate having a significantly reduced organic solvent content using a solvent and / or a poor solvent, and a non-solvent and / or
Alternatively, the content of the poor solvent is 50 ppm or less.
【００１２】ポリカーボネートの有機溶媒溶液から、非
溶媒及び／又は貧溶媒を用いて非溶媒及び／又は貧溶媒
の含有量が５０ppm 以下のポリカーボネートを製造する
方法としては、例えば（１）ポリカーボネートの有機溶
媒溶液を高温の熱水中に投入して急激に溶媒を除去し、
大部分の有機溶媒を除去したポリカーボネートパウダー
と熱水の混合スラリー中に非溶媒及び／又は貧溶媒を添
加攪拌した後分離し、乾燥する方法、（２）予めポリカ
ーボネートの有機溶媒溶液に非溶媒及び／又は貧溶媒を
投入し、この溶液を高温の熱水中に投入して急激に溶媒
を除去した後分離し、乾燥する方法、（３）ポリカーボ
ネートの有機溶媒溶液と非溶媒及び／又は貧溶媒を別々
に高温の熱水中に投入して急激に溶媒を除去した後分離
し、乾燥する方法等によって得られる。ここでいう高温
とは５０℃以上、好ましくは６０〜１００℃であり、か
かる高温の熱水中にポリカーボネートの有機溶媒溶液を
投入して急激に溶媒を除去する方法は、得られるポリカ
ーボネートパウダーは多孔性であって、見掛けの比重が
小さく、取扱性がよくないために顧みられなかったもの
である。As a method for producing a polycarbonate containing 50 ppm or less of the non-solvent and / or the poor solvent from the solution of the polycarbonate in the organic solvent, for example, (1) the organic solvent of the polycarbonate is used. Pour the solution into hot hot water to remove the solvent rapidly,
A method in which a non-solvent and / or a poor solvent are added to a mixed slurry of polycarbonate powder from which most of the organic solvent has been removed and hot water, and the mixture is stirred and then separated, and (2) a non-solvent is added to an organic solvent solution of polycarbonate in advance. / Or a poor solvent is charged, the solution is poured into hot water of high temperature to rapidly remove the solvent, then separated, and dried, (3) an organic solvent solution of polycarbonate and a non-solvent and / or a poor solvent Are separately poured into hot water of high temperature to rapidly remove the solvent, then separated and dried. The high temperature referred to here is 50 ° C. or higher, preferably 60 to 100 ° C. The method for rapidly removing the solvent by pouring the organic solvent solution of the polycarbonate into the hot water of such high temperature is that the obtained polycarbonate powder is porous. It was a property that was not taken into consideration because of its low apparent specific gravity and poor handleability.
【００１３】ここで用いる非溶媒及び貧溶媒は、ポリカ
ーボネート溶液に用いた有機溶媒に可溶で且つポリカー
ボネートを溶解しないか、僅かに溶解するものである。
例えば n−ヘプタン、 n−ヘキサン、シクロヘキサン等
の脂肪族炭化水素類、ベンゼン、トルエン、キシレン、
クロルベンゼン等の芳香族炭化水素類、酢酸ブチル等の
エステル類、アセトン、メチルイソブチルケトン等のケ
トン類があげられる。これらは単独でも、また二種以上
の混合溶液であってもよい。The non-solvent and poor solvent used here are those which are soluble in the organic solvent used for the polycarbonate solution and which do not dissolve or slightly dissolve the polycarbonate.
For example, n-heptane, n-hexane, aliphatic hydrocarbons such as cyclohexane, benzene, toluene, xylene,
Examples thereof include aromatic hydrocarbons such as chlorobenzene, esters such as butyl acetate, and ketones such as acetone and methyl isobutyl ketone. These may be used alone or as a mixed solution of two or more kinds.
【００１４】かくして得られるパウダーは有機溶媒を殆
ど含まず、非溶媒及び貧溶媒の残留量も大幅に低減され
ており、そのまま又はペレットにして成形に供すること
ができ、得られた製品にメタライジングしたものは極め
て優れた密着性、耐久性を示し、更に生産性も良好であ
る。The powder thus obtained contains almost no organic solvent, and the residual amounts of the non-solvent and the poor solvent are greatly reduced. It can be used as it is or in the form of pellets for molding, and the resulting product is metallized. Those obtained showed excellent adhesion and durability, and also had good productivity.
【００１５】上記ポリカーボネートを用いてメタライジ
ング用製品を成形するに際して、ポリカーボネートに、
必要に応じて添加剤、例えば酸化防止剤、帯電防止剤、
離型剤、滑剤、光安定剤、紫外線吸収剤等を添加しても
よく、また例えばポリスチレン、ポリメチルメタクリレ
ート、ＡＳ樹脂、ＡＢＳ樹脂、ポリエステル、ポリフェ
ニレンオキサイド、ナイロン等の如き他の熱可塑性樹脂
を混合してもよい。When molding a metallizing product using the above polycarbonate,
If necessary, additives such as antioxidants, antistatic agents,
Release agents, lubricants, light stabilizers, UV absorbers, etc. may be added, and other thermoplastic resins such as polystyrene, polymethylmethacrylate, AS resin, ABS resin, polyester, polyphenylene oxide, nylon, etc. may be added. You may mix.
【００１６】[0016]
【実施例】以下実施例をあげて更に説明する。なお、実
施例中の部は重量部を示し、％は重量％を示す。また残
留溶媒の定量分析、蒸着、ヒートサイクルテストは下記
の方法で行った。EXAMPLES The present invention will be further described below with reference to examples. In addition, the part in an Example shows a weight part and% shows weight%. Quantitative analysis of residual solvent, vapor deposition, and heat cycle test were performed by the following methods.
【００１７】（ａ）ポリカーボネート中の残留塩化メチ
レン、非溶媒又は貧溶媒の定量分析はガスクロマトグラ
フ［（株）日立製作所製２６３型］を用いた。なお、カ
ラム充填剤はジオクチルセバケート（略称ＤＯＳ）であ
る。(A) Quantitative analysis of residual methylene chloride, non-solvent or poor solvent in polycarbonate was carried out using a gas chromatograph [Type 263 manufactured by Hitachi, Ltd.]. Note that the column packing material is dioctyl sebacate (abbreviation DOS).
【００１８】（ｂ）蒸着は成形品を容積量約１００リッ
トルの真空蒸着装置で実施した。アルミニュームターゲ
ットの加熱は抵抗加熱方式であり、装置内の真空度が１
×１０-5トールに到達後２０秒間蒸着し、膜厚が約６０
０オングストロームのアルミニュームを蒸着した。(B) The vapor deposition was carried out by using a vacuum vapor deposition apparatus having a volume of about 100 liters for the molded product. The aluminum target is heated by the resistance heating method, and the degree of vacuum in the device is 1
After reaching × 10 -5 torr, vapor deposition is performed for 20 seconds, and the film thickness is about 60.
0 angstrom aluminum was deposited.
【００１９】（ｃ）ヒートサイクルテストは、ヒートサ
イクルを４０回繰り返した後膨れ、剥離等の欠点を光学
顕微鏡にて調べた。なおヒートサイクルの１サイクル
は、高温（８５℃）で２時間保持した後室温（２０〜２
７℃）に１時間放置し、更に低温（−１０℃）で２時間
保持した後室温（２０〜２７℃）に１時間放置した。(C) In the heat cycle test, after repeating the heat cycle 40 times, defects such as swelling and peeling were examined with an optical microscope. In addition, 1 cycle of heat cycle WHEREIN: After hold | maintaining at high temperature (85 degreeC) for 2 hours, it is room temperature (20-2.
It was left at 7 ° C for 1 hour, kept at a low temperature (-10 ° C) for 2 hours, and then left at room temperature (20 to 27 ° C) for 1 hour.
【００２０】[0020]
【実施例１】ホスゲン吹込管、温度計及び攪拌機を備え
たステンレス製反応器に、４８．５％の水酸化ナトリウ
ム水溶液９．３２部、水４６．６５部、ハイドロサルフ
ァイト０．０３部、ビスフェノールＡ１１．８３部及び
塩化メチレン３９．３部を投入し、攪拌溶解した。溶解
後攪拌下液温を２２±２℃に保持しつつホスゲン５．９
０部を６０分間かけて吹込み反応させた。吹込み終了後
攪拌下p-tert−ブチルフェノール０．５１部、４８．５
％の水酸化ナトリウム水溶液１．３２部及びトリエチル
アミン０．０２部を加え、液温を３０〜３３℃に保持し
ながら６０分間攪拌して重合を終了した。反応終了後、
更に塩化メチレン４０．０部を加えて攪拌した後静置し
て塩化メチレン層と水層を分離した。分離した塩化メチ
レン溶液に、３５．５％の塩酸０．０７部及び水２０．
０部を加え、攪拌後静置して塩化メチレン層を分離し、
更に、分離した塩化メチレン溶液を充分に水洗した。Example 1 A stainless reactor equipped with a phosgene blow-in tube, a thermometer and a stirrer was charged with 9.32 parts of a 48.5% aqueous sodium hydroxide solution, 46.65 parts of water and 0.03 part of hydrosulfite. Bisphenol A (11.83 parts) and methylene chloride (39.3 parts) were added, and the mixture was stirred and dissolved. After dissolution, phosgene 5.9 was maintained while maintaining the liquid temperature under stirring at 22 ± 2 ° C.
0 part was reacted by blowing for 60 minutes. After the completion of blowing, p-tert-butylphenol 0.51 part and 48.5 with stirring.
% Aqueous sodium hydroxide solution (1.32 parts) and triethylamine (0.02 parts) were added, and the mixture was stirred for 60 minutes while maintaining the liquid temperature at 30 to 33 ° C to complete the polymerization. After the reaction,
Further, 40.0 parts of methylene chloride was added, and the mixture was stirred and then left to stand to separate a methylene chloride layer and an aqueous layer. To the separated methylene chloride solution, 0.07 parts of 35.5% hydrochloric acid and 20.
0 part was added, and after stirring, the mixture was left standing to separate the methylene chloride layer,
Further, the separated methylene chloride solution was thoroughly washed with water.
【００２１】この溶液に n−ヘプタン５．０部を加え、
ニーダーの内温を７５℃に維持しつつ投入攪拌してポリ
カーボネートパウダーを得た。このパウダーを防爆型熱
風乾燥機により１４０℃で８時間乾燥した後、ベント付
溶融押出機によりペレット化した。このペレットの粘度
平均分子量は１５５００、塩化メチレン含有量は１ppm
以下、 n−ヘプタン含有量は１０ppm であった。このペ
レットを１２０℃で６時間乾燥した後射出成形機［住友
重機（株）製ＤＩＳＫ５Ｍ３］によりシリンダ温度３３
０〜３５０℃、金型温度８０〜１２０℃に設定し直径８
６mm、厚さ１．２mmのディスク板を成形した。このディ
スク板に前記条件で真空蒸着し、ヒートサイクルテスト
したところ欠点数は０個であった。5.0 parts of n-heptane was added to this solution,
While maintaining the inner temperature of the kneader at 75 ° C., the mixture was charged and stirred to obtain a polycarbonate powder. This powder was dried at 140 ° C. for 8 hours with an explosion-proof hot air dryer, and then pelletized with a melt extruder with a vent. The viscosity average molecular weight of this pellet is 15500 and the content of methylene chloride is 1ppm.
Hereinafter, the n-heptane content was 10 ppm. After drying the pellets at 120 ° C. for 6 hours, the cylinder temperature was 33 with an injection molding machine [DISK5M3 manufactured by Sumitomo Heavy Industries, Ltd.].
0-350 ℃, mold temperature 80-120 ℃, diameter 8
A disk plate having a thickness of 6 mm and a thickness of 1.2 mm was formed. When this disk plate was vacuum-deposited under the above conditions and subjected to a heat cycle test, the number of defects was 0.
【００２２】[0022]
【比較例１】ニーダーの内温を４５℃に維持する以外は
実施例１と同様にしてポリカーボネートパウダーを得、
以下実施例１と同様にペレット化し、射出成形し、真空
蒸着した。ペレットの粘度平均分子量は１５５００、塩
化メチレン含有量は１ppm 以下、 n−ヘプタン含有量は
８０ppm であった。また真空蒸着ディスク板のヒートサ
イクルテスト後の膜の欠点数は２８個であった。[Comparative Example 1] A polycarbonate powder was obtained in the same manner as in Example 1 except that the inner temperature of the kneader was maintained at 45 ° C.
Thereafter, pelletization, injection molding and vacuum vapor deposition were performed in the same manner as in Example 1. The viscosity average molecular weight of the pellets was 15,500, the methylene chloride content was 1 ppm or less, and the n-heptane content was 80 ppm. Further, the number of defects of the film after the heat cycle test of the vacuum evaporation disk plate was 28.
【００２３】[0023]
【実施例２】実施例１と同様にして得た精製したポリカ
ーボネートの塩化メチレン溶液にアセトン５．０部を加
え、ニーダーの内温を７５℃に維持しつつ投入してポリ
カーボネートパウダーを得た。このパウダーを防爆型熱
風乾燥機により１４０℃で６時間乾燥した後、ベント付
溶融押出機によりペレット化した。このペレットの粘度
平均分子量は１５５００、塩化メチレン含有量は１ppm
以下、アセトン含有量は５ppm であった。実施例１と同
様にしてディスク板を成形し、真空蒸着し、ヒートサイ
クルテストした。ヒートサイクルの後の欠点数は０個で
あった。Example 2 5.0 parts of acetone was added to a methylene chloride solution of purified polycarbonate obtained in the same manner as in Example 1, and the mixture was charged while maintaining the internal temperature of the kneader at 75 ° C. to obtain a polycarbonate powder. This powder was dried at 140 ° C. for 6 hours by an explosion-proof hot air dryer, and then pelletized by a melt extruder with a vent. The viscosity average molecular weight of this pellet is 15500 and the content of methylene chloride is 1ppm.
Hereinafter, the acetone content was 5 ppm. A disk plate was molded in the same manner as in Example 1, vacuum-deposited, and subjected to a heat cycle test. The number of defects after the heat cycle was 0.
【００２４】[0024]
【比較例２】ニーダーの内温を４５℃に維持する以外は
実施例２と同様にしてポリカーボネートパウダーを得
た。このパウダーを熱風乾燥機により１４０℃で６時間
乾燥した後、ベント付溶融押出機によりペレット化し
た。このペレットの粘度平均分子量は１５５００、塩化
メチレン含有量は１ppm 以下、アセトン含有量は１００
ppm であった。実施例１と同様にしてディスク板を成形
し、真空蒸着し、ヒートサイクルテストした。ヒートサ
イクルの後の欠点数は２９個であった。Comparative Example 2 A polycarbonate powder was obtained in the same manner as in Example 2 except that the inner temperature of the kneader was maintained at 45 ° C. This powder was dried at 140 ° C. for 6 hours with a hot air dryer, and then pelletized with a melt extruder with a vent. This pellet has a viscosity average molecular weight of 15500, a methylene chloride content of 1 ppm or less, and an acetone content of 100.
It was ppm. A disk plate was molded in the same manner as in Example 1, vacuum-deposited, and subjected to a heat cycle test. The number of defects after the heat cycle was 29.
【００２５】[0025]
【実施例３】実施例１と同様にして得た精製したポリカ
ーボネートの塩化メチレン溶液にクロルベンゼン１０部
を加え、ニーダーの内温を８０℃に維持しつつ投入して
ポリカーボネートパウダーを得た。このパウダーを防爆
型熱風乾燥機により１４０℃で１０時間乾燥した後、ベ
ント付溶融押出機によりペレット化した。このペレット
の粘度平均分子量は１５５００、塩化メチレン含有量は
１ppm以下、クロルベンゼン含有量は４０ppm であっ
た。実施例１と同様にしてディスク板を成形し、真空蒸
着し、ヒートサイクルテストした。ヒートサイクルの後
の欠点数は１個であった。Example 3 To a solution of purified polycarbonate obtained in the same manner as in Example 1 was added 10 parts of chlorobenzene, and the mixture was charged while keeping the internal temperature of the kneader at 80 ° C to obtain a polycarbonate powder. This powder was dried at 140 ° C. for 10 hours with an explosion-proof hot air dryer, and then pelletized with a melt extruder with a vent. The viscosity average molecular weight of the pellets was 15,500, the methylene chloride content was 1 ppm or less, and the chlorobenzene content was 40 ppm. A disk plate was molded in the same manner as in Example 1, vacuum-deposited, and subjected to a heat cycle test. The number of defects after the heat cycle was one.
【００２６】[0026]
【比較例３】ニーダーの内温を４５℃に維持する以外は
実施例３と同様にしてポリカーボネートパウダーを得
た。このパウダーを熱風乾燥機により１４０℃で１０時
間乾燥した後、ベント付溶融押出機によりペレット化し
た。このものの粘度平均分子量は１５５００、塩化メチ
レン含有量は１ppm 以下、クロルベンゼン含有量は３０
０ppm であった。実施例１と同様の条件でディスク板を
成形し、真空蒸着し、ヒートサイクルテストした。ヒー
トサイクルの後の欠点数は５３個であった。Comparative Example 3 A polycarbonate powder was obtained in the same manner as in Example 3 except that the inner temperature of the kneader was maintained at 45 ° C. This powder was dried at 140 ° C. for 10 hours with a hot air dryer, and then pelletized with a melt extruder with a vent. This product has a viscosity average molecular weight of 15500, a methylene chloride content of 1 ppm or less, and a chlorobenzene content of 30.
It was 0 ppm. A disk plate was formed under the same conditions as in Example 1, vacuum-deposited, and subjected to a heat cycle test. The number of defects after the heat cycle was 53.
【００２７】[0027]
【比較例４】精製したポリカーボネートの塩化メチレン
溶液に n−ヘプタンを加えず、ニーダーの内温を４５℃
に維持する以外は実施例１と同様にしてポリカーボネー
トパウダーを得、以下実施例１と同様にペレット化し、
射出成形し、真空蒸着した。ペレットの粘度平均分子量
は１５５００、塩化メチレン含有量は１００ppm であっ
た。また真空蒸着ディスク板のヒートサイクルスト後の
膜の欠点数は１００個以上であった。[Comparative Example 4] The temperature inside the kneader was kept at 45 ° C without adding n-heptane to the purified methylene chloride solution of polycarbonate.
Polycarbonate powder was obtained in the same manner as in Example 1 except for maintaining
It was injection molded and vacuum evaporated. The viscosity average molecular weight of the pellets was 15,500 and the methylene chloride content was 100 ppm. The number of defects of the film after the heat cycle strike of the vacuum deposition disk plate was 100 or more.
【００２８】以上の結果をまとめて表１に示す。なお表
１中のペレット残留溶媒量の欄のＭＣは塩化メチレンを
意味する。The above results are summarized in Table 1. MC in the column of residual solvent amount of pellets in Table 1 means methylene chloride.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【発明の効果】本発明のポリカーボネート成形材料を用
いて得られる製品に真空蒸着等のドライメタライジング
したものは密着性、耐久性に極めて優れており、その奏
する工業的効果は格別なものである。Industrial Applicability The product obtained by using the polycarbonate molding material of the present invention, which has been dry metalized by vacuum deposition or the like, has excellent adhesion and durability, and its industrial effect is remarkable. ..
フロントページの続き (72)発明者 真鍋 昭良 東京都港区西新橋１丁目６番21号 帝人化 成株式会社内Front page continuation (72) Inventor Akira Manabe 1-6-21 Nishishinbashi, Minato-ku, Tokyo Teijin Kasei Co., Ltd.
Claims (1)
溶媒及び／又は貧溶媒を用いて得られるポリカーボネー
トであって、該ポリカーボネート中に残留する非溶媒及
び／又は貧溶媒量が５０ppm 以下であることを特徴とす
るメタライジング製品用ポリカーボネート成形材料。1. A polycarbonate obtained by using a non-solvent and / or a poor solvent from a solution of a polycarbonate in an organic solvent, wherein the amount of the non-solvent and / or the poor solvent remaining in the polycarbonate is 50 ppm or less. Polycarbonate molding material for metallizing products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34857791A JP3372046B2 (en) | 1991-12-06 | 1991-12-06 | Polycarbonate molding compound for metallizing products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34857791A JP3372046B2 (en) | 1991-12-06 | 1991-12-06 | Polycarbonate molding compound for metallizing products |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000164535A Division JP2001019758A (en) | 2000-01-01 | 2000-06-01 | Polycarbonate molding material for producing metallizing article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05155997A true JPH05155997A (en) | 1993-06-22 |
| JP3372046B2 JP3372046B2 (en) | 2003-01-27 |
Family
ID=18397953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34857791A Ceased JP3372046B2 (en) | 1991-12-06 | 1991-12-06 | Polycarbonate molding compound for metallizing products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3372046B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916980A (en) * | 1996-10-03 | 1999-06-29 | Mitsubishi Gas Chemical Company, Inc. | Polycarbonate resin composition |
-
1991
- 1991-12-06 JP JP34857791A patent/JP3372046B2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916980A (en) * | 1996-10-03 | 1999-06-29 | Mitsubishi Gas Chemical Company, Inc. | Polycarbonate resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3372046B2 (en) | 2003-01-27 |
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| RVOP | Cancellation by post-grant opposition |