EP0159120B1 - Lubricating agents for use in the production of carbon yarns - Google Patents
Lubricating agents for use in the production of carbon yarns Download PDFInfo
- Publication number
- EP0159120B1 EP0159120B1 EP19850301398 EP85301398A EP0159120B1 EP 0159120 B1 EP0159120 B1 EP 0159120B1 EP 19850301398 EP19850301398 EP 19850301398 EP 85301398 A EP85301398 A EP 85301398A EP 0159120 B1 EP0159120 B1 EP 0159120B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- effective component
- represent
- yarns
- lubricating agents
- 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
Links
- 239000000314 lubricant Substances 0.000 title claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052799 carbon Inorganic materials 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims description 25
- -1 polysiloxane Polymers 0.000 claims description 20
- 229920001296 polysiloxane Polymers 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000002243 precursor Substances 0.000 description 19
- 239000000839 emulsion Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
Definitions
- This invention retates to lubricating agents for the production of carbon yarns and more particularly to lubricating agents having specified amino polysiloxanes as effective component.
- these agents can not only give to the precursor a superior filament separabitity and processability, but also prevent adhesion after the infusibilizing process, thus making it possible to produce carbon yarns with superior physical chacacteristics.
- Carbon yarns are generally produced by first obtainind non-flammable yarns from a precursor by a process (hereinafter referred simply as the infusibilizing process) wherein the precursor is heated and burnt at 200 - 3000C in an oxidizing atmosphere; and second by a carbonization process wherein carbonization takes place in an inert atmosphere at a high temperature. e.g. over 700°C.
- a lubricating agent is applied prior to the infusibilizing process, and usually during the process in which the precursor itself is produced.
- silicone-type lubricating agents such as dimethyl polysiloxanes, phenylmethyl polysiloxanes, epoxy polysiloxanes, polyether polysiloxanes, amino polysiloxanes, etc.
- dimethyl polysiloxanes and phenylmethyl polysiloxanes are thermally superior but provide poor filament separability in the precursor and are poor in prevention of adhesion in the infusibilizing process.
- Epoxypolysiloxanes tend to cause fiber-to-fiber fixing due, for example, to the ring-opening polymerization of epoxy groups within their molecules and since they themselves generate tar, they are totally incapable of preventing mutual adhesion during the infusibitity process. Their presence, therefore, makes the problem worse instead of solving it.
- polyether polysiloxanes the ether bonds within, their molecules are thermally weak so that they mostly become decomposed and diffuse away, failing to exercise their capability of preventing adhesion. Moreover, their heat of thermal decomposition becomes a cause of abnormal reactions involving the yarns.
- Amino polysiloxanes of the type proposed in the past although they have more favorable characteristics than the other conventional silicone type lubricating agents discussed above have only one nitrogen atom per amino-modified group within their molecules and this means that only weak polar groups are loosely distributed around. Accordingly their orientation capability with respect to the precursor is inferior and the filament separability and degree of adhesion prevention they provide are not sufficient to be satisfactory.
- a lubricating agent for the production of carbon yarns characterised by comprising at least one amino polysiloxane of the general formula (I) as an effective component, the nitrogen content of said effective component being 1 weight % or less: where A is
- Amino polysiloxanes of formula (I) may be obtained, for example, by condensation of a silane containing an amino group and a diorgano polysiloxane with terminal hydroxyl groups.
- both a single system of amino polysiloxanes shown by (I) and a mixed system of aforementioned amino polysiloxane and a polysiloxane-type compound corresponding to A - OH in (I) can be obtained. depending on the molar ratio between silane containing the amino group and the diorgano polysiloxane with terminal hydroxyl groups.
- Both these systems contain amino polysiloxanes shown by (I) as effective component and hence are lubricating agents according to the present invention but it is a requirement that the nitrogen content of said effective component be 1 weight% or less. If the nitrogen content of the effective component exceeds 1 weight%, the orientation characteristic regarding the precursor becomes improved but the heat resistance becomes worse and tar comes to be generated during the infusibilizing process so the ability to prevent adhesion is significantly affected.
- the viscosity of the effective component at 25°C should preferably be 1-100 cm 2 /s (100 to 10.000 cst (centistokes)) and its nitrogen content should preferably be 0.5 weight% or less.
- the lubricating agents of the present invention may be used together with any known lubricant, softening agent, antistatic agent, surface active agent, antioxidant, antiseptic or conventional lubricating agent for the production of carbon yarns, as long as the desired effects of the present invention are not adversely affected.
- any known lubricant, softening agent, antistatic agent, surface active agent, antioxidant, antiseptic or conventional lubricating agent for the production of carbon yarns as long as the desired effects of the present invention are not adversely affected.
- the amount of the aforementioned effective component to be contained but it should preferably be 40 weight% or greater in view of the required filament separability of the precursor and the required adhesion-preventing property during the infusibilizing process.
- the lubricating agents of the present invention are applied during the precursor production process or before the infusibilizing process. As for the mode of application, they may be applied either as an emulsion, as a solution with an organic solvent or straight. The may be applied by a kiss-roll method, a spray method or a guide-oiling method. The amount to be deposited in these cases is preferably 0.01 to 5 weight% with respect to the precursor in order to obtain the required effects fully but economically.
- the lubricating agents of the present invention containing amino polysiloxanes shown-. by (1) as the effective component have a superior processability in the precursor production process and the infusibilizing process and in particular provide superior filament separability in the precursor and a superior capability of preventing adhesion in the infusibilizing process so that they can show better results than the previously proposed types of amino polysiloxanes.
- amino polysiloxahes of the present invention are clearly different in that they contain amino-modified groups at both ends of their molecules, it may be concluded that amino polysiloxanes of the present invention are more strongly oriented with respect to the precursor, possibly as a result of the aforementioned difference, and that the extent of this orientation property becomes particularly important when the nitrogen content is reduced in view of the required heat resistance characteristics.
- Water emulsions of lubricating agents comprising 85 weight % of the processing agents shown in Table 1 and 15 weight % of POE nonylphenyl ether were prepared.
- Test yarns were prepared by applying these water emulsions to acrylic filament yarns (83 dtex/40 filaments) so that 0.5 ⁇ 0.1 weight % will be deposited on each by the kiss roll method, and the coefficients of friction and generation of static electricity were measured and evaluated by the method to be described.
- the aforementioned water emulsions were applied to acrylic filament yarns (17776 dtex/12000 filaments) at the rate of 0.5 ⁇ 0.1 weight % by immersion method.
- the yarns were then dried for 4 seconds at 115°C by means of a dry heat roller to prepare a precursor tow and this was used as sample to evaluate the filament separability by the method described below.
- the precursor tow was processed for 60 minutes inside an oven of forced circulation type at 240°C to obtain infusibilized fibers and they were used as samples to evaluate their infusibility by the method to be described later.
- the sample was left for 24 hours under the condition of 20°C and 65%RH and caused to run in contact with a cylindrical chromium-plated pin under the same conditions with initial tension 20 g and yarn velocity of 100m/min.
- Coefficient of friction was measured by using a ⁇ -meter (made by Eiko Sokki-sha). The lower the measured value. the better is the result.
- electrostatic voltage of the yarn after the contact with the chromium-plated pin was measured by means of a static electrometer (made by Kasuga Denki Kabushiki Kaisha) and the results were evaluated according to the following standards:
- the sample was cut to 2cm lengths and shaken lightly over a black sheet of paper and its filament separability was evaluated according to the following standards:
- the sample was cut to 2cm and shaken lightly over a white sheet of paper and its infusibility was evaluated according to the following standards:
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Inorganic Fibers (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59039541A JPS60185880A (ja) | 1984-02-29 | 1984-02-29 | 炭素繊維製造用油剤 |
| JP39541/84 | 1984-02-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0159120A1 EP0159120A1 (en) | 1985-10-23 |
| EP0159120B1 true EP0159120B1 (en) | 1987-04-29 |
Family
ID=12555909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19850301398 Expired EP0159120B1 (en) | 1984-02-29 | 1985-02-28 | Lubricating agents for use in the production of carbon yarns |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0159120B1 (enExample) |
| JP (1) | JPS60185880A (enExample) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920000251B1 (ko) * | 1988-02-24 | 1992-01-10 | 다케모도 유시 가부시키가이샤 | 피치섬유의 처리방법 |
| JPH0742613B2 (ja) * | 1988-04-12 | 1995-05-10 | 日本石油株式会社 | ピッチ系炭素繊維の製造方法 |
| JP2589219B2 (ja) * | 1990-12-22 | 1997-03-12 | 東邦レーヨン株式会社 | 炭素繊維製造用プレカ−サ−及びその製造法、並びにそのプレカ−サ−から炭素繊維を製造する方法 |
| JPH0741677A (ja) * | 1993-07-26 | 1995-02-10 | Toray Dow Corning Silicone Co Ltd | 耐熱性に優れたジオルガノポリシロキサン組成物 |
| US5599778A (en) * | 1994-01-28 | 1997-02-04 | Dow Corning Toray Silicone Co., Ltd. | Organosiloxane lubricant compositions |
| JP4036354B2 (ja) * | 1998-10-12 | 2008-01-23 | 信越化学工業株式会社 | オルガノポリシロキサンを主成分とする防水処理剤組成物 |
| TW538096B (en) | 1999-06-25 | 2003-06-21 | Shinetsu Chemical Co | Nitrogen atom-containing polysiloxanes, their preparation, and fiber and fabric finishing agent compositions |
| JP3731639B2 (ja) | 1999-11-15 | 2006-01-05 | 信越化学工業株式会社 | フッ素含有ポリシロキサン、その製造方法、及び繊維処理剤組成物 |
| JP5707690B2 (ja) * | 2009-11-04 | 2015-04-30 | 三菱レイヨン株式会社 | 炭素繊維前駆体アクリル繊維用油剤組成物、および炭素繊維前駆体アクリル繊維束とその製造方法 |
| EP3130620B1 (en) | 2014-04-10 | 2020-08-19 | Shin-Etsu Chemical Co., Ltd. | Silicone composition, silicone emulsion composition, and fiber treatment agent |
| JP6394493B2 (ja) | 2015-05-18 | 2018-09-26 | 信越化学工業株式会社 | ブロックポリイソシアネート含有硬化性シリコーン組成物及びそれを用いた繊維処理剤 |
| JP7003707B2 (ja) | 2018-02-07 | 2022-01-21 | 信越化学工業株式会社 | 繊維処理剤及びその製造方法 |
| US20220251303A1 (en) | 2019-05-22 | 2022-08-11 | Shin-Etsu Chemical Co., Ltd. | Aminoalkyl group-containing organopolysiloxane and fiber treatment agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5234025A (en) * | 1975-09-08 | 1977-03-15 | Japan Exlan Co Ltd | Process for producing carbon fibers having excellent performances |
| CA1134986A (en) * | 1978-11-08 | 1982-11-02 | Peter M. Burrill | Organosilicon polymers |
| JPS6047382B2 (ja) * | 1982-05-26 | 1985-10-21 | 東レ株式会社 | 炭素繊維製造用原糸油剤 |
-
1984
- 1984-02-29 JP JP59039541A patent/JPS60185880A/ja active Granted
-
1985
- 1985-02-28 EP EP19850301398 patent/EP0159120B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS64508B2 (enExample) | 1989-01-06 |
| EP0159120A1 (en) | 1985-10-23 |
| JPS60185880A (ja) | 1985-09-21 |
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