[go: up one dir, main page]

WO2004024347A1 - Procede de formation de revetement fonctionnel - Google Patents

Procede de formation de revetement fonctionnel Download PDF

Info

Publication number
WO2004024347A1
WO2004024347A1 PCT/JP2003/011521 JP0311521W WO2004024347A1 WO 2004024347 A1 WO2004024347 A1 WO 2004024347A1 JP 0311521 W JP0311521 W JP 0311521W WO 2004024347 A1 WO2004024347 A1 WO 2004024347A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
functional
forming
glass
functional film
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.)
Ceased
Application number
PCT/JP2003/011521
Other languages
English (en)
Japanese (ja)
Inventor
Toyoyuki Teranishi
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.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass 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 Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2004535918A priority Critical patent/JPWO2004024347A1/ja
Publication of WO2004024347A1 publication Critical patent/WO2004024347A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings

Definitions

  • the present invention relates to a method for forming a functional film having anti-fogging property and water repellency on a surface of a base material such as a glass plate or a resin plate. This technique is effective, for example, for forming a functional coating on window glass for automobiles.
  • a technique for forming a functional film such as an antifogging property or a water repellent property on the surface of a base material such as a glass plate or a resin plate is conventionally known (for example, see Japanese Patent Application Laid-Open No. H10-194784).
  • a functional film such as an antifogging property or a water repellent property
  • a base material such as a glass plate or a resin plate
  • functional coatings various materials have been developed and used.
  • the former corresponds to a case where a car manufacturer attaches a glass formed with a water-repellent film to a car body
  • the latter corresponds to a case where a car user applies a water-repellent coating agent to the glass assembled to the car body to form a film. Is the case.
  • the method of forming a functional film on the surface of a substrate in advance is often applied only to a highly durable film because the functional film is often rubbed in the process of assembling the substrate to the final product.
  • the functional film on the surface may be easily peeled off, so that the functional film is transferred to another member (for example, a jig for handling) in the process of assembling the final product. This is there. Therefore, in order to solve such a transfer problem, a method of handling a glass article by interposing paper or cloth between an organic functional film and a holding jig has been proposed (see Japanese Unexamined Patent Publication (Kokai) No. 2002-139686). However, before and after the glass article handling step, a step of attaching paper or cloth and a step of removing the paper or cloth are required, which causes an increase in cost.
  • the method of forming a functional film on the surface of the base material after assembling the base material into the final product is difficult to control the environment when forming the film and the cleanness of the base material. Since the method is limited to a method that can be easily processed by general users, the resulting functional film has a drawback of poor durability.
  • An object of the present invention is to provide a functional film having excellent durability, which can prevent deterioration of the functional film and transfer of the functional film to other members in the process of assembling the base material to the final product.
  • An object of the present invention is to provide a method that can be formed on a substrate surface. Disclosure of the invention
  • a base film is previously formed on the substrate surface, and the base material with the base film is used as a final product. After assembling, a method of forming a functional film by forming a functional film by applying a functional coating agent on the base film is provided.
  • a protective layer of the base film is formed, and the protective layer of the base film is removed before applying the functional coating agent.
  • the base film is preferably a silicon-based film having a smooth or uneven surface.
  • the underlayer film is a silica-based film having an uneven shape on the surface by containing silica fine particles.
  • the functional film is preferably an organic functional film.
  • the organic functional film is preferably an antifogging film, a water repellent film, or a super water repellent film.
  • the substrate is preferably a transparent glass plate or a transparent resin plate.
  • FIG. 1 is a flowchart showing the working procedure of the method of the present invention.
  • EI 2 is a flowchart showing a modification of the working procedure of the method of the present invention.
  • a base film for improving the durability of the functional film is formed on the surface of the base material in advance. Then, the base material with the base film is assembled into a final product. Then, in the state of the final product, a functional coating is formed by applying a functional coating agent on the base film. In this way, in the final product assembling process, since the functional film has not yet been formed on the base material surface, there is no problem of deterioration of the functional film or transfer of the functional film to other members. . In addition, since a good base film is already formed on the base material in the state of being assembled into the final product, the functional coating with excellent durability can be easily applied by applying a functional coating agent. A film is obtained. The working procedure of the method of the present invention is shown in FIG.
  • the state of the base film in the state of the final product is determined.
  • the functional film may be formed by removing the protective layer and applying a functional coating agent on the base film. In this way, it is possible to prevent the surface of the base material from being stained or damaged after the formation of the base film and before the formation of the functional film.
  • FIG. 2 shows a modification of the working procedure of the method.
  • the substrate used in the present invention is typically glass, but may be ceramics, synthetic resin, metal or the like.
  • the base film is not particularly limited as long as it is a material having excellent adhesion to the substrate surface, high hardness of the base film itself, and excellent adhesion to the functional film formed thereon.
  • a silica-based film material is particularly preferred from the viewpoint of adhesion to the substrate.
  • the surface of the undercoating film may be smooth or uneven.
  • the functional coating is an anti-fog coating, a water-repellent coating, or a super water-repellent coating
  • the surface of the base coating may be uneven. This is preferred because the shape effect improves hydrophilicity (anti-fogging property) or water repellency.
  • the underlayer may be formed by any method according to the film material, such as a sol-gel method, an evaporation method, a sputtering method, and a CVD method, but the sol-gel method is preferred from the viewpoint of manufacturing cost.
  • a sol-gel method an evaporation method, a sputtering method, and a CVD method
  • the sol-gel method is preferred from the viewpoint of manufacturing cost.
  • flow coating, dip coating, force coating, spin coating, spray coating, no coating, roll coating, brush coating, dip coating It can be applied to the substrate surface by crush adsorption method.
  • fine particles of silica may be added to a coating solution used in the sol-gel method.
  • Examples of the functional film material in the present invention include an anti-fogging agent and a water repellent applied to a front glass for automobiles and the like. According to the present invention, since the base film already formed on the base material assembled into the final product has already been formed, the user simply applies a functional coating agent to the base material in the same manner as in the conventional case, thereby facilitating the operation. A functional film having excellent durability can be obtained.
  • a film that can be washed away with water or an organic solvent, a protective film, and the like can be used, but the present invention is not limited thereto.
  • a membrane that can be washed away with water or an organic solvent can be removed by rinsing with water or an organic solvent (eg, alcohol). If a protective film is used, it can be removed by peeling it off.
  • Hydrolysis-condensation polymerization solution of ethyl silicate (trade name: HAS-10, manufactured by Collcoat Co., Ltd.) 11.8 parts by weight, having a diameter of 10 to 20 nm and a length of 40 ⁇ 300 nm chain silica colloid (trade name: Snowtex 0 UP, manufactured by Nissan Chemical Industries, Ltd., solid content: 15% by weight) 13.3 parts by weight and 2 parts by weight
  • One propanol (74.9 parts by weight) was mixed at room temperature, diluted 3 times by weight with 2-propanol, and stirred at room temperature for 2 hours to obtain a coating solution for an uneven base film.
  • the glass plate that has been polished and cleaned with a cerium oxide-based abrasive, rinsed with pure water, and then dried is immersed in the coating solution for the underlayer film, and pulled up at a speed of 20 cm / min.
  • an uneven base film was applied to the glass plate.
  • the front glass for automobiles is used so that the uneven undercoat film is on the inside of the vehicle.
  • the glass was bent by placing it in a high-temperature furnace at a temperature of 600 or more.
  • the front glass with the uneven base film was assembled to the car body in a line-type automobile assembly process.
  • the front glass is soldered with a suction cup.
  • the glass is usually handled with the same suction cup. However, a part of the previous irregular underlayer was not transferred to the glass.
  • the surfactant is sodium 2-diethylhexylsulfosuccinate (trade name: Lapisol A-30, manufactured by Nippon Yushi Co., Ltd.) was applied by a spray coat method and dried sufficiently at room temperature. After drying, the surface was rubbed with a cotton cloth to remove excess surfactant, and a surfactant layer having a thickness of about 10 nm was formed to obtain an antifogging glass.
  • the anti-fog performance and durability of the obtained anti-fog glass were repeatedly evaluated by an anti-fog test.
  • the method of the repetitive anti-fogging test is as follows in accordance with JISS 400, keeping the outer surface of the glass at 25 ° C, the temperature of 43 ° C and the relative humidity of 95% on the inner surface of the car where the anti-fog film is formed. The humid air of RH was directly blown for 3 minutes, and the degree of cloudiness was visually observed. Then, while keeping the temperature of the outer surface of the vehicle at 25, the inner surface of the vehicle was dried for 2 minutes while directly blowing dry air at 25 ° C and a relative humidity of 10% RH.
  • Table 1 shows the antifogging results 30 seconds after the start of the humid air spraying in the first cycle and the 10th cycle. From these results, the anti-fog glass did not fog at all in the initial stage, and although the image was slightly distorted at the 10th cycle, no fogging occurred. However, it was confirmed that the durability was excellent.
  • Ethanol 98.44 4 parts by weight of chain silica colloid (trade name: Snowtex 0 UP, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by weight) 1.1 3 parts by weight Tetrachlorosilane (trade name: LS-10, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 parts by weight was added with stirring, and the mixture was further stirred at room temperature for 2 hours. A cured coating liquid was obtained.
  • the above-mentioned room-temperature curing coating liquid for uneven base film is applied by flow coating to the interior surface of a front glass plate for automobiles that has been polished and cleaned with a cerium oxide abrasive, and then rinsed with pure water and dried. Then, the glass was dried at room temperature to obtain a front glass with a ground film under the unevenness.
  • Example 1 the front glass with the uneven undercoat film was assembled into an automobile, and then a surfactant was applied thereto.
  • the obtained anti-fog glass was subjected to anti-fog performance and durability performance.
  • Example 1 no fogging occurred at the initial stage, and slight image distortion was observed even at the 10th cycle, but no fogging occurred and extremely durability was achieved. It was confirmed that the performance was excellent.
  • part of the uneven base film was not transferred to other glass in the automobile assembly process.
  • Example 1 After the interior surface of the front glass for automobiles on which the uneven undercoat film formed in Example 1 was formed was thoroughly cleaned with a solvent, the above organosilane coating solution was applied to a cotton cloth, and excess adhesion was observed. The organosilane was wiped with a new cotton cloth to obtain an anti-fog glass.
  • the anti-fog glass obtained was evaluated for anti-fog performance and durability performance in the same manner as in Example 1. As a result, no fogging occurred at the initial stage, and slight image distortion was observed even at the 10th cycle. However, it was confirmed that fogging did not occur and the durability was extremely excellent.
  • Example 1 A surfactant was applied to the interior surface of normal front glass for automobiles in the same manner as in Example 1 to obtain an anti-fog glass.
  • the obtained antifogging glass was evaluated for antifogging performance and durability performance in the same manner as in Example 1. As a result, although no fogging occurred at the initial stage, fogging occurred at the 10th cycle, and the durability performance was improved. It was confirmed to be bad.
  • Example 1 Before assembling the front glass with a concavo-convex base film obtained in the same manner as in Example 1 into an automobile, a surfactant was applied in the same manner as in Example 1 to obtain an antifogging glass.
  • this anti-fog glass was assembled to a car in a line-type assembly process, it was confirmed that the surfactant was transferred to another glass via a suction cup.
  • the anti-fogging performance and the durability performance in the same manner as in Example 1 it was confirmed that the part was partially fogged in the first cycle, and that the anti-fogging performance was poor.
  • Example 2 After forming an uneven undercoat film on a glass plate in the same manner as in Example 1, in the same manner as in Example 1 except that the front glass was processed into an automotive front glass so that the film became the outer surface of the vehicle, the front glass with the uneven undercoat film was used in a line-type automobile assembly process. Assembled on the body. At this time, part of the uneven base film was not transferred to another glass in the automobile assembly process.
  • heptadecafluorodecyl trimethoxysilane (trade name: KBM-7803, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 98 g of ethanol, and 0.1 N hydrochloric acid was further added. was added and stirred at 30 ° C. for 1 hour to obtain a water-repellent liquid.
  • the water repellency of the obtained water repellent glass was evaluated by the contact angle of water.
  • a contact angle meter (“CA-DT", manufactured by Kyowa Interface Science Co., Ltd.)
  • a water droplet having a mass of 2 mg was dropped on the surface of the glass plate, and the static contact angle was measured.
  • Table 2 shows the results of the initial water repellency. From these results, it was confirmed that the water-repellent glass was excellent in water-repellent performance.
  • the weather resistance of the obtained water-repellent glass was evaluated by an outdoor exposure test.
  • the outdoor exposure test involved parking the vehicle with the front glass facing south and exposing the water-repellent glass to direct sunlight and wind and rain.
  • the degree of deterioration of the water repellency of the water repellent glass after 6 months of the outdoor exposure test was measured by the contact angle.
  • the results are also shown in Table 2. From these results, it was confirmed that the water-repellent glass exhibited sufficient water-repellent performance even after 6 months of outdoor exposure and was extremely excellent in weather resistance. This was presumed to be due to the effect of the underlayer. (Example 5)
  • tetrachlorosilane (trade name: LS-10, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and further add room temperature. For 2 hours to obtain a room temperature curing coating liquid for a smooth underlayer.
  • the above-mentioned room-temperature hardening film for a smooth undercoating film is applied to the outer surface of a front glass plate for an automobile, which is polished and washed with a cerium oxide abrasive, rinsed with pure water, and dried.
  • the tinting solution was applied by a flow coating method and dried at room temperature to obtain a front glass with a smooth underlayer.
  • Example 4 the front glass with the smooth undercoating film is assembled into an automobile, and then a water-repellent treatment liquid is applied, and the obtained water-repellent glass is subjected to water repellency and weather resistance.
  • a water-repellent treatment liquid is applied, and the obtained water-repellent glass is subjected to water repellency and weather resistance.
  • the weather resistance was extremely excellent.
  • part of the smooth underlayer was not transferred to other glass during the automobile assembly process.
  • a water-repellent treatment liquid was applied to the outer surface of a normal vehicle front glass in the same manner as in Example 4 to obtain a water-repellent glass.
  • the obtained water-repellent glass was evaluated for water repellency and weather resistance in the same manner as in Example 4. As a result, although the initial water repellency was excellent, the water repellency after 6 months of outdoor exposure was 87 ° C. It was confirmed that the weatherability was poor.
  • the present invention is a method of forming a functional film by forming a base film on the surface of a base material in advance and applying a functional coating agent after assembling the final product. Therefore, there is no functional coating in the process of assembling the base material to the final product, so that the functional coating does not deteriorate and the functional coating does not transfer to other members.
  • a base film is already formed on the base material assembled into the final product, a functional film with excellent durability can be easily formed simply by applying a functional coating agent. You.
  • the undercoat film remains, so a good functional film can be restored by applying a functional coating agent again.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne un procédé de formation d'un revêtement fonctionnel sur une surface de substrat, ledit revêtement présentant une durabilité excellente qui peut permettre d'éviter le transfert du revêtement fonctionnel sur d'autres éléments et la détérioration du revêtement fonctionnel lors de l'étape de fixation d'un substrat sur un produit final. Un film de fondation est formé à l'avance sur une surface de substrat. Le substrat présentant le film de fondation est fixé sur un produit final, puis un agent de revêtement fonctionnel est appliqué sur le film de fondation de façon à ainsi former un revêtement fonctionnel. Le film de fondation est, par exemple, un revêtement de silice présentant une surface lisse ou inégale. La configuration inégale peut être obtenue par incorporation de fines particules de silice. Le revêtement fonctionnel est, par exemple, un revêtement fonctionnel constitué de substance organique présentant des propriétés d'anticondensation ou d'imperméabilisation/super-imperméabilisation. Le substrat est une plaque de verre transparent, une plaque de résine transparente, etc.
PCT/JP2003/011521 2002-09-11 2003-09-09 Procede de formation de revetement fonctionnel Ceased WO2004024347A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004535918A JPWO2004024347A1 (ja) 2002-09-11 2003-09-09 機能性皮膜の形成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002265515 2002-09-11
JP2002-265515 2002-09-11

Publications (1)

Publication Number Publication Date
WO2004024347A1 true WO2004024347A1 (fr) 2004-03-25

Family

ID=31986588

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/011521 Ceased WO2004024347A1 (fr) 2002-09-11 2003-09-09 Procede de formation de revetement fonctionnel

Country Status (2)

Country Link
JP (1) JPWO2004024347A1 (fr)
WO (1) WO2004024347A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0222343A (ja) * 1988-07-11 1990-01-25 Sekisui Chem Co Ltd 防曇プラスチックの製造方法
EP0719821A1 (fr) * 1994-12-27 1996-07-03 Ppg Industries, Inc. Traitement pour hydrofuger des surfaces en matière plastique et les surfaces ainsi traitées
JPH10194784A (ja) * 1996-11-18 1998-07-28 Nippon Sheet Glass Co Ltd 撥水性ガラス
EP0864622A2 (fr) * 1991-01-23 1998-09-16 Matsushita Electric Industrial Co., Ltd Article hydro- et oléophobant

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2500149B2 (ja) * 1991-01-23 1996-05-29 松下電器産業株式会社 撥水撥油性被膜及びその製造方法
JP3197030B2 (ja) * 1991-06-15 2001-08-13 コスモスケミカル株式会社 自動車用撥水型ウインドウオッシャー液
JP3686125B2 (ja) * 1994-07-04 2005-08-24 タイホー工業株式会社 自動車のウインドガラス用撥水剤およびウインドガラスの撥水方法
JPH1087346A (ja) * 1996-09-12 1998-04-07 Takehara:Kk ガラスコーティング剤
JPH10259038A (ja) * 1997-01-24 1998-09-29 Samsung Corning Co Ltd 耐久性撥水ガラス及びその製造方法
JP3738517B2 (ja) * 1997-02-13 2006-01-25 日産自動車株式会社 ワイパ装置
US5889086A (en) * 1997-06-23 1999-03-30 Taiho Industries Co., Ltd. Water repellent for automobile window glass

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0222343A (ja) * 1988-07-11 1990-01-25 Sekisui Chem Co Ltd 防曇プラスチックの製造方法
EP0864622A2 (fr) * 1991-01-23 1998-09-16 Matsushita Electric Industrial Co., Ltd Article hydro- et oléophobant
EP0719821A1 (fr) * 1994-12-27 1996-07-03 Ppg Industries, Inc. Traitement pour hydrofuger des surfaces en matière plastique et les surfaces ainsi traitées
JPH10194784A (ja) * 1996-11-18 1998-07-28 Nippon Sheet Glass Co Ltd 撥水性ガラス

Also Published As

Publication number Publication date
JPWO2004024347A1 (ja) 2006-01-05

Similar Documents

Publication Publication Date Title
JPH09227829A (ja) 光触媒性親水性コーティング組成物、親水性被膜の形成方法および被覆物品
CN103025519A (zh) 防雾有机硅氧烷涂料组合物和涂层
CN105016624B (zh) 亲水性自洁镀膜液及镀膜方法
WO1998055573A1 (fr) Procede de traitement prealable de surface avant formation d'une pellicule hydrophile photocatalytique, detergent et composition de sous-couche mis en application dans ce procede
JPH1150006A (ja) 光触媒性親水性被膜形成前の表面の前処理法並びにそれに用いられる洗浄剤およびアンダーコート組成物
JP2005194170A (ja) プライマー層が形成されたガラス基材及び防曇性物品
CN101098945B (zh) 用于得到滑水性被膜的处理剂及滑水性被膜的制作方法
JP3649585B2 (ja) 撥水性被膜形成用溶液
JP3245522B2 (ja) 塗料組成物
JP2005350502A (ja) 超撥水性被膜被覆物品、その製造方法及び超撥水性被膜形成用塗工材料
JP3245521B2 (ja) 塗料組成物
WO2004024347A1 (fr) Procede de formation de revetement fonctionnel
JP4325076B2 (ja) コーティング膜の形成方法
JP3245519B2 (ja) 塗料組成物
JP4410443B2 (ja) 防汚染性被膜形成品
JP3245520B2 (ja) 塗料組成物
JP2001205747A (ja) 表面処理層を有する基材およびその製造方法
JP4826226B2 (ja) 滑水性被膜を得るための処理剤及び滑水性被膜の作製法
JPH02175784A (ja) 防曇性物品
JPH09255941A (ja) 撥水処理剤およびその製造方法
JP2001295334A (ja) 防汚性を有する水栓及びその製造方法並びに水栓用防汚性コーティング組成物
JP2009263458A (ja) 表面処理組成物及び表面処理方法
TW589288B (en) Substrate having treated surface layers and process for producing it
JP4265925B2 (ja) 滑水性被膜の製造方法および滑水性被膜形成用塗布液
JPS62148535A (ja) 防曇性物品の製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2004535918

Country of ref document: JP

122 Ep: pct application non-entry in european phase