JPH1180379A - Color-developing polymer structure and its production - Google Patents

Color-developing polymer structure and its production

Info

Publication number
JPH1180379A
JPH1180379A JP24941097A JP24941097A JPH1180379A JP H1180379 A JPH1180379 A JP H1180379A JP 24941097 A JP24941097 A JP 24941097A JP 24941097 A JP24941097 A JP 24941097A JP H1180379 A JPH1180379 A JP H1180379A
Authority
JP
Japan
Prior art keywords
color
block copolymer
polymer structure
structure
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP24941097A
Other languages
Japanese (ja)
Other versions
JP3233883B2 (en
Inventor
Katsunori Funaki
Yuko Kanazawa
Kiyoharu Tsutsumi
聖晴 堤
克典 舩木
祐子 金澤
Original Assignee
Katsunori Funaki
Res Dev Corp Of Japan
科学技術振興事業団
克典 舩木
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 Katsunori Funaki, Res Dev Corp Of Japan, 科学技術振興事業団, 克典 舩木 filed Critical Katsunori Funaki
Priority to JP24941097A priority Critical patent/JP3233883B2/en
Publication of JPH1180379A publication Critical patent/JPH1180379A/en
Application granted granted Critical
Publication of JP3233883B2 publication Critical patent/JP3233883B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer structure functioning as a color-developing material as such without coloring the polymer with a pigment or a dye and without requiring a special treatment process, a special film or the like. SOLUTION: This color-developing polymer structure comprises a phaseseparated microstructure formed from two or more kinds of mutually incompatible polymers having different refractive indexes each other. Lattice distances formed between the phases of the phase-separated microstructure are 100-700 mm which correspond to the wavelengths of visible light. The color- developing polymer structure is produced by forming the phase-separated microstructure from the amorphous mixture structure of a block copolymer with a homopolymer compatible with one of the blocks of the block copolymer by lowering temperature or evaporating a solvent. The block copolymer is produced by mutually binding the terminals of two or more kinds of polymer chains which are incompatible with each other and different in refractive indexes. When the amount of the used homopolymer is changed, the polymer structure comprising the same block copolymers but expressing a different color can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer structure which can be used as a decorative plastic plate or a decorative plastic material, and more particularly to a novel color-forming polymer (polymer) structure having a novel structure which does not require a pigment or a dye, and its production. About the method.

[0002]

2. Description of the Related Art Generally, coloring of a plastic material is performed by mixing a pigment or a dye with a plastic. In this method, a pigment / dye is required, and a step of kneading it with a plastic material is required. Further, depending on the environment where the plastic is placed, there is a risk that the pigment / dye may be eluted.

In order to express color without using a pigment such as a pigment or a dye, it is necessary to use light diffraction or interference.
As a typical example thereof, a hologram in which a diffraction grating is formed on a plastic surface to produce a rainbow color is well known, but this is a color development only on the plastic surface.

[0004] As a product of coloring the entire plastic,
A method of forming a color by laminating a polarizing film and an orientation anisotropic film has been reported [Yoshiyo Matsumoto, Surface (Surface Symposium / Colloid Symposium), Vol. 27, No. 11. 893-900, 1989.
]. In addition, by alternately laminating several hundred kinds of two types of polymer thin films each having a thickness of 0.1 μm, a type of color-forming film showing interference colors is known by utilizing the difference in the refractive index of the film. [Kinki Printing, Daiei Paper Trading, Packaging, No. 308, 62-63, 1982]. In order to form these films, a polarizing film was required, or it was necessary to repeatedly laminate and stretch the films.

[0005] In addition to this, a method of forming a color by impregnating a porous polymer with a solvent is also known, but the product obtained by this method requires a means for preventing evaporation of the solvent [Sadao Hayashi, Surface (Surface Symposium / Colloid Symposium, Vol.
32, No.10, 10,656-661, 1994; Sadao Hayashi, Polymer, Vol.4
3, No. 3, 226, 1994; JP-A-56-61437].

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the necessity of using pigments such as pigments and dyes as in the prior art, and to perform complicated operations such as lamination and stretching, or special films such as polarizing films. An object of the present invention is to provide a polymer structure capable of expressing various colors as it is without the need for a polymer structure.

[0007]

According to the present invention, there is provided a micro phase-separated structure composed of two or more polymer phases which are incompatible with each other and have different refractive indices. A color-forming polymer structure is provided, wherein the lattice spacing formed by each phase of the microphase-separated structure is in the range of 100 nm to 700 nm.

Further, according to the present invention, as a method for producing the color-forming polymer structure, a molecular weight of 100,000 to 1,000,000 in which two or more kinds of polymer chains incompatible with each other and having different refractive indices are bonded at each terminal. And a block copolymer of
After forming a disordered mixed state by melting or dissolving a homopolymer compatible with one of each block chain of the block copolymer in a common solvent, by lowering the temperature or evaporating the solvent, A method is provided for forming a microphase-separated structure in which a lattice spacing formed by each phase is 100 nm or more. In a preferred embodiment of the method for producing a color-forming polymer structure according to the present invention, a block copolymer having a molecular weight of 200,000 or more is used. In the method for producing a color-forming polymer structure of the present invention, the color developed is adjusted by adjusting the amount of the homopolymer used.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been completed by utilizing the micro phase separation structure of a block copolymer. It is known that block copolymers in which mutually incompatible polymer chains are chemically bonded at each end form a regular microphase-separated structure in which the size and spacing of each polymer phase are uniform. The inventor has
Focusing on this phenomenon, a block copolymer is used to form a microphase-separated structure composed of two or more polymer phases that are incompatible with each other and have different refractive indices.
By increasing the size or interval of each phase of the microphase-separated structure so as to exhibit a lattice interval capable of diffracting visible light (wavelength of about 350 to 700 nm), that is, a lattice interval of 100 nm to 700 nm, high chromogenicity is obtained. I thought that a molecular structure could be obtained.

The present inventor has further found a method by which such a color-forming polymer structure can be easily produced. As described above, in order for the structure to diffract visible light and exhibit color, the lattice spacing of the structure needs to be 100 nm or more (preferably 150 nm to 700 nm). However, the molecular weight of the commonly used block copolymer (sum of the molecular weights of the two block chains)
The microphase-separated structure formed by a block copolymer having a molecular weight of 100,000 or less has an interstitial distance of several tens nm, and the structure is too small to develop color. In order to form a colored structure only with a block copolymer, a molecular weight of 5,000,000 to 50,000,000 is required.
And the synthesis is very difficult in practice.

As a result of repeated studies, the present inventor has found that by mixing a homopolymer compatible with those block chains into a generally copolymerizable block copolymer having a molecular weight, a lattice spacing of 100 nm or more can be obtained. It has been found that a microphase-separated structure with uniform lattice spacing can be obtained. However, when the molecular weight of the block copolymer is 100,000 or less, the amount of the homopolymer to be mixed increases, and the regularity of the formed microphase separation structure is easily disturbed. Will happen. Therefore, the molecular weight of the block copolymer used must be 100,000 or more, preferably 150,000 or more. In order to maintain the regularity of the microphase-separated structure, it is desirable that the amount of the mixed homopolymer is small, and for this purpose, the molecular weight of the block copolymer is 200,
000 or more, more preferably,
300,000 or more. The upper limit molecular weight of the block copolymer is not particularly limited, but is preferably 1,000,000 or less from the viewpoint of easy synthesis.

Each block chain of the block copolymer used in the present invention is incompatible with each other and has a different refractive index, so that a disordered state can be formed by melting or dissolving in a solvent as described below. As long as the difference is large, the difference in refractive index is preferably as large as possible in order to express a strong color. Block copolymers suitable for obtaining the color-forming polymer structure of the present invention include, for example, block copolymers composed of polystyrene and polyisoprene and block copolymers composed of poly (2-vinylpyridine) and polyisoprene. In addition, a block copolymer composed of polymethyl methacrylate (PMMA) and polyisoprene or polybutadiene can be used.

According to the present invention, a color-forming polymer structure is produced by using a block copolymer as described above and performing a phase separation forming method known in the art to form a micro phase separation structure. . That is, these block copolymers are mixed with a homopolymer compatible with one of the respective block chains (polymer chains), and heated to a temperature higher than the "order-disorder transition temperature (T ODT )" of the system and melted. , Or by dissolving them in a common solvent, they form a completely mixed disordered state. Then, by lowering the temperature to T ODT or less or evaporating the solvent, a regular ordered structure is formed, and a microphase-separated structure composed of each polymer phase (block chain phase) having a lattice spacing of 100 nm or more is formed. The lattice spacing of the microphase-separated structure can be confirmed by observing the obtained structure with a transmission electron microscope.

At this time, each block chain phase (polymer phase)
By volume fraction (including contaminated homopolymer)
Microphase-separated structures such as "sphere", "cylinder", "lamella", and "co-continuous" can be obtained, but any structure may be used from the viewpoint of color development. When the fraction φ is about 0.33, a bicontinuous structure can be obtained, and a cylinder structure can be obtained on the basis of 0.18 <φ <0.32.

According to the method of the present invention, the phase-separated structure formed by the block copolymer is regular, and even if a small amount of homopolymer is contained, the lattice size is increased while maintaining the regularity of the structure. it can. However, if the weight of the added homopolymer exceeds the weight of the block copolymer, the regularity of the microphase-separated structure tends to be disordered, and the conditions for maintaining the ordered structure (type of block copolymer, type of added homopolymer, formation rate, Temperature, etc.) are narrow. When the molecular weight of the block copolymer is 200,000 or more, the amount of the added homopolymer may be smaller than the weight of the block copolymer,
The conditions under which a regular structure can be formed are relaxed, and a color-forming structure using any type of block copolymer can be formed.

Thus, in the method of the present invention, the lattice spacing can be controlled by adjusting the amount of the homopolymer to be added, and the color developed by the structure can be changed using the same block copolymer. Further, by increasing the molecular weight of the block copolymer within the above-described conditions, the control range of the color tone of the polymer structure can be widened.

[0017]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Example 1 Block copolymer PS-b-PI composed of polystyrene (PS) and polyisoprene (PI) Number average molecular weight Mn = 100,000-b-
172,000), and a homopolymer of PS and PI was added under the following conditions and dissolved in toluene to form a disordered mixed state. Then, the solvent was evaporated to prepare a cast film having a bicontinuous microphase-separated structure.

<Sample> (1) Block copolymer: PS-b-PI (Mn = 100,000-b-PI)
172,000) (3) Mixing weight ratio: PS-b-PI: PS: PI = 100: a: b
(A = 10, 25, 50: b = 0, 10, 25, 50) (4) Initial concentration of polymer solution: 5% by weight Table 1 summarizes the color development results of the cast film obtained. Among these, all of the colored ones exhibited relatively pale pearly luster.

[0019]

An example of the cast film obtained (10% homopolymer blended with 10% PI and 10% PS)
1 is shown in FIG. Since the PI block is stained and observed, the black part is the PI phase and the white part is the PS phase. As shown in the figure, each polymer phase forms a regular microphase-separated structure with good size and spacing, and exhibits a lattice spacing capable of diffracting visible light (in this case, purple). Understood.

Example 2 A block copolymer (P2VP-b-PI) composed of poly (2-vinylpyridine) (P2VP) and polyisoprene (PI) (Mn =
Based on 126,000-b-41,200), a homopolymer of PI was added under the following conditions, dissolved in benzene, and the solvent was evaporated to form a cast film (co-continuous microphase separation structure).

<Sample> (1) Block copolymer: P2VP-b-PI (Mn = 126,000-
b-41,200) (2) Homopolymer: PI (Mn = 41,200) (3) Mixing weight ratio: P2VP-b-PI / PI = 80/20 (4) Initial concentration of polymer solution: 5% by weight Cast films showing different colors could be obtained. In other words, this film exhibited a colored portion (reflected light having a purple to blue color) and a reflected light having a pale blue to green (a transmitted light having a red to yellow color) having a metallic luster of red to yellow.

[0023]

The polymer structure of the present invention functions as a pearlescent luster coloring material without being colored by pigments or dyes and without any special processing step or film. For example, it can be used as a decorative board or a plastic material for decorative purposes.

Further, according to the production method of the present invention, such a block copolymer comprising a general-purpose monomer unit is used without using a special polymer species or an ultra-high molecular weight polymer which is very difficult to synthesize. A color-forming polymer structure can be obtained. According to the method of the present invention, a single block copolymer can be used to produce various types of color-forming structures that exhibit various colors simply by changing the amount of the added homopolymer.

[Brief description of the drawings]

FIG. 1 is a transmission electron micrograph showing a crystal structure of one example of a color-forming polymer structure of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuko Kanazawa 1-31-6-1 Enri Ono, Sumiyoshi-ku, Osaka-shi, Osaka

Claims (4)

[Claims]
1. A microphase-separated structure composed of two or more polymer phases which are incompatible with each other and have different refractive indices, and a lattice spacing formed by each phase of the microphase-separated structure is 100 nm to 700 nm. A chromophoric polymer structure characterized by the following formula:
2. The method for producing a color-forming polymer structure according to claim 1, wherein two or more polymer chains incompatible with each other and having different refractive indices are bonded at each terminal.
0 to 1,000,000 block copolymer and a homopolymer compatible with one of the respective block chains of the block copolymer are melted or dissolved in a common solvent to form a disordered mixed state, and then the temperature is reduced or A method for producing a color-forming polymer structure, comprising forming a microphase-separated structure in which the lattice spacing formed by each phase is 100 nm or more by evaporating a solvent.
3. The method for producing a color-forming polymer structure according to claim 2, wherein a block copolymer having a molecular weight of 200,000 or more is used.
4. The color developed by adjusting the amount of a homopolymer to be used is adjusted.
Alternatively, the method for producing the color-forming polymer structure according to claim 3.
JP24941097A 1997-08-29 1997-08-29 Color-forming polymer structure and method for producing the same Expired - Fee Related JP3233883B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP24941097A JP3233883B2 (en) 1997-08-29 1997-08-29 Color-forming polymer structure and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP24941097A JP3233883B2 (en) 1997-08-29 1997-08-29 Color-forming polymer structure and method for producing the same

Publications (2)

Publication Number Publication Date
JPH1180379A true JPH1180379A (en) 1999-03-26
JP3233883B2 JP3233883B2 (en) 2001-12-04

Family

ID=17192568

Family Applications (1)

Application Number Title Priority Date Filing Date
JP24941097A Expired - Fee Related JP3233883B2 (en) 1997-08-29 1997-08-29 Color-forming polymer structure and method for producing the same

Country Status (1)

Country Link
JP (1) JP3233883B2 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000058760A1 (en) * 1999-03-31 2000-10-05 Cpfilms Inc. Film composites
JP2005146023A (en) * 2003-11-11 2005-06-09 Daicel Chem Ind Ltd Coating film made of chromogenic polymer structure, coating film-forming method and coating material
US7166872B2 (en) 2002-08-22 2007-01-23 Seiko Epson Corporation Device substrate, production method therefor, electronic device, production method therefor, optic device, production method therefor, and electronic apparatus
JP2007138052A (en) * 2005-11-18 2007-06-07 Hitachi Ltd Polymeric thin film, preparation method of pattern base plate, pattern transcriptional body, and pattern vehicle for magnetic recording
JP2008520450A (en) * 2004-11-22 2008-06-19 ウィスコンシン・アラムナイ・リサーチ・ファウンデーションWisconsin Alumni Research Foundation Method and composition for non-periodic pattern copolymer films
JP2010056256A (en) * 2008-08-28 2010-03-11 Hitachi Ltd Polymer thin film with microstructure, and method of manufacturing pattern substrate
JP2010056257A (en) * 2008-08-28 2010-03-11 Hitachi Ltd Method for manufacturing microstructure
JP2012228207A (en) * 2011-04-26 2012-11-22 Hamamatsu Univ School Of Medicine Organism mimic
JP2013010315A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Resin molded body
JP2013010314A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Structural color development
JP2013011804A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Structural color body
JP2013011805A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Structural color body
JP2013082795A (en) * 2011-10-07 2013-05-09 Hamamatsu Photonics Kk Microphase separation structure film and laminate
JP2014062236A (en) * 2012-08-29 2014-04-10 Tokyo Univ Of Science Structural color developing base material and method for manufacturing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201804010D0 (en) * 2018-03-13 2018-04-25 Univ Kyoto Structured nanoporous materials, manufacture of structured nanoporous materials and applications of structured nanoporous materials

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6720061B1 (en) 1999-03-31 2004-04-13 Anthony B. Port Film composites
WO2000058760A1 (en) * 1999-03-31 2000-10-05 Cpfilms Inc. Film composites
US7166872B2 (en) 2002-08-22 2007-01-23 Seiko Epson Corporation Device substrate, production method therefor, electronic device, production method therefor, optic device, production method therefor, and electronic apparatus
JP2005146023A (en) * 2003-11-11 2005-06-09 Daicel Chem Ind Ltd Coating film made of chromogenic polymer structure, coating film-forming method and coating material
JP4581377B2 (en) * 2003-11-11 2010-11-17 トヨタ自動車株式会社 Coating film comprising coloring polymer structure, coating film forming method, and coating material
JP2008520450A (en) * 2004-11-22 2008-06-19 ウィスコンシン・アラムナイ・リサーチ・ファウンデーションWisconsin Alumni Research Foundation Method and composition for non-periodic pattern copolymer films
JP2007138052A (en) * 2005-11-18 2007-06-07 Hitachi Ltd Polymeric thin film, preparation method of pattern base plate, pattern transcriptional body, and pattern vehicle for magnetic recording
CN102123941A (en) * 2008-08-28 2011-07-13 株式会社日立制作所 Microfine structure and process for producing same
JP2010056256A (en) * 2008-08-28 2010-03-11 Hitachi Ltd Polymer thin film with microstructure, and method of manufacturing pattern substrate
JP2010056257A (en) * 2008-08-28 2010-03-11 Hitachi Ltd Method for manufacturing microstructure
JP4654280B2 (en) * 2008-08-28 2011-03-16 株式会社日立製作所 Manufacturing method of fine structure
JP2012228207A (en) * 2011-04-26 2012-11-22 Hamamatsu Univ School Of Medicine Organism mimic
JP2013010315A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Resin molded body
JP2013010314A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Structural color development
JP2013011804A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Structural color body
JP2013011805A (en) * 2011-06-30 2013-01-17 Hamamatsu Photonics Kk Structural color body
JP2013082795A (en) * 2011-10-07 2013-05-09 Hamamatsu Photonics Kk Microphase separation structure film and laminate
JP2014062236A (en) * 2012-08-29 2014-04-10 Tokyo Univ Of Science Structural color developing base material and method for manufacturing the same

Also Published As

Publication number Publication date
JP3233883B2 (en) 2001-12-04

Similar Documents

Publication Publication Date Title
Sperling Interpenetrating polymer networks and related materials
CN104823087B (en) Photocurable adhesive agent composition, polarization plates and its manufacture method, optical component and liquid crystal display device
US6416827B1 (en) SPD films and light valves comprising same
US5643673A (en) Black electrophoretic particles and method of manufacture
US7018686B2 (en) Switchable volume hologram materials and devices
US6646772B1 (en) Holographic illumination system
US7420733B1 (en) Electrically switchable polymer-dispersed liquid crystal materials including switchable optical couplers and reconfigurable optical interconnects
US7582231B2 (en) Essentially water-free polymerized crystalline colloidal array composites having tunable radiation diffracting properties
Jethmalani et al. Diffraction of visible light by ordered monodisperse silica− Poly (methyl acrylate) composite films
CN102533135B (en) Photocurable adhesive composition, polaroid and manufacture method thereof, optics and liquid crystal indicator
EP0852599B1 (en) Improved colored articles and compositions
Liberman‐Martin et al. Application of bottlebrush block copolymers as photonic crystals
JP2667029B2 (en) Manufacturing method of composite material used for liquid crystal display device, liquid crystal display device, and composite material used for liquid crystal display device
JP2530687B2 (en) Polymer composition
KR100668580B1 (en) Morphology Trapping and Materials Suitable for Use Therewith
CA1340228C (en) Dispersion of liquid crystal droplets in a photopolymerized matrix, and devices made therefrom
US5096282A (en) Polymer dispersed liquid crystal film devices
CN100514092C (en) Chromatic diffractive pigments and foils
EP0740168B1 (en) Non-birefringent optical resin material and method of manufacturing the same, and member of liquid crystal elements using optical resin material
US7029745B2 (en) Security articles having diffractive surfaces and color shifting backgrounds
JP4475813B2 (en) Holographic illumination device
CN101253425B (en) Diffractive optical element and imaging apparatus using such diffractive optical element
KR101572284B1 (en) Optical film and image forming apparatus having the same
EP0720753B1 (en) Coloured material
JP3153238B2 (en) Acrylic-filled thermoformable acrylic sheet

Legal Events

Date Code Title Description
R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313532

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

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

Year of fee payment: 7

Free format text: PAYMENT UNTIL: 20080921

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

Free format text: PAYMENT UNTIL: 20080921

Year of fee payment: 7

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

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

Free format text: PAYMENT UNTIL: 20080921

Year of fee payment: 7

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

Year of fee payment: 7

Free format text: PAYMENT UNTIL: 20080921

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

Free format text: PAYMENT UNTIL: 20090921

Year of fee payment: 8

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

Free format text: PAYMENT UNTIL: 20100921

Year of fee payment: 9

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

Year of fee payment: 10

Free format text: PAYMENT UNTIL: 20110921

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

Year of fee payment: 10

Free format text: PAYMENT UNTIL: 20110921

R370 Written measure of declining of transfer procedure

Free format text: JAPANESE INTERMEDIATE CODE: R370

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313117

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

Year of fee payment: 10

Free format text: PAYMENT UNTIL: 20110921

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

LAPS Cancellation because of no payment of annual fees