JP2004033824A - UV-resistant self-assembled monolayer with polyaromatic compounds - Google Patents
UV-resistant self-assembled monolayer with polyaromatic compounds Download PDFInfo
- Publication number
- JP2004033824A JP2004033824A JP2002191031A JP2002191031A JP2004033824A JP 2004033824 A JP2004033824 A JP 2004033824A JP 2002191031 A JP2002191031 A JP 2002191031A JP 2002191031 A JP2002191031 A JP 2002191031A JP 2004033824 A JP2004033824 A JP 2004033824A
- Authority
- JP
- Japan
- Prior art keywords
- assembled monolayer
- self
- resistant self
- polyaromatic
- substrate
- 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
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
【課題】紫外線耐性を有する自己組織化単分子膜を提供する。
【解決手段】式
【化１】
［式中、Ｘは基板表面に化学吸着することができる官能基を表し、Ｒは水素原子または置換基を表し、ｍは１〜１０の整数であり、ｎは１以上の整数である］で表される多芳香環化合物、特にターフェニルメタンチオールからなる自己組織化単分子膜。この単分子膜は紫外線照射に対する耐性が高い。
【選択図】 なしA self-assembled monolayer having ultraviolet resistance is provided.
SOLUTION: The formula:
[Wherein, X represents a functional group capable of being chemically adsorbed on the substrate surface, R represents a hydrogen atom or a substituent, m is an integer of 1 to 10, and n is an integer of 1 or more] A self-assembled monolayer composed of the polyaromatic ring compound represented, particularly terphenylmethanethiol. This monomolecular film has high resistance to ultraviolet irradiation.
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、紫外線耐性に優れた自己組織化単分子膜に係る。
【０００２】
【従来の技術】
近年、作製が容易・簡便でありさまざまな特性に優れていることからいわゆる自己組織化単分子膜（ＳＡＭ）が大いに注目されている。従来、ＳＡＭの研究は主としてアルカンチオールやシランカップリング剤を用いて行われている。このようなＳＡＭは金属表面の表面コーティングやレジストを含めて広範囲の用途への応用が期待されている。
【０００３】
ＳＡＭの特性の研究において、テトラデカンチオールのようなアルカンチオールからなるＳＡＭは耐熱性に問題があることが判明した。この耐熱性の問題を解決するために、本発明者らは、用いる有機分子としてターフェニル系チオールを提案した（Ｔ， Ｉｓｈｉｄａ， ｅｔ ａｌ．， Ｌａｎｇｍｕｉｒ， ２００２， １８， ８３−９２）。
【０００４】
【発明が解決しようとする課題】
ＳＡＭの特性をさらに高めるべく研究が続けられている。たとえば、上記の耐熱性に加えて、紫外線に対する耐性があればさらに望ましいが、従来紫外線耐性の問題は研究されていない。このような紫外線耐性は特に、たとえばネガ光レジストや金属の表面保護材（酸化・腐食を防ぐ）の分野で必要とされる。
したがって、本発明の目的は、紫外線耐性を有する自己組織化単分子膜を提供することである。
【０００５】
【課題を解決するための手段】
本発明者らは、この紫外線耐性の問題に着目し、種々検討した結果、デカンチオールのようなアルカンチオールやベンゼンメルカプタンのようなチオール化合物は紫外線に対する耐性が十分ではないことを見出した。さらに研究を続けたところ、多芳香環構造の骨格を有する有機化合物を使用すると顕著に高い紫外線耐性が得られることが判明した。
すなわち、本発明は、次式で表される多芳香環化合物からなる紫外線耐性自己組織化単分子膜を提供する。
【０００６】
【化２】
【０００７】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明は、上記式で表される多芳香環構造を有する化合物を使用することをその特徴とする。このような化合物、たとえばターフェニルメタンチオール誘導体から作製した自己組織化単分子膜が耐熱性を有することはすでに開示されているが（Ｔ， Ｉｓｈｉｄａ， ｅｔ ａｌ．， Ｌａｎｇｍｕｉｒ， ２００２， １８， ８３−９２）、そのような自己組織化単分子膜の紫外線耐性については教示も示唆もされていない。これらの多芳香環化合物、たとえばターフェニルメタンチオールから得られる自己組織化単分子膜が優れた紫外線耐性を有することは、後述の実施例にも記載されているように、紫外線照射実験によって充分に確かめられている。
【０００８】
前記式中のＸは、基板表面に化学吸着することができる官能基を表すが、従来から自己組織化単分子膜を形成することができるものとして知られているものがすべて使用できる。たとえば、Ｘはチオール基またはシランカップリング基であることができ、特にチオール基が好ましい。なお、シランカップリング剤の例としては、シラン、アルコキシシラン、たとえばトリメトキシシランなどがある。
【０００９】
また、式中のＲは水素原子または置換基を表し、置換基としては従来から自己組織化単分子膜を形成することができるものとして知られているものでよく、さらには紫外線耐性を強化するものであると好ましい。たとえば、メチル、エチルなどのアルキル基、塩素、臭素などのハロゲン原子、ニトリル基、シアノ基、トリフルオロメチル基、などが挙げられる。
【００１０】
式中のｍとｎは整数であり、ｍは１〜１０の整数であり、ｎは１以上の整数である。ｍとｎが両方とも１であるのが好ましい。
上記式で表される多芳香環化合物のうち、特に好ましいのはターフェニルメタンチオールである。
【００１１】
上記式で表される多芳香環化合物から自己組織化単分子膜を作製するには、従来の方法に従えばよい。すなわち、本発明の多芳香環化合物を溶かすことができる溶媒、たとえばジクロロメタンなどの溶媒に溶解した溶液中に基板を浸漬するだけでよい。この溶媒の選択、溶液の濃度、温度、浸漬の時間などは当業者が容易に決定することができる。また、基板としては、金、銀、その他従来から自己組織化単分子膜の基板として用いられているものでよい。
本発明によると、多芳香環構造を有する化合物を使用して自己組織化単分子膜に紫外線耐性を付与することができる。
本発明の多芳香環化合物からなる自己組織化単分子膜は、紫外線耐性に優れているため、特にネガ光レジストや金属の表面保護材のような用途に有用である。
【００１２】
【実施例】
以下、限定することのない実施例を参照して本発明をさらに詳細に説明する。実施例１
ターフェニルメタンチオール（保土ヶ谷コントラクトラボ社製。以後ＴＰと略す）をジクロロメタン中に１ｍＭの濃度に希釈した溶液中に室温で金基板を２４時間浸漬した。
【００１３】
次に、この試料のＸ線光電子スペクトル（ＸＰＳ）を測定した。その結果、Ｃ（１ｓ）領域（束縛エネルギー２８４．０ｅＶ）およびＳ（２ｐ）領域（１６２ｅＶ）に金に吸着した分子の硫黄に由来するピークが検出され、金基板表面に単分子膜が形成されていることが明らかになった。
比較として、デカンチオール（ＣＨ３（ＣＨ２）９ＳＨ、以後Ｃ１０と略す）およびベンゼンメルカプタン（以後ＢＭと略す）と溶媒としてエタノールを用いて同様に浸漬を行った。その結果、ＸＰＳの測定により、金基板表面に単分子膜が形成されていることが明らかになった。
【００１４】
実施例２
次にこれらＳＡＭの試料に２５４ｎｍの波長の光を照射した後、試料のＸＰＳを測定した。照射時間は１時間、３時間、６時間と変化させた。
その結果、Ｃ１０とＢＭのＳＡＭにおいてＳ（２ｐ）領域に金に吸着した分子の硫黄のピーク（１６２ｅＶ）のみならず、分子の硫黄が酸化されてＳＯ３に変化したものと帰属できるピーク（１６８ｅＶ）も検出された。また、Ｃ（１ｓ）ピークの強度も弱くなっていた。さらに、３時間光照射したＳＡＭの表面を走査型トンネル顕微鏡（ＳＴＭ）で観察したところ部分的な脱離が確認された。これは、２５４ｎｍの光照射においてＳＡＭの硫黄が活性化され、大気中の酸素または水分などと反応して、硫黄が酸化され、分子と金基板の結合が弱まり、分子が一部分脱離したものと考えられる。
【００１５】
これに対し、ＴＰのＳＡＭにおいては、光照射後もＳ（２ｐ）領域に金に吸着した分子の硫黄のピーク（１６２ｅＶ）のみしか観察されず、ＳＴＭ観察においても分子の金基板表面からの脱離は全く観察されなかった。さらに、２４時間の紫外光照射でも殆ど分子の脱離が見られなかった。すなわち、ＴＰのＳＡＭは紫外線照射に対して耐性が高いことが確認された。
【００１６】
【発明の効果】
本発明により、紫外線に対して優れた耐性を有する自己組織化単分子膜を形成することができる。この自己組織化単分子膜は、たとえばネガ光レジストや金属の表面保護材などを始めとする広範囲の用途において特に有利である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a self-assembled monolayer excellent in ultraviolet light resistance.
[0002]
[Prior art]
In recent years, so-called self-assembled monolayers (SAMs) have attracted much attention because they are easy and simple to manufacture and are excellent in various properties. Conventionally, SAM research has been mainly performed using alkane thiols and silane coupling agents. Such a SAM is expected to be applied to a wide range of uses including a surface coating on a metal surface and a resist.
[0003]
In studies of the properties of SAMs, it has been found that SAMs composed of alkanethiols such as tetradecanethiol have problems with heat resistance. In order to solve the problem of heat resistance, the present inventors have proposed a terphenyl thiol as an organic molecule to be used (T, Ishida, et al., Langmuir, 2002, 18, 83-92).
[0004]
[Problems to be solved by the invention]
Research is ongoing to further enhance the properties of SAM. For example, in addition to the above-mentioned heat resistance, it is more desirable to have resistance to ultraviolet light, but the problem of ultraviolet light resistance has not been studied so far. Such UV resistance is particularly required in the fields of, for example, negative resists and metal surface protective materials (to prevent oxidation and corrosion).
Accordingly, it is an object of the present invention to provide a self-assembled monolayer having UV resistance.
[0005]
[Means for Solving the Problems]
The present inventors have focused on this problem of ultraviolet light resistance, and as a result of various studies, have found that alkane thiols such as decane thiol and thiol compounds such as benzene mercaptan have insufficient resistance to ultraviolet light. Further studies have shown that the use of an organic compound having a polyaromatic ring skeleton results in significantly higher UV resistance.
That is, the present invention provides a UV-resistant self-assembled monolayer comprising a polyaromatic ring compound represented by the following formula.
[0006]
Embedded image
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The present invention is characterized by using a compound having a polyaromatic ring structure represented by the above formula. It has already been disclosed that a self-assembled monolayer formed from such a compound, for example, a terphenylmethanethiol derivative has heat resistance (T, Ishida, et al., Langmuir, 2002, 18, 83-). 92), there is no teaching or suggestion about the UV resistance of such self-assembled monolayers. The self-assembled monolayer obtained from these polyaromatic ring compounds, for example, terphenylmethanethiol, has excellent UV resistance, as described in Examples below. Has been verified.
[0008]
X in the above formula represents a functional group that can be chemically adsorbed on the substrate surface, and any of those conventionally known as those capable of forming a self-assembled monolayer can be used. For example, X can be a thiol group or a silane coupling group, with a thiol group being particularly preferred. Examples of the silane coupling agent include silane, alkoxysilane, for example, trimethoxysilane.
[0009]
Further, R in the formula represents a hydrogen atom or a substituent, and the substituent may be any of those conventionally known as those capable of forming a self-assembled monolayer, and further enhances ultraviolet light resistance. It is preferred that it is. Examples include an alkyl group such as methyl and ethyl, a halogen atom such as chlorine and bromine, a nitrile group, a cyano group, and a trifluoromethyl group.
[0010]
In the formula, m and n are integers, m is an integer of 1 to 10, and n is an integer of 1 or more. Preferably, m and n are both 1.
Of the polyaromatic ring compounds represented by the above formula, terphenylmethanethiol is particularly preferred.
[0011]
In order to prepare a self-assembled monolayer from the polyaromatic ring compound represented by the above formula, a conventional method may be used. That is, it is only necessary to immerse the substrate in a solution in which the polyaromatic ring compound of the present invention can be dissolved, for example, a solvent such as dichloromethane. Those skilled in the art can easily determine the selection of the solvent, the concentration of the solution, the temperature, the immersion time, and the like. The substrate may be gold, silver, or any other substrate conventionally used as a substrate for a self-assembled monolayer.
According to the present invention, UV resistance can be imparted to a self-assembled monolayer using a compound having a polyaromatic ring structure.
The self-assembled monomolecular film comprising the polyaromatic ring compound of the present invention is excellent in ultraviolet light resistance, and thus is particularly useful for applications such as negative photoresists and metal surface protective materials.
[0012]
【Example】
Hereinafter, the present invention will be described in more detail with reference to non-limiting examples. Example 1
The gold substrate was immersed in a solution of terphenylmethanethiol (manufactured by Hodogaya Contract Lab Co., Ltd .; hereinafter abbreviated as TP) at a concentration of 1 mM in dichloromethane at room temperature for 24 hours.
[0013]
Next, the X-ray photoelectron spectrum (XPS) of this sample was measured. As a result, peaks derived from sulfur of molecules adsorbed on gold are detected in the C (1s) region (binding energy 284.0 eV) and the S (2p) region (162 eV), and a monomolecular film is formed on the surface of the gold substrate. It became clear that.
For comparison, immersion was similarly performed using decanethiol (CH 3 (CH 2 ) 9 SH, hereinafter abbreviated as C10), benzenemercaptan (hereinafter abbreviated as BM), and ethanol as a solvent. As a result, XPS measurement revealed that a monomolecular film was formed on the gold substrate surface.
[0014]
Example 2
Next, the SAM samples were irradiated with light having a wavelength of 254 nm, and the XPS of the samples was measured. The irradiation time was changed to 1 hour, 3 hours, and 6 hours.
As a result, in the SAM of C10 and BM, not only the peak (162 eV) of the sulfur of the molecule adsorbed on gold in the S (2p) region, but also the peak (168 eV) attributable to the oxidation of the sulfur of the molecule to SO 3. ) Was also detected. Also, the intensity of the C (1s) peak was weak. Further, when the surface of the SAM irradiated with light for 3 hours was observed with a scanning tunneling microscope (STM), partial desorption was confirmed. This is because the SAM sulfur is activated by 254 nm light irradiation, reacts with oxygen or moisture in the atmosphere, oxidizes sulfur, weakens the bond between the molecule and the gold substrate, and partially removes the molecule. Conceivable.
[0015]
On the other hand, in the SAM of TP, only the sulfur peak (162 eV) of the molecule adsorbed on gold was observed in the S (2p) region even after irradiation with light, and the desorption of the molecule from the surface of the gold substrate was observed in the STM observation. No detachment was observed. Further, almost no molecule desorption was observed even after irradiation with ultraviolet light for 24 hours. That is, it was confirmed that the SAM of TP had high resistance to ultraviolet irradiation.
[0016]
【The invention's effect】
According to the present invention, a self-assembled monolayer having excellent resistance to ultraviolet light can be formed. This self-assembled monolayer is particularly advantageous in a wide range of applications including, for example, negative photoresists and metal surface protective materials.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002191031A JP4723161B2 (en) | 2002-06-28 | 2002-06-28 | UV-resistant self-assembled monolayers with polyaromatic ring compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002191031A JP4723161B2 (en) | 2002-06-28 | 2002-06-28 | UV-resistant self-assembled monolayers with polyaromatic ring compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004033824A true JP2004033824A (en) | 2004-02-05 |
| JP4723161B2 JP4723161B2 (en) | 2011-07-13 |
Family
ID=31700772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002191031A Expired - Lifetime JP4723161B2 (en) | 2002-06-28 | 2002-06-28 | UV-resistant self-assembled monolayers with polyaromatic ring compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4723161B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014125527A1 (en) | 2013-02-12 | 2014-08-21 | 独立行政法人科学技術振興機構 | Electronic device using organic thin film, and electronic apparatus containing same |
| JP2017510066A (en) * | 2014-02-19 | 2017-04-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Methoxyaryl surface modifier and organic electronic devices containing such methoxyaryl surface modifier |
| US10305052B2 (en) | 2014-07-15 | 2019-05-28 | Japan Science And Technology Agency | Triptycene derivative useful as material for forming self-assembled film, method for manufacturing said triptycene derivative, film using same, method for manufacturing said film, and electronic device using said method |
| CN117504840A (en) * | 2023-12-20 | 2024-02-06 | 南方海洋科学与工程广东省实验室(广州) | Self-assembled monomolecular membrane and its preparation method and application |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8604265B2 (en) | 2010-04-16 | 2013-12-10 | Kci Licensing, Inc. | Dressings and methods for treating a tissue site on a patient |
| US8403902B2 (en) | 2010-05-18 | 2013-03-26 | Kci Licensing, Inc. | Reduced-pressure medical systems and methods employing a moisture processing device |
-
2002
- 2002-06-28 JP JP2002191031A patent/JP4723161B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014125527A1 (en) | 2013-02-12 | 2014-08-21 | 独立行政法人科学技術振興機構 | Electronic device using organic thin film, and electronic apparatus containing same |
| US9825232B2 (en) | 2013-02-12 | 2017-11-21 | Japan Science And Technology Agency | Electronic device using organic thin film, and electronic apparatus containing the same |
| JP2017510066A (en) * | 2014-02-19 | 2017-04-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Methoxyaryl surface modifier and organic electronic devices containing such methoxyaryl surface modifier |
| US10305052B2 (en) | 2014-07-15 | 2019-05-28 | Japan Science And Technology Agency | Triptycene derivative useful as material for forming self-assembled film, method for manufacturing said triptycene derivative, film using same, method for manufacturing said film, and electronic device using said method |
| CN117504840A (en) * | 2023-12-20 | 2024-02-06 | 南方海洋科学与工程广东省实验室(广州) | Self-assembled monomolecular membrane and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4723161B2 (en) | 2011-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8263192B2 (en) | Methods for modifying surfaces | |
| Cooper et al. | Influence of tail-group hydrogen bonding on the stabilities of self-assembled monolayers of alkylthiols on gold | |
| Chinwangso et al. | Multidentate adsorbates for self-assembled monolayer films | |
| Pujari et al. | Covalent surface modification of oxide surfaces | |
| US8173347B2 (en) | Micropatterning of molecular surfaces via selective irradiation | |
| Kang et al. | Self-assembled rigid monolayers of 4 ‘-substituted-4-mercaptobiphenyls on gold and silver surfaces | |
| Ron et al. | Self-assembled monolayers on oxidized metals. 4. Superior n-alkanethiol monolayers on copper | |
| Mekhalif et al. | Self-assembled monolayers of n-dodecanethiol on electrochemically modified polycrystalline nickel surfaces | |
| US9296870B2 (en) | Modification of surfaces with nanoparticles | |
| Sinapi et al. | Self-assembly of (3-mercaptopropyl) trimethoxysilane on polycrystalline zinc substrates towards corrosion protection | |
| JP4065962B2 (en) | Fabrication method and utilization of self-assembled monolayer | |
| KR101458058B1 (en) | Composition for surface treatment forming self-assembled monolayer easily surface coating and removing | |
| Vance et al. | XAS and XPS characterization of monolayers derived from a dithiol and structurally related disulfide-containing polyamides | |
| Huisman et al. | Surface‐Confined Metallodendrimers: Isolated Nanosize Molecules | |
| KR960014112B1 (en) | Hydrophilic chemically absorbed film and method of manufacturing the same | |
| JP4723161B2 (en) | UV-resistant self-assembled monolayers with polyaromatic ring compounds | |
| Iqbal et al. | Chemical manipulation by X-rays of functionalized thiolate self-assembled monolayers on Au | |
| US20050221081A1 (en) | Stabilization of self-assembled monolayers | |
| Luo et al. | In situ hydrolysis of imine derivatives on au (111) for the formation of aromatic mixed self-assembled monolayers: Multitechnique analysis of this tunable surface modification | |
| Denayer et al. | Self-assembly of amine terminated alkylthiol and alkyldithiol films on a polycrystalline copper substrate | |
| Wang et al. | Formation, characterization, and sub-50-nm patterning of organosilane monolayers with embedded disulfide bonds: An engineered self-assembled monolayer resist for electron-beam lithography | |
| JP5301082B2 (en) | Compound, film-forming composition and method for producing laminate | |
| Min et al. | A photoswitchable methylene-spaced fluorinated aryl azobenzene monolayer grafted on silicon | |
| JP4376540B2 (en) | Metal surface modifiers and new sulfur-containing compounds | |
| CN101185879A (en) | Preparation method and application of molecular self-assembled monolayer film/quartz sand adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050425 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071017 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20071023 |
|
| RD13 | Notification of appointment of power of sub attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7433 Effective date: 20071113 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071220 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071129 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090310 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20090511 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110307 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110407 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140415 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4723161 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| 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 |
|
| 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 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |