JP7178078B2 - Surface treatment method for polymer material - Google Patents
Surface treatment method for polymer material Download PDFInfo
- Publication number
- JP7178078B2 JP7178078B2 JP2018106183A JP2018106183A JP7178078B2 JP 7178078 B2 JP7178078 B2 JP 7178078B2 JP 2018106183 A JP2018106183 A JP 2018106183A JP 2018106183 A JP2018106183 A JP 2018106183A JP 7178078 B2 JP7178078 B2 JP 7178078B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer material
- present
- reaction
- aminoalkyl
- nitrogen
- 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.)
- Active
Links
Images
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
本発明は、ポリマー材料の表面改質の技術、具体的には、ポリマー表面に親水性を付与し、また金属との親和性を高めることで、親水性部材、異種材料接合、電池用部材、回路基板、導電性部材、無電解めっきの基材等として適切なポリマー材料を提供する技術に関する。 The present invention provides a technology for modifying the surface of polymer materials, specifically, by imparting hydrophilicity to the surface of the polymer and increasing affinity with metals, hydrophilic members, dissimilar material bonding, battery members, The present invention relates to a technique for providing a polymer material suitable for circuit boards, conductive members, base materials for electroless plating, and the like.
従来、ポリマー材料表面にアミノ基などの窒素官能基を導入し、親水性を付与し、また金属との親和性を高める方法として、基材表面上への窒素プラズマによる処理（特許文献１）、アンモニアプラズマによる処理（特許文献２）、アンモニア水溶液を用いたレーザー照射処理（特許文献３）、ヒドラジン共存下でのレーザー照射処理（特許文献４）等が知られている。
しかしながら、これらの方法においては大型装置が必要である、或いは、有毒であって、その取り扱いが困難であるアンモニアガスやヒドラジンを使用する必要がある等の課題がある。また、このようなガスや薬剤を使用する場合、特殊な反応容器が必要となり、操作も煩雑となる。
脂肪族ニトリルの光反応を利用した表面改質法として、本発明者はカーボン系材料表面のアミノアルキル化に関する手法を開発している（特許文献５）が、当該手法が加熱や光照射に敏感なポリマー材料表面改質に適用可能かどうかは不明であった。
Conventionally, as a method of introducing a nitrogen functional group such as an amino group to the surface of a polymer material to impart hydrophilicity and increase affinity with metals, the substrate surface is treated with nitrogen plasma (Patent Document 1), Ammonia plasma treatment (Patent Document 2), laser irradiation treatment using an aqueous ammonia solution (Patent Document 3), laser irradiation treatment in the presence of hydrazine (Patent Document 4), and the like are known.
However, these methods have problems such as the need for a large-sized apparatus or the need to use ammonia gas or hydrazine, which are toxic and difficult to handle. Moreover, when using such a gas or chemical, a special reaction vessel is required, which complicates the operation.
As a surface modification method using the photoreaction of aliphatic nitriles, the present inventors have developed a technique for aminoalkylation of the surface of carbon-based materials (Patent Document 5), but this technique is sensitive to heating and light irradiation. It was unclear whether it could be applied to various polymer material surface modification.
本発明は、従来この種の方法に用いられてきたアンモニア等の有毒ガスを使用することなく、プラズマ処理のための大型装置を使用することなく、また取り扱いに注意が必要な薬剤を使用することなく、安全、かつ簡便にポリマー材料表面上に窒素官能基であるアミノアルキル基を導入する方法を提供することを課題とし、また、種類によっては耐熱性、耐光性に劣るポリマー材料表面上に、基材を加熱することなく、光照射による基材劣化を起こすことなく、アミノアルキル基を導入する方法を提供することを課題とする。 The present invention does not use toxic gases such as ammonia, which have been used in this type of method in the past, does not use large equipment for plasma treatment, and uses chemicals that require careful handling. It is an object of the present invention to provide a method for safely and simply introducing an aminoalkyl group, which is a nitrogen functional group, onto the surface of a polymer material without causing any damage to the surface of the polymer material. An object of the present invention is to provide a method for introducing an aminoalkyl group without heating the substrate and without causing deterioration of the substrate due to light irradiation.
本発明者らは、ポリマー材料に、脂肪族ニトリル存在下に紫外線を照射すると、ポリマー材料表面上にアミノアルキル基を化学的に結合させることができることを見いだし、本発明を完成させた。 The inventors of the present invention have found that by irradiating a polymer material with ultraviolet rays in the presence of an aliphatic nitrile, it is possible to chemically bond aminoalkyl groups on the surface of the polymer material, thereby completing the present invention.
すなわち、本出願は、以下の発明を提供するものである。
〈１〉アミノアルキル基がその表面に化学結合していることを特徴とするポリマー材料。
〈２〉ポリマー材料と下記一般式（１）で表される脂肪族ニトリルに紫外線を照射することにより、ポリマー材料の表面にアミノアルキル基を化学結合させることを特徴とするポリマー材料の表面処理方法。
ＣＨ3(ＣＨ2)nＣＮ （１）
（式中、ｎは０～４の整数を示す。）
〈３〉波長１７０～３００ｎｍの紫外光を照射することを特徴とする、〈２〉に記載のポリマー材料の表面処理方法。
〈４〉光量を０．１～１００ｍＷ／ｃｍ2の範囲で照射することを特徴とする、〈２〉又は〈３〉に記載のポリマー材料の表面処理方法。
That is, the present application provides the following inventions.
<1> A polymer material characterized in that aminoalkyl groups are chemically bonded to its surface.
<2> A method for surface treatment of a polymer material, which comprises chemically bonding an aminoalkyl group to the surface of the polymer material by irradiating the polymer material and an aliphatic nitrile represented by the following general formula (1) with ultraviolet rays. .
CH3 ( CH2 ) nCN (1)
(In the formula, n represents an integer of 0 to 4.)
<3> The method for surface treatment of a polymer material according to <2>, characterized by irradiating with ultraviolet light having a wavelength of 170 to 300 nm.
<4> The method for surface treatment of a polymer material according to <2> or <3>, characterized in that the amount of light applied is in the range of 0.1 to 100 mW/cm 2 .
本発明は、脂肪族ニトリルに紫外線照射をするだけの簡便な反応操作により、ポリマー材料表面上にアミノアルキル基を導入することができるという優れた効果を有する。本発明によれば、従来用いられてきた有毒ガスを使用することがなく、安全に、煩雑さを伴うことなく、ポリマー材料の表面に、前記アミノアルキル基を結合させることができるという著しい効果がある。
本発明の反応は室温下で可能であり、本発明の反応手法を用いることにより、種類によっては耐熱性、耐薬品性、耐光性に劣る広範囲のポリマー材料に対し、光照射による基材劣化を起こすことなく、ポリマー材料表面上にアミノアルキル基を導入することができる。
ADVANTAGE OF THE INVENTION This invention has the outstanding effect that an aminoalkyl group can be introduce|transduced on the polymer material surface by the simple reaction operation which only irradiates an aliphatic nitrile with ultraviolet rays. According to the present invention, it is possible to bond the aminoalkyl group to the surface of the polymer material safely without using the conventionally used toxic gas and without any complications. be.
The reaction of the present invention can be performed at room temperature, and by using the reaction method of the present invention, a wide range of polymer materials, depending on the type, have poor heat resistance, chemical resistance, and light resistance. Aminoalkyl groups can be introduced onto the surface of the polymeric material without causing a reaction.
本発明の方法で用いられるポリマー材料は、各種汎用性ポリマーおよび機能性ポリマーを使用することができる。ポリマー材料の形状には特に制限はなく、板状、膜状、粉末状、ペレット状等広く使用することができる。 Various general-purpose polymers and functional polymers can be used as the polymer material used in the method of the present invention. The shape of the polymer material is not particularly limited, and a wide variety of shapes such as plate, film, powder and pellets can be used.
前記ポリマー材料表面にアミノアルキル基を化学結合させるために用いる脂肪族ニトリルは、下記一般式（１）で表される化合物である。
ＣＨ3(ＣＨ2)nＣＮ （１）
（式中、ｎは０～４の整数を示す。）
前記アミノアルキル基の炭素数はその炭素数が２～６、好ましくは、２～４のものである。
本発明方法の反応においては、これらの脂肪族ニトリルの鎖長による反応性の差はない。上記の脂肪族ニトリルは例示であり、他の脂肪族ニトリルを使用することもできる。
The aliphatic nitrile used for chemically bonding aminoalkyl groups to the polymer material surface is a compound represented by the following general formula (1).
CH3 ( CH2 ) nCN (1)
(In the formula, n represents an integer of 0 to 4.)
The aminoalkyl group has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
In the reaction of the method of the present invention, there is no difference in reactivity due to the chain length of these aliphatic nitriles. The above aliphatic nitriles are exemplary and other aliphatic nitriles can be used.
本発明の方法に際しては、原料物質である前記脂肪族ニトリルを液体としてポリマー材料に接触させる手法、脂肪族ニトリルを気体として反応容器に導入する手法、などドライプロセスおよびウェットプロセスの双方を利用することができる。 In the method of the present invention, both a dry process and a wet process, such as a method of bringing the aliphatic nitrile, which is a raw material, into contact with the polymer material as a liquid, and a method of introducing the aliphatic nitrile as a gas into the reaction vessel, are used. can be done.
反応に際しては、前記脂肪族ニトリルのラジカル解離反応により発生した水素ラジカルによってニトリル基がアミノ基に変換されることが必要であることから、このために紫外線照射下に行う。波長は１７０ｎｍ～３００ｎｍとするのが好適である。
光源としては公知のものが用いることができる。その例を挙げると、低圧水銀灯、高圧水銀灯、ＡｒＦまたはＸｅＣｌエキシマレーザー、エキシマランプ等である。このように、本発明は、広範囲の波長の光を利用できる。
反応の高効率化のためには、２００ｎｍ以下の波長を有する紫外線照射下に反応を行うことが好ましい。
照射される光量の好ましい範囲は、０．１～１００ｍＷ／ｃｍ2の範囲である。また、照射時間は、１～３０分程度とするのが望ましい。これらの条件は、前記範囲外の条件を使用することも可能である。前記は好ましい範囲であり、必ずしもこれに特に制限されるものではない。
In the reaction, the nitrile group must be converted into an amino group by the hydrogen radical generated by the radical dissociation reaction of the aliphatic nitrile, so the reaction is carried out under ultraviolet irradiation. A wavelength of 170 nm to 300 nm is suitable.
A well-known thing can be used as a light source. Examples include low-pressure mercury lamps, high-pressure mercury lamps, ArF or XeCl excimer lasers, excimer lamps, and the like. Thus, the present invention can utilize light of a wide range of wavelengths.
In order to improve the efficiency of the reaction, it is preferable to carry out the reaction under UV irradiation having a wavelength of 200 nm or less.
A preferable range of the amount of light to be irradiated is 0.1 to 100 mW/cm 2 . Also, the irradiation time is preferably about 1 to 30 minutes. These conditions can also use conditions outside the above range. The above is a preferred range and is not necessarily particularly limited thereto.
本発明の反応は、室温下で容易に進行する。これは、本発明の大きな特徴の一つでもある。しかし、加熱を否定するものではない。必要に応じて加熱することも可能である。 The reactions of the present invention readily proceed at room temperature. This is also one of the major features of the present invention. However, it does not deny heating. It is also possible to heat if necessary.
このようにして得られるアミノアルキル化ポリマー材料を分析機器により、表面に前記アミノアルキル基が化学結合しているかどうかを確認する。各種の分析機器を用いることができるが、ＸＰＳなどによりアミノ基の存在を確認することができ、水に対する接触角測定によってアミノ基導入による親水性を確認することができる。また、アミノアルキル基はポリマー材料表面上にのみ化学結合しており、基材であるポリマー材料のバルク特性には影響を与えないことから、透明性を有するポリマー材料に本発明の手法を適用した場合には、ポリマー材料基材の透明度を保持することが可能である。 The thus-obtained aminoalkylated polymer material is analyzed with an analytical instrument to confirm whether or not the aminoalkyl group is chemically bonded to the surface. Although various analytical instruments can be used, the presence of amino groups can be confirmed by XPS or the like, and the hydrophilicity due to the introduction of amino groups can be confirmed by measuring the contact angle with water. In addition, since the aminoalkyl group is chemically bonded only to the surface of the polymer material and does not affect the bulk properties of the base polymer material, the technique of the present invention was applied to transparent polymer materials. In some cases, it is possible to retain the transparency of the polymeric material substrate.
本発明では、ポリマー材料にアミノアルキル基を化学結合させることができる結果、窒素原子を含んだ官能基をその表面に結合させることで、ポリマー材料に親水性、金属との親和性を付与することができる。 In the present invention, as a result of being able to chemically bond aminoalkyl groups to polymer materials, it is possible to impart hydrophilicity and affinity to metals to polymer materials by bonding functional groups containing nitrogen atoms to their surfaces. can be done.
以下、実施例により、本発明をさらに詳細に説明する。 The present invention will be described in more detail below with reference to examples.
（実施例１）
シート状のポリマー材料（ポリイミド、ポリエチレンテレフタレート 各５０μｍ厚）、および板状のポリマー材料（ポリエチレン、ポリプロピレン、ポリ塩化ビニル 各１ｍｍ厚）にアセトニトリルを塗布し、これにキセノンエキシマランプ（エム・ディ・コム製 光量１００ｍＷ／ｃｍ2）を室温で、シート状基材には３分間、板状基材には２分間、照射した。紫外線照射の波長は１７２ｎｍである。
その後、ポリマー材料を純水で洗浄し、減圧下で乾燥を行った。反応後のポリマー材料のＸＰＳ測定を行ったところ、非窒素含有ポリマー材料においては新規に窒素に由来するピークが観測され、含窒素ポリマー材料については窒素ピークの強度が増加し、表面上にアミノアルキル基が導入されたことが確認された（図１）。また、水に対する接触角が２３～４３°を示し、親水性が付与された（表１）。さらに、透明性ポリマー材料（ポリエチレンテレフタレート）について紫外可視分光光度計を用いて透過度を測定したところ、アミノアルキル化ポリマー材料の透過度は反応処理前と比較してほぼ変化がなく、アミノアルキル基導入の基材への影響は少ないことが確認された（図２）。
(Example 1)
Acetonitrile was applied to sheet-shaped polymer materials (polyimide and polyethylene terephthalate each 50 μm thick) and plate-shaped polymer materials (polyethylene, polypropylene and polyvinyl chloride each 1 mm thick), and a xenon excimer lamp (M.D.com) was applied. A light amount of 100 mW/cm 2 ) was applied at room temperature to the sheet-like substrate for 3 minutes and to the plate-like substrate for 2 minutes. The wavelength of ultraviolet irradiation is 172 nm.
After that, the polymer material was washed with pure water and dried under reduced pressure. When the XPS measurement of the polymer material after the reaction was performed, a new peak derived from nitrogen was observed in the non-nitrogen-containing polymer material, the intensity of the nitrogen peak increased in the nitrogen-containing polymer material, and the aminoalkyl It was confirmed that the group was introduced (Fig. 1). Further, the contact angle with water was 23 to 43°, and hydrophilicity was imparted (Table 1). Furthermore, when the transmittance of the transparent polymer material (polyethylene terephthalate) was measured using an ultraviolet-visible spectrophotometer, the transmittance of the aminoalkylated polymer material remained almost unchanged compared to before the reaction treatment, indicating that the aminoalkyl group It was confirmed that the introduction had little effect on the substrate (Fig. 2).
（実施例２）
板状のポリマー材料（ポリメチルメタクリレート、ポリカーボネート、ABS樹脂 各１ｍｍ厚）に１０％アセトニトリル水溶液を塗布し、これにキセノンエキシマランプ（エム・ディ・コム製 光量１００ｍＷ／ｃｍ2）を室温で１分間照射した。紫外線照射の波長は１７２ｎｍである。
その後、ポリマー材料を純水で洗浄し、減圧下で乾燥を行った。反応後のポリマー材料のＸＰＳ測定を行ったところ、非窒素含有ポリマー材料においては新規に窒素に由来するピークが観測され、含窒素ポリマー材料については窒素ピークの強度が増加し、表面上にアミノアルキル基が導入されたことが確認された（図３）。また、水に対する接触角が２６～３８°を示し、親水性が付与された（表２）。
(Example 2)
A 10% aqueous solution of acetonitrile was applied to a plate-shaped polymer material (polymethyl methacrylate, polycarbonate, ABS resin, each with a thickness of 1 mm), and a xenon excimer lamp (light intensity: 100 mW/cm 2 manufactured by M.D.com) was applied to the plate at room temperature for 1 minute. irradiated. The wavelength of ultraviolet irradiation is 172 nm.
After that, the polymer material was washed with pure water and dried under reduced pressure. When the XPS measurement of the polymer material after the reaction was performed, a new peak derived from nitrogen was observed in the non-nitrogen-containing polymer material, the intensity of the nitrogen peak increased in the nitrogen-containing polymer material, and aminoalkyl It was confirmed that the group was introduced (Fig. 3). Moreover, the contact angle with water was 26 to 38°, and hydrophilicity was imparted (Table 2).
本発明により表面に親水性が付与され、また金属との親和性が高められたポリマー材料は、親水性部材、異種材料接合、電池用部材、回路基板、導電性部材、無電解めっきの基材等として、各種用途に使用可能である。 A polymer material having a hydrophilic surface imparted with hydrophilicity and enhanced affinity with metals according to the present invention can be used as a hydrophilic member, dissimilar material bonding, battery member, circuit board, conductive member, base material for electroless plating. etc., and can be used for various purposes.
Claims (3)
ＣＨ３（ＣＨ２）ｎＣＮ （１）
（式中、ｎは０～４の整数を示す。） By irradiating a polymer material and an aliphatic nitrile represented by the following general formula (1) with ultraviolet rays having a wavelength of 170 to 200 nm, an amino group converted from the nitrile group of the aliphatic nitrile is formed on the surface of the polymer material. A method for treating the surface of a polymer material, characterized by chemically bonding aminoalkyl groups contained therein.
CH3 ( CH2 ) nCN (1)
(In the formula, n represents an integer of 0 to 4.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018106183A JP7178078B2 (en) | 2018-06-01 | 2018-06-01 | Surface treatment method for polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018106183A JP7178078B2 (en) | 2018-06-01 | 2018-06-01 | Surface treatment method for polymer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019210349A JP2019210349A (en) | 2019-12-12 |
| JP7178078B2 true JP7178078B2 (en) | 2022-11-25 |
Family
ID=68846373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018106183A Active JP7178078B2 (en) | 2018-06-01 | 2018-06-01 | Surface treatment method for polymer material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7178078B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151914A (en) | 1999-09-13 | 2001-06-05 | Fuji Xerox Co Ltd | Method and apparatus for surface modification of fluororesin |
| JP2004225035A (en) | 2002-11-25 | 2004-08-12 | Shiseido Co Ltd | Material surface modification method |
| CN1986614A (en) | 2006-12-15 | 2007-06-27 | 清华大学 | Process of optically grafting long fatty carbon chain pyridine salt to the surface of polymer |
| JP2013189595A (en) | 2012-03-15 | 2013-09-26 | Nitto Denko Corp | Polymer electrolyte membrane having graft chain and production method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259716A (en) * | 1995-03-22 | 1996-10-08 | Japan Atom Energy Res Inst | Surface modification method of fluoropolymer by light irradiation with aliphatic amine |
-
2018
- 2018-06-01 JP JP2018106183A patent/JP7178078B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151914A (en) | 1999-09-13 | 2001-06-05 | Fuji Xerox Co Ltd | Method and apparatus for surface modification of fluororesin |
| JP2004225035A (en) | 2002-11-25 | 2004-08-12 | Shiseido Co Ltd | Material surface modification method |
| CN1986614A (en) | 2006-12-15 | 2007-06-27 | 清华大学 | Process of optically grafting long fatty carbon chain pyridine salt to the surface of polymer |
| JP2013189595A (en) | 2012-03-15 | 2013-09-26 | Nitto Denko Corp | Polymer electrolyte membrane having graft chain and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019210349A (en) | 2019-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Studies on surface graft polymerization of acrylic acid onto PTFE film by remote argon plasma initiation | |
| Ruiz et al. | Fabrication and characterisation of amine‐rich organic thin films: Focus on stability | |
| TWI666055B (en) | Grafted ultra high molecular weight polyethylene microporous membranes | |
| JPS6392658A (en) | Radical polymerization method in the presence of dissolved air oxygen to modify surface of high-molecular material | |
| Kang et al. | Surface modifications of polyaniline films by graft copolymerization | |
| JP5597814B2 (en) | Optical surface modification of hydrophobic polymer materials | |
| Truica‐Marasescu et al. | Vacuum‐ultraviolet (VUV) Photo‐polymerization of Amine‐rich Thin Films from Ammonia–Hydrocarbon Gas Mixtures | |
| JPH05505837A (en) | Polymer surface modification | |
| JP3993096B2 (en) | Modified polymer having improved properties and method for producing the same | |
| Abbas et al. | Preparation and multi‐characterization of plasma polymerized allylamine films | |
| Ershov et al. | Derivatization of free radicals in an isopropanol plasma polymer film: the first step toward polymer grafting | |
| JP7178078B2 (en) | Surface treatment method for polymer material | |
| Wirsén et al. | Solvent-free vapor-phase photografting of acrylamide onto poly (ethylene terephthalate) | |
| Asamoto et al. | Use of polyethylene films photografted with 2‐(dimethylamino) ethyl methacrylate as a potential adsorbent for removal of chromium (VI) from aqueous medium | |
| Vig | UV/ozone cleaning of surfaces: A review | |
| Barış et al. | Synthesis, characterization and use of amphoteric hydrogels in cationic and anionic dye adsorption | |
| Jirásek et al. | Plasma treatment of detonation and HPHT nanodiamonds in diffuse coplanar surface barrier discharge in H2/N2 flow | |
| Martínez-Cocoletzi et al. | Primary-amine surface functionalization of polytetrafluoroethylene films by radiation grafting of aminated polyacryloyl chloride | |
| Akbulut Söylemez | Synthesis and characterization of tetracycline‐imprinted membranes: a detailed positron annihilation lifetime spectroscopy investigation | |
| Kraus et al. | Surface treatment of polymers by an ultraviolet laser to improve adhesion quality | |
| JP6019738B2 (en) | Method for producing substrate having hydrophilic layer | |
| JP2023053773A (en) | Surface treatment method for polymer material substrate and method for producing polymer material | |
| JPH03281544A (en) | Production of surface-modified fluorine resin | |
| Ladner et al. | Surface functionalization of COC microfluidic materials by plasma and click chemistry processes | |
| Mérai et al. | The Influence of Irradiation Wavelength on the Growth of Polymer Brushes by SI‐PET‐RAFT Polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210423 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220216 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220302 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220420 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220705 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20220817 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221018 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20221101 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20221107 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7178078 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |