CN113980679A - 一种TiO2:Yb,Er上转换发光防伪荧光粉的制备和应用 - Google Patents
一种TiO2:Yb,Er上转换发光防伪荧光粉的制备和应用 Download PDFInfo
- Publication number
- CN113980679A CN113980679A CN202111032233.6A CN202111032233A CN113980679A CN 113980679 A CN113980679 A CN 113980679A CN 202111032233 A CN202111032233 A CN 202111032233A CN 113980679 A CN113980679 A CN 113980679A
- Authority
- CN
- China
- Prior art keywords
- tio
- counterfeiting
- fluorescent powder
- powder material
- erucl
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000004020 luminiscence type Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 6
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 abstract description 8
- 238000004061 bleaching Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract 1
- 230000008859 change Effects 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 4
- 239000011368 organic material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000013532 laser treatment Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
本发明涉及一种TiO2:Yb,Er上转换发光防伪荧光粉的制备和应用,属于光致变色防伪识别技术领域。TiO2:Yb,Er是一种发光防伪荧光粉材料,其化学成分为TiO2:Yb,Er为TiO2:x%Yb,y%Er,其中x=0.1‑1,y=0.1‑1。首先将TiO2(金红石),Yb2O3,Er2O3按组成式的摩尔比混合均匀,得到混合料,所得混合料在空气中1000‑1200℃加热5‑10h,然后冷却至在室温下,研磨得到光滑的粉末防伪材料,将得到的粉末材料压制成颗粒,即UCL防伪荧光粉材料。UCL防伪荧光粉材料颗粒可用于防伪领域,具有改变UCL强度的附加能力,TiO2:Yb,Er的发光改性可通过着色漂白工艺进行控制,并且由980nm激光的强度决定。
Description
技术领域
本发明属于光致变色防伪认证技术范畴,具体涉及一种TiO2: Yb3+,Er3+上转换发光防伪荧光粉材料及其制备方法和用途。
背景技术
光致变色(PC)材料是一种在外部电场、磁场、热、应力或光的刺激下会改变颜色的材料。当物质的颜色发生变化时,材料的折射率、电导率和吸收光谱都会发生变化。因此,PC材料在光开关、光数据存储、复写纸、分子开关、成像、防伪标记、指纹采集、生物传感、逻辑门、分子线和光电器件等方面具有重要用途。PC材料可分为有机变色材料、无机变色材料、有机无机混合变色材料。常规有机PC 材料包括偶氮苯、双噻唑基香豆素、二芳基乙烯、螺吡喃等,但它们在高温下的稳定性较差,加热会对材料结构造成不可逆的破坏,化学稳定性差,合成成本高,使用环境要求高;另外,由于有机类材料易挥发,对人体危害较大,很容易造成环境污染。与传统有机材料相比,无机变色材料具有优异的显色性和热稳定性、优异的抗疲劳性、合成成本低、环境污染小,并可实现大面积显示优势,弥补了有机变色的不足。随着无机变色材料的发展,利用电场、磁场、光照射、应力或加热等外场作用使材料变色或脱色,已有大量研究,但仍存在一些问题。例如颜色变化响应时间慢、颜色变化单一、可逆性差或漂白方法。
发明内容
针对上述专利权利要求中的问题和不足,本发明提供了一种 TiO2:Yb,ErUCL防伪荧光粉材料及其制备方法和使用方法。与未掺杂Yb和Er的纯TiO2荧光粉相比,本发明的TiO2:Yb,ErUCL防伪荧光粉材料表现出优异的变色质量、快速的变色响应时间和高热稳定性。可利用优异的抗疲劳性能和光刺激优势实现变色和漂白。在实际应用中,TiO2:Yb,ErUCL荧光粉只需要LED光照射即可感知辐射。在 405nm照射下,照射区域变为淡粉色,808nm激光处理后可恢复到自然的白色状态。此外,与纯TiO2相比,TiO2:Yb,ErUCL防伪荧光粉材料具有发光特性。在980nm的近红外激光照射激发下形成可见的UCL,且通过变色特性能可逆调控其上转化发光。由于TiO2:Yb, ErUCL荧光粉具有颜色和发光双重可逆调控,在防伪领域具有广泛的应用潜力。本发明通过下列具体方案使得以实现。
一种TiO2:Yb,ErUCL防伪荧光粉材料,其化学式为 TiO2:x%Yb,y%Er,其中x=0.1~1,y=0.1~1;
优选的,所述TiO2:Yb,ErUCL防伪荧光粉材料的制备方法,其特征在于,包括以下步骤:
S1:首先将TiO2、Yb2O3、Er2O3按化学成分式的摩尔比混合均匀研磨;
S2:将步骤S1所得混合物在空气中1000~1200℃保温5~10h,冷却至室温;
S3:将S2得到的材料研磨,压成颗粒,得到TiO2:Yb,ErUCL 防伪荧光粉材料。
本发明的有益效果是:
(1)本发明制备的TiO2:Yb,ErUCL防伪荧光粉材料在405nm LED光和473nm激光照射下样品颜色由白色变为淡粉色。
(2)本发明的有色(浅粉色)样品经808nm激光处理后恢复为原来的白色。通过将荧光粉交替暴露于405nm和808nm激光,它可以经历从白色到浅粉色的可逆转变,其可逆性非常好。
(3)在近红外980nm激光刺激下,TiO2:x%Yb,y%Er(x=0.1~1, y=0.1~1)荧光粉呈现Er上转换发光并转变为淡粉色。随后上转换发光减弱,经808nm激光漂白后发光强度恢复。上转换发光可以使用着色漂白方法进行可逆调制,这在防伪专业中有广泛的应用。
(4)本发明的荧光粉TiO2:x%Yb,y%Er(x=0.1~1,y=0.1~1)具有显着的变色效果和防伪光致变色特性。预计它是一种伟大的工业产品,并具有大规模生产的潜力。
附图说明
图1为本发明的TiO2:Yb,ErUCL防伪荧光粉材料合成流程图。
图2为实施例1中制备的TiO2:1%Yb,0.1%Er荧光粉的示意图。
图3为本发明实施例1中TiO2:1%Yb,0.1%Er荧光粉的UCL光谱和发光图像。
具体实施方式
下面结合附图和具体实施方式,对本发明作进一步说明。
实施例1
如图1所示,TiO2:Yb,ErUCL防伪荧光粉材料的化学成分为 TiO2:x%Yb,y%Er,其中x=1,y=0.1。
TiO2:Yb,Er,UCL防伪荧光粉材料的制备方法,具体步骤如下:
S1:首先将TiO2,Yb2O3,Er2O3按98.9:1:0.1的摩尔比混合均匀研磨,得到混合料;
S2:将S1所得材料在空气中1150℃保温10h,冷却至室温;
S3:将S2中得到的材料研磨、冷却,压成颗粒,得到TiO2:1%Yb、 0.1%ErUCL防伪荧光粉材料。
TiO2:1%Yb,0.1%ErUCL防伪荧光粉材料在405nm的LED可见光线下,由原来的白色变为浅粉色,在405nm的LED光照射下变色;再用808nm激光照射,淡粉色已经完全褪色。漂白后,颜色从粉红色变为原来的颜色(白色)。变色效果如图2所示;说明了TiO2:1%Yb,0.1%Er荧光粉的变色。在可见的405nmLED光照射下,材料从原来的白色变为浅粉色。在808nm激光照射下由浅粉色变为白色(原色)。
TiO2:1%Yb,0.1%Er颗粒经405nmLED光照射后颜色由白色变为淡粉色;有色样品被980nm近红外激光激发,峰位于551nm和664 nm处。UCL逐渐减弱,发光光谱和发光照片如图3所示。TiO2:1%Yb, 0.1%Er荧光粉粒经808nm激光照射后漂白;808nm激光照射后,淡粉色完全褪色,UCL恢复。TiO2:1%Yb,0.1%Er荧光粉的UCL光谱和发光照片如图3所示;当被980nm激光照射时产生可见的上转换发光,在808nm激光照射(漂白)后恢复发光。
暴露于405nmLED光照射后,TiO2:1%Yb,0.1%Er荧光粉会变成淡粉色,并在808nm激光照射下变回原来的白色。由于TiO2:Yb,Er UCL荧光粉具有颜色和发光双重可逆调控,这在防伪和认证领域具有实用的可能性。
实施例2
TiO2:Yb,ErUCL防伪荧光粉材料,化学成分为TiO2:x%Yb,y%Er,其中x=1,y=0.25。
TiO2:1Yb,0.25ErUCL防伪荧光粉材料的制备方法,具体步骤如下:
S1:首先将TiO2,Yb2O3,Er2O3按98.75:1:0.25的摩尔比混合均匀研磨,得到混合料;
S2:将S1所得材料在空气中1050℃保温10h,冷却至室温;
S3:将S2中得到的材料研磨、冷却,压成颗粒,得到TiO2:1%Yb, 0.25%ErUCL防伪荧光粉材料颗粒。
通过上述制备TiO2:Yb,ErUCL防伪荧光粉材料的方法制备的 TiO2:1%Yb,0.25%ErUCL防伪荧光粉材料可用于防伪领域。
实施例3
TiO2:Yb,ErUCL防伪荧光粉材料,化学成分为TiO2:x%Yb,y%Er,其中x=1,y=1。
TiO2:1Yb,1ErUCL防伪荧光粉材料的制备方法,具体步骤如下:
S1:首先将TiO2,Yb2O3,Er2O3按98:1:1的摩尔比混合均匀研磨,得到混合料;
S2:将S1所得材料在空气中1000℃保温5h,冷却至室温;
S3:将S2中得到的材料研磨、冷却,压成颗粒,得到TiO2:1%Yb, 1%ErUCL防伪荧光粉材料颗粒。
通过上述制备TiO2:Yb,ErUCL防伪荧光粉材料的方法制备的 TiO2:1%Yb,1%ErUCL防伪荧光粉材料可用于防伪领域。
如前所述,上述发明提供了本发明工作方式的具体细节。除了先前指定的实施例之外,本发明不限于这种方式。当应用于本领域的常规技术时,所呈现的方法和系统也可以在不偏离本发明的核心原理的情况下执行。为了满足当前和即将到来的工业技术时代的需要,可能会进行各种更改。
Claims (2)
1.一种TiO2:Yb,Er UCL防伪荧光粉材料,其化学式为TiO2:x%Yb,y%Er,其中x=0.1~1,y=0.1~1。
2.根据权利要求1所述一种TiO2:Yb,ErUCL防伪荧光粉材料,其特征在于,所述TiO2:Yb,ErUCL防伪荧光粉材料的制备方法包括以下步骤:
S1:首先将TiO2、Yb2O3、Er2O3按化学成分式的摩尔比混合均匀研磨;
S2:将步骤S1所得混合物在空气中1000~1200℃保温5~10h,冷却至室温;
S3:将S2得到的材料研磨,压成颗粒,得到TiO2:Yb,ErUCL防伪荧光粉材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111032233.6A CN113980679A (zh) | 2021-09-03 | 2021-09-03 | 一种TiO2:Yb,Er上转换发光防伪荧光粉的制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111032233.6A CN113980679A (zh) | 2021-09-03 | 2021-09-03 | 一种TiO2:Yb,Er上转换发光防伪荧光粉的制备和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113980679A true CN113980679A (zh) | 2022-01-28 |
Family
ID=79735336
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111032233.6A Pending CN113980679A (zh) | 2021-09-03 | 2021-09-03 | 一种TiO2:Yb,Er上转换发光防伪荧光粉的制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113980679A (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103045245A (zh) * | 2011-10-17 | 2013-04-17 | 海洋王照明科技股份有限公司 | 镨镱共掺杂二氧化钛上转换发光材料、制备方法及其应用 |
CN103397302A (zh) * | 2013-07-01 | 2013-11-20 | 复旦大学 | 一种上转换发光的Er/Yb共掺杂TiO2薄膜的制备方法 |
CN103571471A (zh) * | 2012-07-27 | 2014-02-12 | 海洋王照明科技股份有限公司 | 镝钬共掺杂二氧化钛上转换发光材料、制备方法及应用 |
CN104178151A (zh) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | 钐镱共掺杂二氧化钛上转换发光材料、制备方法及其应用 |
CN108192607A (zh) * | 2018-01-09 | 2018-06-22 | 南京大学 | 一种上转换强红光发射TiO2纳米材料的制备及应用 |
-
2021
- 2021-09-03 CN CN202111032233.6A patent/CN113980679A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103045245A (zh) * | 2011-10-17 | 2013-04-17 | 海洋王照明科技股份有限公司 | 镨镱共掺杂二氧化钛上转换发光材料、制备方法及其应用 |
CN103571471A (zh) * | 2012-07-27 | 2014-02-12 | 海洋王照明科技股份有限公司 | 镝钬共掺杂二氧化钛上转换发光材料、制备方法及应用 |
CN104178151A (zh) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | 钐镱共掺杂二氧化钛上转换发光材料、制备方法及其应用 |
CN103397302A (zh) * | 2013-07-01 | 2013-11-20 | 复旦大学 | 一种上转换发光的Er/Yb共掺杂TiO2薄膜的制备方法 |
CN108192607A (zh) * | 2018-01-09 | 2018-06-22 | 南京大学 | 一种上转换强红光发射TiO2纳米材料的制备及应用 |
Non-Patent Citations (2)
Title |
---|
刘丽静: "纳米Yb3+-Er3+/TiO2的制备及其在降解染料废水中的应用", 《四川大学学报(自然科学版)》 * |
董俊: "镱铒铥掺杂二氧化钛多晶的制备及上转换发光性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Shi et al. | Excitation wavelength-dependent dual-mode luminescence emission for dynamic multicolor anticounterfeiting | |
Zhang et al. | Self‐quenching‐resistant red emissive carbon dots with high stability for warm white light‐emitting diodes with a high color rendering index | |
Shi et al. | Highly efficient and thermally stable CaYMgSbO 6: Mn 4+ double perovskite red phosphor for indoor plant growth | |
Song et al. | RGB tricolor and multimodal dynamic optical information encryption and decoding for anti-counterfeiting applications | |
Li et al. | External-field-dependent tunable emissions of Er3+-In3+ Co-doped Cs2AgBiCl6 for applications in anti-counterfeiting | |
Jin et al. | Excitation wavelength-dependent multi-color emitting phosphor Ba2GdTaO6: Mn4+, Er3+ for application in anti-counterfeiting | |
Xiong et al. | Self‐activated persistent luminescence from Ba2Zr2Si3O12 for information storage | |
Lavanya et al. | One material, many possibilities via enrichment of luminescence in La2Zr2O7: Tb3+ nanophosphors for forensic stimuli aided applications | |
Wen et al. | Wide-range time-dependent color-tunable light-response afterglow materials via absorption compensation for advanced information encryption | |
Jin et al. | Dual-mode multicolor luminescence based on lanthanide-doped Na2CaGe2O6 phosphor for anticounterfeiting application | |
Girisha et al. | Stimuli-responsive color-tunable BaLa2ZnO5: Bi3+ phosphor for the encryption and authentication of security patterns and latent fingerprint detection | |
Liu et al. | An excitation wavelength-dependent color-tunable La4GeO8: Bi3+, Er3+ phosphor for multicolor anticounterfeiting | |
Singh et al. | Luminescence features of green-emitting CaLa4Si3O13: Ho3+ phosphors | |
Shi et al. | Variable halide perovskites: diversification of anti-counterfeiting applications | |
Pei et al. | Achieving mechano-upconversion-downshifting-afterglow multimodal luminescence in a lanthanide-doped LaCaAl3O7 phosphor for multidimensional anticounterfeiting | |
Shen et al. | Novel photo-responsive composite fibers fabricated by facile wet-spinning process for UV detection and high-level encryption | |
Shen et al. | Long-lived luminescence and photochromic cellulose acetate-based fiber: Preparation, characterization, and potential applications | |
Li et al. | Photomodulated cryogenic temperature sensing through a photochromic reaction in Na 0.5 Bi 2.5 Ta 2 O 9: Er/Yb multicolour upconversion | |
Kanmani et al. | A new Milarite type KMLS: Eu3+ orange-red-emitting phosphor for pc-white LEDs and Forensic applications | |
Chen et al. | NaYF4 upconversion crystals with red light emission by low Er3+ concentration doping | |
CN111484846A (zh) | 一种类变色龙稀土无机材料、其制备方法与其在荧光防伪中的应用 | |
Jiang et al. | Dynamic photoluminescent and photochromic properties of CaAl12O19: Eu, Tb: A novel phosphor for advanced dual-modal multicolor anticounterfeiting | |
He et al. | Eu3+ hypersensitive transition modulation: A novel red garnet phosphors with high color purity and excellent thermal stability | |
CN113980679A (zh) | 一种TiO2:Yb,Er上转换发光防伪荧光粉的制备和应用 | |
CN110066173B (zh) | 一种BaMgSiO4:Yb,Tb上转换发光防伪陶瓷材料、制备方法及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220128 |
|
RJ01 | Rejection of invention patent application after publication |