CN104558622A - Modified amino silicone oil - Google Patents
Modified amino silicone oil Download PDFInfo
- Publication number
- CN104558622A CN104558622A CN201510040897.5A CN201510040897A CN104558622A CN 104558622 A CN104558622 A CN 104558622A CN 201510040897 A CN201510040897 A CN 201510040897A CN 104558622 A CN104558622 A CN 104558622A
- Authority
- CN
- China
- Prior art keywords
- silicon oil
- polyether
- modified amino
- coupling agent
- silane coupling
- 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
- 229920013822 aminosilicone Polymers 0.000 title abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000003921 oil Substances 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- -1 amido silicon Chemical compound 0.000 claims description 22
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical class [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- UXJQYGQJYYXQEV-UHFFFAOYSA-N 3-piperazin-1-ylpropylsilane Chemical group [SiH3]CCCN1CCNCC1 UXJQYGQJYYXQEV-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000004902 Softening Agent Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 241000322338 Loeseliastrum Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WWBITQUCWSFVNB-UHFFFAOYSA-N 3-silylpropan-1-amine Chemical compound NCCC[SiH3] WWBITQUCWSFVNB-UHFFFAOYSA-N 0.000 description 1
- 0 CN(*)C(*)[Si](C)[Si](C)O Chemical compound CN(*)C(*)[Si](C)[Si](C)O 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention discloses a modified amino silicone oil. A preparation method of the modified amino silicone oil comprises the following steps: (1) preparing an amino silicone oil: adding a lineament WS-62M, a silane coupling agent and KOH into a reactor in sequence, stirring uniformly, increasing the temperature of the reactor to 110-130 DEG C under the protection of nitrogen, carrying out reaction at a constant temperature for 4 hours, and removing low-boiling-point substances at the pressure of 60kPa to obtain the amino silicone oil; and (2) synthesizing the polyether modified amino silicone oil: adding the amino silicone oil, an active polyether and isopropanol into the reactor in sequence, stirring uniformly, increasing the temperature of the reactor to 80-90 DEG C, carrying out reaction at a constant temperature, and removing low-boiling-point substances at the pressure of 60kPa to obtain the polyether modified amino silicone oil.
Description
Technical field
The present invention relates to a kind of modified amino silicon oil.
Background technology
Softening agent refers to that one can be adsorbed in textile fiber surface, gives the textile auxiliary agent of its characteristic such as smooth, soft.
Silicone softening agent also claims silicone oil, refers to siloxane polymer and their derivative, is one of best flexibility post-finishing agent of the finishing effect of generally acknowledging at present.Compared with traditional non-silicon class softening agent, because Si-O key has the rotation free energy lower than C-O key, organopolysiloxane second-order transition temperature is lower, segment is more submissive, surface energy is little, can be as tough and tensile in fiber surface forms one deck at the material that surface energy is high, the continuous film that can stretch, the frictional coefficient of fiber surface is reduced, the easier relatively sliding of fiber under the effect of extraneous stress, thus make fabric have softness, level and smooth feel, good ventilation property, surface luster, wear-resisting, the characteristics such as snugness of fit, be applicable to different textiles (natural fibers, synthon, mixed fibre etc.) arrangement.Therefore, after 20 century 70s, along with the development of organosilicon chemistry, silicone softening agent has developed by leaps and bounds as a kind of novel polymer finishing composition, and between short decades, adopted by enterprise rapidly, widely, progressively instead of traditional non-silicon class softening agent, become the leading product in softening agent market.Account for the market of textiles soft finishing agent more than 90% at present.
Along with development and the growth in the living standard of society, people to the aspects such as attractive in appearance, fashion, the top grade of clothes require more and more higher while, also very high requirement is had to comfortable features of clothing and health, traditional silicone softening agent is difficult to take into account above-mentioned multi-functional requirement, therefore the synthesis of novel organosilicon softening agent becomes study hotspot, and the fabric of organosilicon post-finishing agent of processability excellence has great importance.
With existing technique synthesizing amino silicone oil, then carrying out hydrophilic modification to it is the most general thinking.And raw material octamethylcyclotetrasiloxane (D conventional at present
4) in usually with mixed methylcyclosiloxane D
3~ D
12deng impurity, this can cause amino skewness in product structure, detrimentally affect is had to use properties, and there is primary amine groups and secondary amino group in N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane coupling agent simultaneously, its collaborative accelerated oxidation effect makes the anti-yellowing change ability of product reduce.
Summary of the invention
The technical problem to be solved in the present invention improves the yellowing resistance energy of amido silicon oil.
The present invention is achieved through the following technical solutions:
A kind of modified amino silicon oil, chemical formula is as follows:
Wherein:
A preparation method for modified amino silicon oil, comprises the following steps:
1) amido silicon oil preparation: add linear body WS-62M, silane coupling agent and KOH successively in reactor, stir, after being warming up to 110 ~ 130 DEG C under nitrogen protection, isothermal reaction 4h, then obtains amido silicon oil after de-low-boiling-point substance under 60kPa condition;
2) synthesis of polyether-containing aminopolysiloxane: add amido silicon oil, active polyether and Virahol successively in reactor, stir, is warming up to 80 ~ 90 DEG C, isothermal reaction 4h, then under 60kPa condition, obtains polyether-containing aminopolysiloxane after de-low-boiling-point substance.
Further, the weight ratio of linear body WS-62M, silane coupling agent and KOH is 2 ~ 3:5 ~ 7:0.5 ~ 1.
Further, the weight ratio of amido silicon oil, active polyether and Virahol is 3 ~ 5:10 ~ 20:30 ~ 50.
Further, described silane coupling agent is 3-piperazinopropyl silane coupling agent or hexanaphthene amino silane coupling agent.
Compared with prior art, amido silicon oil provided by the invention is used for softening agent, and its yellowing resistance energy and softness make moderate progress.
Accompanying drawing explanation
Fig. 1 is that yellowing resistance can be schemed.
Fig. 2 is wetting ability performance map.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
1) in reactor, add linear body WS-62M, silane coupling agent and KOH successively, stir, after being warming up to 110 ~ 130 DEG C under nitrogen protection, isothermal reaction 4h, then obtains amido silicon oil after de-low-boiling-point substance under 60kPa condition;
2) synthesis of polyether-containing aminopolysiloxane: add amido silicon oil, active polyether and Virahol successively in reactor, stir, is warming up to 80 ~ 90 DEG C, isothermal reaction 4h, then under 60kPa condition, obtains polyether-containing aminopolysiloxane after de-low-boiling-point substance.
The weight ratio of linear body WS-62M, silane coupling agent and KOH is 2:5:0.5.
The weight ratio of amido silicon oil, active polyether and Virahol is 5:20:50.
Be coupling agent in order to YDH 602 (N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane).
Embodiment 2
1) in reactor, add linear body WS-62M, silane coupling agent and KOH successively, stir, after being warming up to 110 ~ 130 DEG C under nitrogen protection, isothermal reaction 4h, then obtains amido silicon oil after de-low-boiling-point substance under 60kPa condition;
2) synthesis of polyether-containing aminopolysiloxane: add amido silicon oil, active polyether and Virahol successively in reactor, stir, is warming up to 80 ~ 90 DEG C, isothermal reaction 4h, then under 60kPa condition, obtains polyether-containing aminopolysiloxane after de-low-boiling-point substance.
The weight ratio of linear body WS-62M, silane coupling agent and KOH is 3:7:1.
The weight ratio of amido silicon oil, active polyether and Virahol is 3:10:30.
In order to the polyether-containing aminopolysiloxane that γ-aminopropylsilane coupling agent prepares.
Embodiment 3
1) in reactor, add linear body WS-62M, silane coupling agent and KOH successively, stir, after being warming up to 110 ~ 130 DEG C under nitrogen protection, isothermal reaction 4h, then obtains amido silicon oil after de-low-boiling-point substance under 60kPa condition;
2) synthesis of polyether-containing aminopolysiloxane: add amido silicon oil, active polyether and Virahol successively in reactor, stir, is warming up to 80 ~ 90 DEG C, isothermal reaction 4h, then under 60kPa condition, obtains polyether-containing aminopolysiloxane after de-low-boiling-point substance.
The weight ratio of linear body WS-62M, silane coupling agent and KOH is 3:5:1.
The weight ratio of amido silicon oil, active polyether and Virahol is 3:10:50.
In order to the polyether-containing aminopolysiloxane that 3-piperazinopropyl silane coupling agent prepares.
Embodiment 4
In reactor, add linear body WS-62M, silane coupling agent and KOH successively, stir, after being warming up to 110 ~ 130 DEG C under nitrogen protection, isothermal reaction 4h, then obtains amido silicon oil after de-low-boiling-point substance under 60kPa condition;
2) synthesis of polyether-containing aminopolysiloxane: add amido silicon oil, active polyether and Virahol successively in reactor, stir, is warming up to 80 ~ 90 DEG C, isothermal reaction 4h, then under 60kPa condition, obtains polyether-containing aminopolysiloxane after de-low-boiling-point substance.
The weight ratio of linear body WS-62M, silane coupling agent and KOH is 3:5:1.
The weight ratio of amido silicon oil, active polyether and Virahol is 3:10:50.
In order to the polyether-containing aminopolysiloxane that hexanaphthene amino silane coupling agent prepares.
Embodiment 5
Get the polyether-containing aminopolysiloxane 30g of 2.2.3.1 synthesis, by acetic acid titration adjust ph to 7, slowly to add water for 20 times self-emulsifying at agitation condition, obtain the silicon emulsion that concentration is 30%.Then get 3 parts of silicon emulsions to add in 97 parts of water and stir, obtain Final finishing working fluid.
Impregnated in Final finishing working fluid by under cotton calico normal temperature, small-sized padding machine one soaks one and rolls, pick-up about 70%, 180 DEG C × 200s drying and shaping.
Cloth specimen after arranging at room temperature is placed one week, then temperature be 20 DEG C ± 5 DEG C, relative humidity carries out performance test after placing 24h under being the condition of 65% ± 2%.
Yellowing resistance can measure: every one side of fabric is got 4 different some SBDY-1 type digital display whiteness instrument and test, totally eight times, get its mean value, compare the difference of the average whiteness of calico before and after process.Measurement result as shown in Figure 1.
Wetting ability measures: adopt water droplet penetration method, namely use standard dropper (25/ml) to drip water from the fabric face sprawled from the height of fabric 2cm to level, measure fabric under quiescent conditions and absorbed 1 and drip (water is no-reflection on fabric) time used.Test result as shown in Figure 2.
All simple distortion of making when not departing from core of the present invention or amendment all fall into protection scope of the present invention.
Claims (5)
1. a modified amino silicon oil, is characterized in that,
Wherein:
2. a preparation method for modified amino silicon oil, is characterized in that, comprises the following steps:
1) amido silicon oil preparation: add linear body WS-62M, silane coupling agent and KOH successively in reactor, stir, after being warming up to 110 ~ 130 DEG C under nitrogen protection, isothermal reaction 4h, then obtains amido silicon oil after de-low-boiling-point substance under 60kPa condition;
2) synthesis of polyether-containing aminopolysiloxane: add amido silicon oil, active polyether and Virahol successively in reactor, stir, is warming up to 80 ~ 90 DEG C, isothermal reaction 4h, then under 60kPa condition, obtains polyether-containing aminopolysiloxane after de-low-boiling-point substance.
3. the preparation method of a kind of modified amino silicon oil according to claim 2, is characterized in that, the weight ratio of linear body WS-62M, silane coupling agent and KOH is 2 ~ 3:5 ~ 7:0.5 ~ 1.
4. the preparation method of a kind of modified amino silicon oil according to claim 2, is characterized in that, the weight ratio of amido silicon oil, active polyether and Virahol is 3 ~ 5:10 ~ 20:30 ~ 50.
5. the preparation method of a kind of modified amino silicon oil according to claim 2, is characterized in that, described silane coupling agent is 3-piperazinopropyl silane coupling agent or hexanaphthene amino silane coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510040897.5A CN104558622A (en) | 2015-01-27 | 2015-01-27 | Modified amino silicone oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510040897.5A CN104558622A (en) | 2015-01-27 | 2015-01-27 | Modified amino silicone oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104558622A true CN104558622A (en) | 2015-04-29 |
Family
ID=53075754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510040897.5A Pending CN104558622A (en) | 2015-01-27 | 2015-01-27 | Modified amino silicone oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558622A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367974A (en) * | 2016-08-29 | 2017-02-01 | 枣阳市金鹏化工有限公司 | Softening agent containing amino silicone oil and preparation method thereof |
| CN107163841A (en) * | 2017-07-12 | 2017-09-15 | 合肥轻风飏电气科技有限责任公司 | It is a kind of to be used for the antirust paint of machinery |
| CN108484918A (en) * | 2018-03-23 | 2018-09-04 | 江苏宇道生物科技有限公司 | A kind of novel silicon polymeric system and preparation method thereof |
| CN109608643A (en) * | 2018-12-15 | 2019-04-12 | 广东传化富联精细化工有限公司 | A kind of organosilicon crude oil, siliceous stiffening agent and preparation method thereof |
| CN109666115A (en) * | 2017-10-16 | 2019-04-23 | 万华化学集团股份有限公司 | A kind of amino-silane terminated modified polyurethane resin and preparation method thereof |
-
2015
- 2015-01-27 CN CN201510040897.5A patent/CN104558622A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 章莹: "有机硅柔软剂的改性研究", 《中国优秀硕士学位论文全文数据库（电子期刊），工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367974A (en) * | 2016-08-29 | 2017-02-01 | 枣阳市金鹏化工有限公司 | Softening agent containing amino silicone oil and preparation method thereof |
| CN107163841A (en) * | 2017-07-12 | 2017-09-15 | 合肥轻风飏电气科技有限责任公司 | It is a kind of to be used for the antirust paint of machinery |
| CN109666115A (en) * | 2017-10-16 | 2019-04-23 | 万华化学集团股份有限公司 | A kind of amino-silane terminated modified polyurethane resin and preparation method thereof |
| CN108484918A (en) * | 2018-03-23 | 2018-09-04 | 江苏宇道生物科技有限公司 | A kind of novel silicon polymeric system and preparation method thereof |
| CN108484918B (en) * | 2018-03-23 | 2021-03-30 | 多恩生物科技有限公司 | Novel silicon polymer system and preparation method thereof |
| CN109608643A (en) * | 2018-12-15 | 2019-04-12 | 广东传化富联精细化工有限公司 | A kind of organosilicon crude oil, siliceous stiffening agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086779B (en) | Sliding block silicone oil of a kind of ultra-soft and preparation method thereof | |
| CN101497697B (en) | Preparation of block water-soluble silicon oil | |
| CN104558622A (en) | Modified amino silicone oil | |
| CN101914206B (en) | Quaternized modified amino silicone oil softener and preparation and application thereof | |
| CN102549046B (en) | Novel polysiloxanes having quaternary ammonium groups and use thereof | |
| CN102206921B (en) | Polyether block amino silicone softening finishing agent, its preparation method and application | |
| CN107129578B (en) | Preparation method of amino modified silicone oil finishing agent with net structure | |
| CN101418518A (en) | Method for preparing durable hydrophilic polyether modified amino polysiloxane soft agent | |
| CN104672460B (en) | Polyether block piperazine silicone oil, preparation method and its application in Cotton Fabric | |
| CN105755837B (en) | A kind of preparation method of quaternised modified amino-silicone oil softener and application | |
| CN103193981B (en) | A kind of hydrophilic amido silicon oil and its production and use | |
| CN103333339B (en) | A kind of hydroxy-end capped phenyl amino polyether modified silicon oil | |
| CN102644200B (en) | Super-soft finishing agent of silicone oil | |
| CN110656500B (en) | Non-silicon type hydrophilic softening agent and preparation method and application thereof | |
| CN105694046A (en) | Preparation method of highly-branched block polyether-aminosiloxane finishing agent | |
| CN106750324A (en) | A kind of poly- quaternary ammonium polyethers dimethyl silicone polymer and preparation method thereof and hand feel finishing agent | |
| CN111877020B (en) | Modified silicone oil softening agent and preparation method thereof | |
| CN104628990B (en) | It is a kind of to play silicone oil, preparation method and applications for the sliding of textile | |
| CN102660029B (en) | Cation modified supersoft hydrophilic block silicone oil compound and preparation method and application | |
| CN103193984A (en) | Hydrophilic aminosilicon oil, and preparation method and uses thereof | |
| CN112726211A (en) | Preparation method of polyurethane modified organic silicon softening agent | |
| CN103741490B (en) | Textile shuttle-woven fabric anti tear finishing agent and preparation method | |
| CN113651961A (en) | Modified organosilicon waterproofing agent and preparation method thereof | |
| CN111286987B (en) | Organic silicon quaternary ammonium salt fabric finishing agent based on block silicone oil and preparation method thereof | |
| CN105274851B (en) | Durable, antistatic and dustproof finishing agent for flocking fabrics and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150429 |