CN107163473A - A kind of preparation method and applications of environment-friendly type non-bittern combustion inhibitor - Google Patents
A kind of preparation method and applications of environment-friendly type non-bittern combustion inhibitor Download PDFInfo
- Publication number
- CN107163473A CN107163473A CN201710403261.1A CN201710403261A CN107163473A CN 107163473 A CN107163473 A CN 107163473A CN 201710403261 A CN201710403261 A CN 201710403261A CN 107163473 A CN107163473 A CN 107163473A
- Authority
- CN
- China
- Prior art keywords
- preparation
- environment
- parts
- friendly type
- type non
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A kind of preparation method and applications of environment-friendly type non-bittern combustion inhibitor, belong to technical field of flame retardant.The preparation method comprises the following steps：By lubricant, SiO2, poly- aryl ethane resin, magnesium hydroxide and coupling agent disperse in ammonia spirit, stir；By the mixture heating after stirring, electric heating synthesis is carried out after pressurization；After the completion of reaction, by distillation dehydration, reactant is cooled down standby；Epoxy hardener is added into the reactant after cooling；It is dried after the completion of reaction to be solidified, is crushed to Subnano-class, obtains final products.Fire retardant prepared by the present invention, Halogen, without antimony environment-friendly high-efficiency, without pernicious gas, electrical conductivity is superior, is 45 ~ 55nS/cm, is suitable for the processing of electronic apparatus plastic packaging material, beneficial to environment, formaldehydeless, heavy metal component, all raw materials can reclaim cyclic process and use.Good with resin compatible, impact strength is good.High temperature resistant is up to 500 DEG C ~ 600 DEG C, and ageing-resistant performance is strong.
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of preparation method of environment-friendly type non-bittern combustion inhibitor and its should
With.
Background technology
Fire retardant, is a kind of functional aid, combustible polymers can be made fire retardant, primarily directed to the resistance of high polymer material
Combustion design, fire retardant has polytype, is divided into additive flame retardant and reactive flame retardant by application method.Addition property is fire-retardant
Agent is to be added to by the method for mechanical mixture in polymer, polymer is possessed anti-flammability, and addition fire retardant mainly has at present
Organic fire-retardant and inorganic combustion inhibitor, halogenated flame retardant and non-halogen fire retardant.Organic fire-retardant is with bromine system, phosphorus nitrogen system and red phosphorus
And compound is some fire retardants of representative, inorganic combustion inhibitor is mainly the fire retardants such as the antimony of tri-chlorination two, aluminium hydroxide, silicon systems
System.Reactive flame retardant is then to participate in polymerisation as a kind of monomer, polymer is contained flame-retardant composition in itself, its advantage is
Performance influence on polymeric material is smaller, and anti-flammability is lasting.
Red phosphorus is a kind of preferable fire retardant in non-halogen fire retardant, with addition is few, flame retarding efficiency is high and low cigarette,
Low toxicity, it is widely used the advantages of；The inorganic combustion inhibitor compounding use such as red phosphorus and aluminium hydroxide, expansile graphite, is made compound
Phosphorus/magnesium；Phosphorus/aluminium；The non-halogen fire retardants such as phosphorus/graphite, can make amount of flame-retardant agent decline to a great extent, so as to improve the processing of plastic products
Performance and material resources mechanical performance.But common red phosphorus is oxidizable in atmosphere, moisture absorption, easily cause dust explosion, transport difficult,
With the defect such as high polymer material poor compatibility, application is restricted.
The defect that the preparation technology of existing halogen-free flame retardants is present：（1）Preparation process is complicated, and cost is high；（2）Finished product is stable
Property is poor, and with high polymer material poor compatibility, electrical conductivity is higher, loss of properties on aging.
The content of the invention
The technical problem of solution：For above-mentioned technical problem, the present invention provides a kind of environment-friendly type non-bittern combustion inhibitor and its should
With, compared with bromide fire retardant, this product is more environmentally-friendly, and electrical conductivity is superior, good with high polymer material compatibility, and impact strength is good,
Preparation process is simple, and cost is relatively low.
Technical scheme：A kind of preparation method of environment-friendly type non-bittern combustion inhibitor, the preparation method comprises the following steps：
（1）By weight, by 0.1 ~ 2 part of lubricant, 0.1 ~ 5 part of SiO2, 15 ~ 33 parts of poly- aryl ethane resin, 5 ~ 20 parts of hydrogen
Magnesia and 1 ~ 3 part of coupling agent are dispersed in 55 ~ 80 parts of mass concentrations in 30% ~ 60% ammonia spirit, to stir；
（2）Mixture after stirring is heated to 170 ~ 250 DEG C, electric heating is synthesized under 0.05 ~ 1.5MPa, reacts 60 ~ 90 min；
（3）After the completion of reaction, by distillation dehydration, by reactant be cooled to 70 ~ 80 DEG C it is standby；
（4）To step（3）1 ~ 2.5 part by weight of epoxy hardener, solidification 90 ~ 120 are added in reactant after cooling
min；
（5）It is dried after the completion of reaction to be solidified, is crushed to Subnano-class, obtains final products.
Preferably, the step（1）By weight, by 1 part of lubricant, 2 parts of SiO2, 20 parts of poly- aryl ethane trees
Fat, 15 parts of magnesium hydroxides and 2 parts of coupling agents are dispersed in 65 parts of mass concentrations in 45% ammonia spirit.
Preferably, the step（1）Middle lubricant is stearic acid, zinc stearate or calcium stearate.
Preferably, the step（1）Middle coupling agent is silane coupler ZQ-560 or Silane coupling agent KH550.
Preferably, the step（2）Mixture after stirring is heated to 200 DEG C, electric heating is synthesized under 0.9 MPa,
React 80 min.
Preferably, the step（3）Reactant is cooled to 80 DEG C.
Preferably, the step（4）It is middle to step（3）2 parts by weight of ring is added in reactant after cooling
Oxygen curing agent, solidifies 90 min.
Preferably, the step（4）Middle epoxy hardener is epoxy curing agent or epoxy polyamide curing agent.
Another of the invention technical scheme be the preparation method epoxy resin, unsaturated-resin, electronics plastic packaging material and
Application during rail locomotive housing is flame-retardant modified.
Beneficial effect：Fire retardant prepared by the present invention, Halogen, without antimony environment-friendly high-efficiency, without pernicious gas, electrical conductivity is excellent
More, it is 45 ~ 55nS/cm, is suitable for the processing of electronic apparatus plastic packaging material, beneficial to environment, formaldehydeless, heavy metal component, all raw materials
Cyclic process can be reclaimed to use.Good with resin compatible, impact strength is good.High temperature resistant is resistance to old up to 500 DEG C ~ 600 DEG C
Change performance strong.
Embodiment
Embodiment 1
A kind of preparation method of environment-friendly type non-bittern combustion inhibitor, the preparation method comprises the following steps：
（1）By weight, by 0.1 part of lubricant, 0.1 part of SiO2, 15 parts of poly- aryl ethane resins, 5 parts of magnesium hydroxides and 1 part
Coupling agent is dispersed in 55 parts of mass concentrations in 30% ammonia spirit, to stir；
（2）Mixture after stirring is heated to 170 DEG C, electric heating is synthesized under 0.05 MPa, reacts 60 min；
（3）After the completion of reaction, by distillation dehydration, by reactant be cooled to 70 DEG C it is standby；
（4）To step（3）1 part by weight of epoxy hardener is added in reactant after cooling, solidifies 90 min；
（5）It is dried after the completion of reaction to be solidified, is crushed to Subnano-class, obtains final products.
Wherein lubricant is stearic acid, and coupling agent is silane coupler ZQ-560, and epoxy hardener is epoxy resin cure
Agent.
Fire retardant prepared by the present invention, Halogen, without antimony environment-friendly high-efficiency, without pernicious gas, electrical conductivity is superior, is 55nS/
Cm, is suitable for the processing of electronic apparatus plastic packaging material, beneficial to environment, formaldehydeless, heavy metal component, all raw materials can reclaim circulation
Processing is used.Good with resin compatible, impact strength is good.High temperature resistant is up to more than 500 DEG C, and ageing-resistant performance is strong.
Embodiment 2
A kind of preparation method of environment-friendly type non-bittern combustion inhibitor, the preparation method comprises the following steps：
（1）By weight, by 2 parts of lubricants, 5 parts of SiO2, 33 parts of poly- aryl ethane resin, 20 parts of magnesium hydroxides and 3 parts of idols
Connection agent is dispersed in 80 parts of mass concentrations in 60% ammonia spirit, to stir；
（2）Mixture after stirring is heated to 250 DEG C, electric heating is synthesized under 1.5 MPa, reacts 90 min；
（3）After the completion of reaction, by distillation dehydration, by reactant be cooled to 80 DEG C it is standby；
（4）To step（3）2.5 parts by weight of epoxy hardener is added in reactant after cooling, solidifies 120 min；
（5）It is dried after the completion of reaction to be solidified, is crushed to Subnano-class, obtains final products.
Wherein lubricant is zinc stearate, and coupling agent is Silane coupling agent KH550, and epoxy hardener is solid for epoxy polyamide
Agent.
Fire retardant prepared by the present invention, Halogen, without antimony environment-friendly high-efficiency, without pernicious gas, electrical conductivity is superior, is 50 nS/
Cm, is suitable for the processing of electronic apparatus plastic packaging material, beneficial to environment, formaldehydeless, heavy metal component, all raw materials can reclaim circulation
Processing is used.Good with resin compatible, impact strength is good.High temperature resistant is up to more than 580 DEG C, and ageing-resistant performance is strong.
Embodiment 3
A kind of preparation method of environment-friendly type non-bittern combustion inhibitor, the preparation method comprises the following steps：
（1）By weight, by 1 part of lubricant, 2 parts of SiO2, 20 parts of poly- aryl ethane resin, 15 parts of magnesium hydroxides and 2 parts of idols
Connection agent is dispersed in 65 parts of mass concentrations in 45% ammonia spirit, to stir；
（2）Mixture after stirring is heated to 200 DEG C, electric heating is synthesized under 0.9 MPa, reacts 80 min；
（3）After the completion of reaction, by distillation dehydration, by reactant be cooled to 80 DEG C it is standby；
（4）To step（3）2 parts by weight of epoxy hardener is added in reactant after cooling, solidifies 90 min；
（5）It is dried after the completion of reaction to be solidified, is crushed to Subnano-class, obtains final products.
Wherein lubricant is calcium stearate, and coupling agent is silane coupler ZQ-560, and epoxy hardener is epoxy polyamide
Curing agent.
Fire retardant prepared by the present invention, Halogen, without antimony environment-friendly high-efficiency, without pernicious gas, electrical conductivity is superior, is 45 nS/
Cm, is suitable for the processing of electronic apparatus plastic packaging material, beneficial to environment, formaldehydeless, heavy metal component, all raw materials can reclaim circulation
Processing is used.Good with resin compatible, impact strength is good.High temperature resistant is up to more than 600 DEG C, and ageing-resistant performance is strong.
Comparative example 1
By step described in embodiment 3（1）By weight, make into 1 part of lubricant, 2 parts of SiO2, 15 parts of magnesium hydroxides and 2 parts
Coupling agent is dispersed in 85 parts of mass concentrations in 45% ammonia spirit, to stir.Remaining step is constant.
After testing, the nS/cm of electrical conductivity 60, good with resin compatible, impact strength is good, and high temperature resistant is up to more than 400 DEG C.
Claims (9)
1. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor, it is characterised in that the preparation method comprises the following steps：
（1）By weight, by 0.1 ~ 2 part of lubricant, 0.1 ~ 5 part of SiO2, 15 ~ 33 parts of poly- aryl ethane resin, 5 ~ 20 parts of hydrogen-oxygens
Change magnesium and 1 ~ 3 part of coupling agent is dispersed in 55 ~ 80 parts of mass concentrations in 30% ~ 60% ammonia spirit, to stir；
（2）Mixture after stirring is heated to 170 ~ 250 DEG C, electric heating is synthesized under 0.05 ~ 1.5MPa, reacts 60 ~ 90 min；
（3）After the completion of reaction, by distillation dehydration, by reactant be cooled to 70 ~ 80 DEG C it is standby；
（4）To step（3）1 ~ 2.5 part by weight of epoxy hardener, solidification 90 ~ 120 are added in reactant after cooling
min；
（5）It is dried after the completion of reaction to be solidified, is crushed to Subnano-class, obtains final products.
2. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor according to claim 1, it is characterised in that the step
（1）By weight, by 1 part of lubricant, 2 parts of SiO2, 20 parts of poly- aryl ethane resin, 15 parts of magnesium hydroxides and 2 parts of coupling agents
65 parts of mass concentrations are dispersed in in 45% ammonia spirit.
3. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor according to claim 1, it is characterised in that the step
（1）Middle lubricant is stearic acid, zinc stearate or calcium stearate.
4. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor according to claim 1, it is characterised in that the step
（1）Middle coupling agent is silane coupler ZQ-560 or Silane coupling agent KH550.
5. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor according to claim 1, it is characterised in that the step
（2）Mixture after stirring is heated to 200 DEG C, electric heating is synthesized under 0.9 MPa, reacts 80 min.
6. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor according to claim 1, it is characterised in that the step
（3）Reactant is cooled to 80 DEG C.
7. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor according to claim 1, it is characterised in that the step
（4）It is middle to step（3）2 parts by weight of epoxy hardener is added in reactant after cooling, solidifies 90 min.
8. a kind of preparation method of environment-friendly type non-bittern combustion inhibitor according to claim 1 or 7, it is characterised in that the step
Suddenly（4）Middle epoxy hardener is epoxy curing agent or epoxy polyamide curing agent.
9. based on preparation method described in claim 1 in epoxy resin, unsaturated-resin, electronics plastic packaging material and rail locomotive housing
Application in flame-retardant modified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710403261.1A CN107163473A (en) | 2017-06-01 | 2017-06-01 | A kind of preparation method and applications of environment-friendly type non-bittern combustion inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710403261.1A CN107163473A (en) | 2017-06-01 | 2017-06-01 | A kind of preparation method and applications of environment-friendly type non-bittern combustion inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107163473A true CN107163473A (en) | 2017-09-15 |
Family
ID=59821202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710403261.1A Pending CN107163473A (en) | 2017-06-01 | 2017-06-01 | A kind of preparation method and applications of environment-friendly type non-bittern combustion inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107163473A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736450A (en) * | 2022-03-10 | 2022-07-12 | 金发科技股份有限公司 | High-thermal-shrinkage-resistance and high-toughness thermo-oxidative-aging-resistance polyolefin material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814697A (en) * | 2006-02-21 | 2006-08-09 | 南通瑞森科技合成材料有限公司 | Sub-nano silica-magnesia whisker halogen-less flame-retardant agent |
| CN101851399A (en) * | 2009-03-30 | 2010-10-06 | 山东兴强阻燃科技有限公司 | Halogen-free flame retardant polyester product and preparation method thereof |
| CN105198926A (en) * | 2015-09-29 | 2015-12-30 | 上海应用技术学院 | Halogen-free reactive phosphorus/silicon synergistic flame retardant and preparation method thereof |
| CN105295049A (en) * | 2015-12-04 | 2016-02-03 | 江苏涌新材料科技有限公司 | Halogen-free environment-friendly synergistic organic silicon flame retardant, flame retardant composition as well as preparation method and application of synergistic organic silicon flame retardant |
| CN106380788A (en) * | 2016-10-24 | 2017-02-08 | 西华大学 | Halogen-free flame retardant, halogen-free flame-retarding epoxy resin and preparation method thereof |
-
2017
- 2017-06-01 CN CN201710403261.1A patent/CN107163473A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814697A (en) * | 2006-02-21 | 2006-08-09 | 南通瑞森科技合成材料有限公司 | Sub-nano silica-magnesia whisker halogen-less flame-retardant agent |
| CN101851399A (en) * | 2009-03-30 | 2010-10-06 | 山东兴强阻燃科技有限公司 | Halogen-free flame retardant polyester product and preparation method thereof |
| CN105198926A (en) * | 2015-09-29 | 2015-12-30 | 上海应用技术学院 | Halogen-free reactive phosphorus/silicon synergistic flame retardant and preparation method thereof |
| CN105295049A (en) * | 2015-12-04 | 2016-02-03 | 江苏涌新材料科技有限公司 | Halogen-free environment-friendly synergistic organic silicon flame retardant, flame retardant composition as well as preparation method and application of synergistic organic silicon flame retardant |
| CN106380788A (en) * | 2016-10-24 | 2017-02-08 | 西华大学 | Halogen-free flame retardant, halogen-free flame-retarding epoxy resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736450A (en) * | 2022-03-10 | 2022-07-12 | 金发科技股份有限公司 | High-thermal-shrinkage-resistance and high-toughness thermo-oxidative-aging-resistance polyolefin material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103819666B (en) | High flame retardant nylon resin and its preparation method | |
| CN104448702B (en) | Halogen-free resin composition as well as prepreg and laminated board made of halogen-free resin composition | |
| PH26191A (en) | Moulding composition comprising a thermoset component and thermoplast component | |
| CN103435887A (en) | High-fluidity low-smoke zero-halogen flame retardant polyolefin composite and preparation method thereof | |
| CN111004501A (en) | Modified bio-based nylon 56 material and preparation method and application thereof | |
| CN111278884B (en) | Composition for curing resin, cured product of the composition, method for producing the composition and the cured product, and semiconductor device | |
| CN107778638B (en) | Halogen-free flame-retardant ultra-high molecular weight polyethylene material and preparation method thereof | |
| CN110092905B (en) | Preparation method and application of cast nylon/black phosphorus flame-retardant composite material | |
| CN109438976B (en) | Copolymerized nylon product and preparation method thereof | |
| CN108912169B (en) | Compound di- (4-aminophenyl) phenylphosphonate and synthesis method thereof | |
| WO2013056411A1 (en) | Epoxy resin composition and prepreg and copper clad laminate manufactured by using the same | |
| JPH0624715A (en) | Filler for heat-conductive plastic material | |
| CN105131449A (en) | Expanded antiflaming environment-friendly polystyrene | |
| WO2004080897A1 (en) | Heat-resistant aluminum hydroxide and method for preparation thereof | |
| CN107163473A (en) | A kind of preparation method and applications of environment-friendly type non-bittern combustion inhibitor | |
| US5364914A (en) | Moulding composition comprising a thermoset component and thermoplast component | |
| Gao et al. | Property of intrinsic flame retardant epoxy resin cured by functional magnesium organic composite salt and diethylenetriamine | |
| CN113348195A (en) | Resin composition and method for producing same | |
| CN108441153A (en) | A kind of high-performance epoxy resin base electron pouring sealant and its preparation process | |
| CN111117109B (en) | Silica gel-like soft heat-resistant PVC and preparation method thereof | |
| CN102061072A (en) | Environment-friendly halogen-free non-phosphorus flame-retardant polycarbonate resin composition | |
| CN108084660B (en) | A kind of expansion type fire retarding epoxide resin and preparation method thereof | |
| CN114350113B (en) | Flame-retardant epoxy resin, preparation method and application | |
| CN108409916A (en) | A kind of preparation method of LSOH anti-flaming unsaturated polyester resin composite material | |
| CN107163474A (en) | A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170915 |