CN107415074A - A kind of gutta-percha for formed at normal temp processing and with the preparation method of elastomeric compound - Google Patents
A kind of gutta-percha for formed at normal temp processing and with the preparation method of elastomeric compound Download PDFInfo
- Publication number
- CN107415074A CN107415074A CN201710303543.4A CN201710303543A CN107415074A CN 107415074 A CN107415074 A CN 107415074A CN 201710303543 A CN201710303543 A CN 201710303543A CN 107415074 A CN107415074 A CN 107415074A
- Authority
- CN
- China
- Prior art keywords
- gutta
- percha
- rubber
- parts
- preparation
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A kind of gutta-percha for formed at normal temp processing and with the preparation method of elastomeric compound, is related to a kind of rubber-moulding processing method.Rubber is put into banbury, screw extruder or mill and plasticates and then the natural gum parked is mixed into 20 60 parts of carbon black, 30 80 parts of white carbon, 2 10 parts of plasticizer in the said equipment, rubber rubber master batch is made, parks 2 24 hours；Gutta-percha is put into banbury, screw extruder or mill to plasticate and add other compounding ingredients gutta-percha elastomeric compound is made；The bark of eucommia elastomeric compound and rubber rubber master batch do not parked while add in banbury or mill（Keep 35 DEG C of operations of low temperature 25 DEG C）It is kneaded uniformly, then slice.It is of the invention effectively to reduce gutta-percha and its blend compounds elastomeric compound hardness; increase gutta-percha and with the plasticity of elastomeric compound; ensure the plasticity for reaching normal elastomeric compound, be easy to the sequence of operations such as calendering under normal condition, extrusion and shaping, there is preferable actual application value.
Description
Technical field
The present invention relates to a kind of preparation method of elastomeric compound, more particularly to a kind of gutta-percha for formed at normal temp processing
And with the preparation method of elastomeric compound.
Background technology
The bark of eucommia is the distinctive industrial crops in China, contains abundant gutta percha in its plant（Trans-polyisoprene）
It is the isomer of natural rubber, gutta-percha is crystalline material at room temperature, and the characteristic of rigid plastics is shown under normal temperature,
Its heat distortion temperature Tm=60℃.It is of particular importance that there are three stage features in gutta percha, in sulfidation in non-friendship
It has thermoplastic property during connection.Gutta percha turns into a kind of thermoelastic with shape memory function during compared with low cross-linking degree
Property body.In high crosslinking degree as the elastomer of rubber-type.Therefore, the dosage of vulcanizing agent is controlled to be obtained with required intensity
Gutta percha.
Because the extraction process of gutta-percha is complicated, raw material dosage is big, the reasons such as yield is low, limits gutta percha and its answers
The use of condensation material.The method of traditional extraction gutta percha is to be combined with inorganic with organic solvent, and physics is mutually tied with chemical
Close, glue is leached out from shell and cured leaf, glue precipitation is separated by freezing.This method passes through raw material in advance
To cross and smash, alkali leaching, a small amount of toluene make collodion silk separate out, with solvent extraction, are precipitated out gutta-percha by freezing or distilling,
And substantial amounts of impurity not precipitating, it can so obtain purer gutta percha.It is smart glue further to be purified with acetone, is purified through acetone
Lily gutta-percha can be made.
Synthetic method industrially is taken, isoprene monomer is polymerize under catalyst action, obtains the poly- isoamyl of trans Isosorbide-5-Nitrae
Diene, i.e. TPI.
Gutta-percha particularly natural gutta-percha is the distinctive Novel glue kind of China, has preferable endurance, anti-aging
Feature, it is that can switch to elastomer after the technique such as crystalline state, crosslinked, chlorination, epoxidation and hydrogenation under normal temperature, can uses it for
The rubber products such as tire, conveyer belt, product, it is the following Novel rubber material up for further developing.
Due to crystallization property under the normal temperature of gutta-percha, it is set to be used alone and during with other rubber blendings, elastomeric compound is hard
Spend larger, it is difficult to processing and forming under normal temperature, therefore decline its hardness, it is necessary to improve forming temperature or the special technique of use,
And ensure that its physical property does not decline, there is significant meaning and value.
The content of the invention
It is an object of the invention to provide a kind of gutta-percha for formed at normal temp processing and with the preparation method of elastomeric compound,
Rubber is softened on the basis of not destroyed in process the invention enables rubber crystal property, its physical property not by
Influence, improve moulding processability, save mass energy.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of gutta-percha blend compounds for formed at normal temp processing, the gutta-percha and natural rubber, synthesis rubber
Glue and various auxiliary agents are kneaded uniformly, prepare the gutta-percha elastomeric compound that processing and forming can be carried out under normal temperature；Processing step is：
（1）Rubber is put into banbury, screw extruder or mill and plasticated（Normal temperature）10-20 minutes to bag roller, park 3-5
Hour, the natural gum parked is then mixed into carbon black 20-60 parts, white carbon 30-80 parts, plasticizer 2-10 in the said equipment
Part, rubber rubber master batch is made, parks 2-24 hours；
（2）Gutta-percha is put into banbury, screw extruder or mill and plasticated（Control 50 DEG C -70 DEG C of processing temperature）10-
To bag roller, zinc oxide 4-8 parts, stearic acid 2-5 parts, age resistor 2-4 parts, accelerator 1.2-2.6 are then sequentially added within 15 minutes
Part, sulphur 2.5-4 parts and other auxiliary agents 5-50 parts, treat that sizing material is sufficiently mixed and plasticate, gutta-percha elastomeric compound is made；
（3）The bark of eucommia elastomeric compound and rubber rubber master batch do not parked while add in banbury or mill（Keep low temperature 25 DEG C -35
DEG C operation）It is kneaded uniformly, then slice.
A kind of preparation method of described gutta-percha blend compounds for formed at normal temp processing, the gutta-percha are synthesis
（TPI）Or natural gutta-percha（EUG）, number-average molecular weight is in 10-50 ten thousand, molecular weight distributing index PI values 1.5-3；Natural gutta-percha
Leaf, skin and fruit in bark of eucommia plant stick up contained Gutta extraction thing.
A kind of preparation method of described gutta-percha blend compounds for formed at normal temp processing, other described rubber are natural
Rubber, butadiene-styrene rubber, butadiene rubber, isoprene rubber, neoprene, nitrile rubber, EP rubbers, butyl rubber, halobutyl
Rubber, tire reclaimed rubber.
A kind of preparation method of described gutta-percha blend compounds for formed at normal temp processing, the carbon black be N110,
One or more in N330, N339, N220, N324, N326, N375, N550, N660 are used in combination.
A kind of preparation method of described gutta-percha blend compounds for formed at normal temp processing, the age resistor are
One or more in 4010NA, 4020, H, RD, D are used in combination.
A kind of preparation method of described gutta-percha blend compounds for formed at normal temp processing, the step（1）In it is used
Auxiliary agent is pine tar, aromatic naphtha, naphthenic oil, white oil, machine oil, soybean oil, epoxidized soybean oil, pitch, rosin, paraffin, coumarone
Resin.
A kind of preparation method of described gutta-percha blend compounds for formed at normal temp processing, the accelerator be DZ, CZ,
M, the one or more in DM are used in combination.
Advantages of the present invention is with effect：
The present invention is processed using specialized processes so that rubber crystal property makes rubber on the basis of not destroyed in process
Soften, its physical property is not affected, and the shaping for substantially increasing raising tire under moulding processability, especially normal temperature adds
Work performance, improve process safety, save mass energy.
The present invention is being vulcanized by specialized processes change gutta-percha and the processing characteristics with other rubber, increase gutta-percha
Preceding plasticity, viscosity, in order to the sequence of operations such as roll, extrude and be molded, meanwhile, it is easy to filler in rubber mass
Acceleration disperse so that the processing characteristics and physical property of gutta-percha and other rubber blending glue are improved.
Feature of the present invention is that processing technology is simple, rubber master batch is first made using two kinds of glue kinds such as gutta-percha, then carry out low temperature and mix
Refining, saves the time.Elastomeric compound is good compared with conventional machining process gutta-percha elastomeric compound plasticity, is used directly for machine-shaping, section
Save the energy.
Embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment
（1）Natural rubber is put into mill and plasticated（Normal temperature）10-20 minutes to bag roller, park 3-5 hours, then will parked
Carbon black is added in good natural gum, plasticizer, caouttchouc rubber master batch is made.
（2）Gutta-percha is put into mill and plasticated（Control 50 DEG C -70 DEG C of processing temperature）10-15 minutes to bag roller, with
After sequentially add 4 parts of zinc oxide, 2 parts of stearic acid, 1.2 parts of 2 parts of 4010NA, NOBS, 2.5 parts of sulphur, treat that sizing material is sufficiently mixed
Plasticate, bark of eucommia elastomeric compound is made.
（3）Bark of eucommia elastomeric compound and caouttchouc rubber master batch are added in mill simultaneously（Normal temperature）, multiple triangle bag is beaten, directly
To being mixed, bottom sheet is parked.
（4）After elastomeric compound parks 24h, processing and forming can be carried out.
（5）Blend after plasticating is put into mould, press cure, curing temperature 150 are heated with vulcanizing press
DEG C, cure time is the time for measuring curing curve.
Embodiment：Utilize a kind of preparation method of the gutta-percha blend compounds for formed at normal temp processing.According to matching somebody with somebody as follows
Scheme is tested, and obtains the result of implementation of correlation.
Table 1：Embodiment 1 is formulated (phr)
Table 2：The physical property of the sample of embodiment 1
Table 3：The vulcanization characteristics of the sample of embodiment 1
Using institute's application method, tested according to following formula scheme.
Table 4：Embodiment 2 is formulated (phr)
Table 5：The physical property of the sample of embodiment 2
Table 6：The vulcanization characteristics of the sample of embodiment 2
。
Claims (8)
1. the preparation method of a kind of gutta-percha blend compounds for formed at normal temp processing, it is characterised in that the gutta-percha and day
T PNR, synthetic rubber and various auxiliary agents are kneaded uniformly, prepare the gutta-percha elastomeric compound that processing and forming can be carried out under normal temperature；Work
Skill step is：
（1）Blend rubber is put into banbury, screw extruder or mill and plasticated（Normal temperature）10-20 minutes to bag roller, stop
3-5 hours are put, the natural gum parked is then mixed into carbon black 20-60 parts, white carbon 30-80 parts, plasticising in the said equipment
Agent 2-10 parts, are made rubber rubber master batch, park 2-24 hours；
（2）Gutta-percha is put into banbury, screw extruder or mill and plasticated（Control 50 DEG C -70 DEG C of processing temperature）10-
To bag roller, zinc oxide 4-8 parts, stearic acid 2-5 parts, age resistor 2-4 parts, accelerator 1.2-2.6 are then sequentially added within 15 minutes
Part, sulphur 2.5-4 parts and other auxiliary agents 5-50 parts, treat that sizing material is sufficiently mixed and plasticate, gutta-percha elastomeric compound is made；
（3）The bark of eucommia elastomeric compound and rubber rubber master batch do not parked while add in banbury or mill（Keep low temperature 25 DEG C -35
DEG C operation）It is kneaded uniformly, then slice.
2. a kind of preparation method of gutta-percha blend compounds for formed at normal temp processing according to claim 1, its feature
It is, the gutta-percha is synthesis（TPI）Or natural gutta-percha（EUG）, in 10-50 ten thousand, molecular weight distribution refers to number-average molecular weight
Number PI values 1.5-3；Leaf, skin and the fruit that natural gutta-percha is derived from bark of eucommia plant stick up contained Gutta extraction thing.
3. a kind of preparation method of gutta-percha blend compounds for formed at normal temp processing according to claim 1, its feature
It is, the blend rubber is natural rubber, butadiene-styrene rubber, butadiene rubber, isoprene rubber, neoprene, nitrile rubber, second third
Rubber, butyl rubber, halogenated butyl rubber, tire reclaimed rubber.
4. a kind of preparation method of gutta-percha blend compounds for formed at normal temp processing according to claim 1, its feature
Be, the carbon black be in N110, N330, N339, N220, N324, N326, N375, N550, N660 it is one or more simultaneously
With.
5. a kind of preparation method of gutta-percha blend compounds for formed at normal temp processing according to claim 1, its feature
It is, the age resistor is that the one or more in 4010NA, 4020, H, RD, D are used in combination.
6. a kind of preparation method of gutta-percha blend compounds for formed at normal temp processing according to claim 1, its feature
It is, the step（1）In it is adjuvant used for pine tar, aromatic naphtha, naphthenic oil, white oil, machine oil, soybean oil, epoxidized soybean oil,
Pitch, rosin, paraffin, coumarone indene resin.
7. a kind of preparation method of gutta-percha blend compounds for formed at normal temp processing according to claim 1, its feature
It is, the accelerator is that the one or more in DZ, CZ, M, DM are used in combination.
8. a kind of preparation method of gutta-percha blend compounds for formed at normal temp processing according to claim 1, its feature
It is, other auxiliary agents are that the one or more of the inorganic fillers such as tackifier, antiscorching agent, calcium carbonate, clay are used in combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710303543.4A CN107415074B (en) | 2017-05-03 | 2017-05-03 | A kind of gutta-percha for formed at normal temp processing and with the preparation method of rubber compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710303543.4A CN107415074B (en) | 2017-05-03 | 2017-05-03 | A kind of gutta-percha for formed at normal temp processing and with the preparation method of rubber compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107415074A true CN107415074A (en) | 2017-12-01 |
| CN107415074B CN107415074B (en) | 2019-05-03 |
Family
ID=60425334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710303543.4A Active CN107415074B (en) | 2017-05-03 | 2017-05-03 | A kind of gutta-percha for formed at normal temp processing and with the preparation method of rubber compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107415074B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519342A (en) * | 2016-09-26 | 2017-03-22 | 沈阳化工大学 | Weather-resistant and salt-resistant gutta-percha/nitrile rubber blended vulcanized rubber and preparation method thereof |
| CN108794821A (en) * | 2018-06-07 | 2018-11-13 | 浙江环能传动科技有限公司 | A kind of method of plasticating of natural gum |
| CN113817239A (en) * | 2021-08-22 | 2021-12-21 | 茂泰(福建)鞋材有限公司 | Preparation method of modified biological calcium carbonate rubber outsole |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2047987A (en) * | 1935-06-17 | 1936-07-21 | Marbo Patents Inc | Low temperature preparation of rubber hydrohalides |
| CN101550245A (en) * | 2009-05-04 | 2009-10-07 | 杭州中策橡胶有限公司 | Tire compound composition using trans isoprene rubber and application thereof |
| CN103965405A (en) * | 2014-05-07 | 2014-08-06 | 沈阳化工大学 | Method for mixing and synthesizing modified gutta percha at room temperature |
| CN105801925A (en) * | 2016-04-12 | 2016-07-27 | 沈阳化工大学 | Natural and fatigue-resistant gutta-percha vulcanized rubber and preparation method thereof |
| CN105801924A (en) * | 2016-04-12 | 2016-07-27 | 沈阳化工大学 | Salt-fog-resistant natural or synthetic rubber and preparation method thereof |
| CN105906877A (en) * | 2016-04-23 | 2016-08-31 | 北京化工大学 | Gutta-percha masterbatch co-blended material capable of being directly used as traditional rubber material |
-
2017
- 2017-05-03 CN CN201710303543.4A patent/CN107415074B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2047987A (en) * | 1935-06-17 | 1936-07-21 | Marbo Patents Inc | Low temperature preparation of rubber hydrohalides |
| CN101550245A (en) * | 2009-05-04 | 2009-10-07 | 杭州中策橡胶有限公司 | Tire compound composition using trans isoprene rubber and application thereof |
| CN103965405A (en) * | 2014-05-07 | 2014-08-06 | 沈阳化工大学 | Method for mixing and synthesizing modified gutta percha at room temperature |
| CN105801925A (en) * | 2016-04-12 | 2016-07-27 | 沈阳化工大学 | Natural and fatigue-resistant gutta-percha vulcanized rubber and preparation method thereof |
| CN105801924A (en) * | 2016-04-12 | 2016-07-27 | 沈阳化工大学 | Salt-fog-resistant natural or synthetic rubber and preparation method thereof |
| CN105906877A (en) * | 2016-04-23 | 2016-08-31 | 北京化工大学 | Gutta-percha masterbatch co-blended material capable of being directly used as traditional rubber material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519342A (en) * | 2016-09-26 | 2017-03-22 | 沈阳化工大学 | Weather-resistant and salt-resistant gutta-percha/nitrile rubber blended vulcanized rubber and preparation method thereof |
| CN108794821A (en) * | 2018-06-07 | 2018-11-13 | 浙江环能传动科技有限公司 | A kind of method of plasticating of natural gum |
| CN113817239A (en) * | 2021-08-22 | 2021-12-21 | 茂泰(福建)鞋材有限公司 | Preparation method of modified biological calcium carbonate rubber outsole |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107415074B (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0445486B1 (en) | Polypropylene reinforced rubber | |
| CN101418087B (en) | Airtight rubber of all-steel radial tyre and preparation method thereof | |
| CN107415074B (en) | A kind of gutta-percha for formed at normal temp processing and with the preparation method of rubber compound | |
| CN105646959B (en) | A kind of rubber composition, preparation method and its application in 3D printing air core tyre | |
| CN103865122B (en) | Sidewall sizing material and preparation method thereof for tire | |
| CN107108966A (en) | Rubber composition and tire comprising sustainable resource and associated method | |
| EP2465898B1 (en) | Tire having rubber composition and a rubber component containing short fiber reinforcement with a comptabilizer | |
| AU2013267384B2 (en) | Tire tread and method of making the same | |
| EP3628702B1 (en) | Rubber composition and tire with tread | |
| CN108440807B (en) | Sole material and preparation method thereof | |
| EP3009472B1 (en) | Pre-formed apex/bead composite and tire with pre-apexed bead | |
| CN109735013A (en) | A kind of formula and preparation method thereof of tire curing bladder sizing material | |
| CN102189897A (en) | Tire having tread with an internal softer transition rubber layer containing short fiber reinforcement | |
| CN102977428A (en) | Method for preparing blend composite material by virtue of performing blending modification on kaolin/white carbon black | |
| CN1100084C (en) | Waste rubber regenerating process and waste rubber regenerant | |
| CN1013118B (en) | High-elastic rubber products gutta percha | |
| CN109503913B (en) | Inflation-free micro-foaming manpower vehicle tire raw material, inflation-free micro-foaming manpower vehicle tire and preparation method thereof | |
| CN108276622B (en) | Low-rolling-resistance tread inner liner rubber composition and application thereof | |
| CN110087906B (en) | Elastomeric composition for a tire component comprising natural rubber from guayule and tire comprising said tire component | |
| CN105802545B (en) | Half hot melt adhesive of motorcycle tyre and preparation method | |
| US7087660B2 (en) | Preparation of components and articles with directed high frequency energy heated silica-rich rubber components containing high softening point polymer and sulfur curative | |
| CN110684293A (en) | Preparation method of tire curing bladder | |
| CN102492188B (en) | Preparation method of composite material of eucommia ulmoides rubber and lignin | |
| CN110819015A (en) | Preparation method of tire vulcanization capsule containing modified gutta-percha | |
| CN103214702A (en) | Vacuum booster diaphragm |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |