CN101709063A - Organosilicon compound containing amino groups - Google Patents
Organosilicon compound containing amino groups Download PDFInfo
- Publication number
- CN101709063A CN101709063A CN200910198615A CN200910198615A CN101709063A CN 101709063 A CN101709063 A CN 101709063A CN 200910198615 A CN200910198615 A CN 200910198615A CN 200910198615 A CN200910198615 A CN 200910198615A CN 101709063 A CN101709063 A CN 101709063A
- Authority
- CN
- China
- Prior art keywords
- formula
- silicone oil
- pigment
- compound containing
- amino groups
- 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
Images
Landscapes
- Cosmetics (AREA)
Abstract
The invention relates to an organosilicon compound containing amino groups, which is used for dispersing pigment granules of cosmetics. The organosilicon compound containing amino groups is obtained by modifying the traditional organosilicon compounds by secondary amine. Experiments prove that the organosilicon compound containing amino groups, which is designed and prepared in the invention, can be used as a pigment dispersing agent of cosmetics, and lessenes the grain diameter of the pigment granules while improving the dispersity of pigment, thereby enabling the arrangement of the granules to be more compact, enhancing the refractive index and enabling the cosmetics to have high glossiness.
Description
Technical field
The present invention relates to a kind of silicoorganic compound, particularly a kind of makeup dispersed color particulate that is used for contains the amido organosilicon compound.
Background technology
In general, grease used in the makeup all belongs to lipophilicity substance, and its effect is to make makeup have moisture retention.And in some makeup (as color make-up), except grease,, also comprise pigment in the prescription in order to reach different effects (as painted).Yet granules of pigments can not be dissolved in the medium usually, also is not easy to be dispersed at the bottom of the fat-based or in the carrier, in order to obtain stable prescription, often need with dispersion agent make granules of pigments stable be dispersed in grease mutually in.
Can be used for makeup dispersed color particulate silicoorganic compound at present mainly contains: Methyl Hydrogen Polysiloxane Fluid and polydimethylsiloxane.When the former is used for handling pigment, can make pigment have high water-repellancy, thereby improve the persistence of makeup cosmetic, but shortcoming is the pigment handled with containing hydrogen silicone oil, its Si-H key also is present in the molecule, may discharge hydrogen after for some time, this in addition containing hydrogen silicone oil is not suitable for handles temperature-sensitive pigments such as iron oxide yellow and Prussian blue.Though and the shortcoming of appearance can avoid handling for the pigment that latter's polydimethylsiloxane is handled the time with containing hydrogen silicone oil, but owing to lack reactive group in the polydimethylsiloxane molecule, be difficult at low temperatures be adsorbed on the surface of pigments, if and elevated temperature, greatly in the time of 200~350 ℃, autohemagglutination will take place in polydimethylsiloxane, just can not bring into play its advantage.
EP 1 103 581 has reported a kind of silicoorganic compound through the fluoro-containing group modification, though these silicoorganic compound have overcome the defective that above-mentioned Methyl Hydrogen Polysiloxane Fluid and polydimethylsiloxane exist during granules of pigments in disperseing makeup, but the preparation cost of fluorine-containing silicoorganic compound is higher, and its application is subjected to certain restriction.
Summary of the invention
The objective of the invention is to, provide a kind of preparation cost lower and can be used for disperseing the silicoorganic compound of makeup granules of pigments.
Its main chain of silicoorganic compound is made up of the softish siloxane bond; in medium, can fully stretch; to guarantee that being dispersed in the granules of pigments surface forms enough thick protective layer; simultaneously on its side chain, can connect some anchoring groups; by interactions such as ionic linkage, covalent linkage, hydrogen bond and Van der Waals forces; tightly be adsorbed on the granules of pigments, prevent the dispersion agent desorption.According to such structure, when the granules of pigments that is adsorbed with dispersion agent interacts because of Van der Waals force, flick mutually, thereby realize the stable dispersion of particle in non-aqueous media owing to the spatial obstacle between the adsorption layer makes particle.In addition, silicoorganic compound also have lower surface tension, can reduce the surface tension between particle and the medium when organosilicon is adsorbed on the granules of pigments surface, thereby has better wettability.
In view of the above, contriver's design has also prepared a kind of amino silicoorganic compound that contain, experimental results show that: the silicoorganic compound that contain amino of the present invention's design and preparation can be as the cosmetic pigment dispersion agent, this compound is when improving pigment-dispersing, the granules of pigments particle diameter diminishes, thereby can make between the particle and to arrange closelyr, improve refractive index, therefore can make makeup have high glossiness.
Silicoorganic compound of the present invention have structure shown in the formula (1):
In the formula (1): R
1And R
2Be selected from respectively in H, alkyl or the substituted alkyl a kind of, the substituting group in the wherein said substituted alkyl be hydroxyl (OH) or/and group shown in the formula (2):
In the formula (2): R
3And R
4Be selected from H or C respectively
1~C
6A kind of in the alkyl; n
1(mean polymerisation degree) is 10~200; n
2(mean polymerisation degree) is 1~50.
In optimized technical scheme of the present invention, R
1And R
2Be selected from C respectively
1~C
20The C of alkyl or replacement
1~C
6A kind of in the alkyl, the C of said replacement wherein
1~C
6Substituting group in the alkyl be hydroxyl (OH) or group shown in the formula (2); R
3And R
4Be selected from H or C respectively
1~C
6A kind of in the alkyl;
Best R
1And R
2Be selected from respectively: CH
3CH
2-, HOCH
2CH
2-, CH
3(CH
2)
16CH
2-or (CH
3)
2NCH
2CH
2CH
2-in a kind of.
In another optimized technical scheme of the present invention, n
1(mean polymerisation degree) is 10~100.
In a further preferred technical solution of the present invention, n
2(mean polymerisation degree) is 3~20.
The said silicoorganic compound that contain amino of the present invention, it is at first by containing hydrogen silicone oil and glycidyl allyl ether reaction, and products therefrom obtains target product [compound shown in the formula (1)] with secondary amine [its structure is as the formula (3)] reaction again.
In the formula (3): R
1And R
2Implication described identical with preamble, do not repeat them here.Synthetic route is as follows:
Description of drawings
Fig. 1 is: through the distribution plan of compound dispersive dispersion particle diameters shown in the formula (1a)~(1e).
Embodiment
A kind ofly prepare the method that contains amino silicoorganic compound of the present invention, comprise the steps:
(1) (mol ratio 1 of containing hydrogen silicone oil and glycidyl allyl ether wherein: (1~2) places reactor in required ratio with containing hydrogen silicone oil, glycidyl allyl ether and solvent, under the condition that catalyzer and rare gas element (as nitrogen etc.) exist, reaction system is warming up to 60 ℃~80 ℃, and under this temperature, kept at least 4 hours, cooling, steaming desolventize the back and add amount of methanol, leave standstill, remove the impurity phase, get intermediate [compound shown in the formula (4)]:
Wherein said catalyzer is that concentration is the aqueous isopropanol of the Platinic chloride of 1.0wt%, and catalyst consumption is 0.05%~0.10% of a reactant gross weight.
(2) will place reactor by prepared intermediate of step (1) [compound shown in the formula (4)] and solvent, under the condition that rare gas element (as nitrogen etc.) exists, compound shown in the formula (3) is added drop-wise to [the compound mol ratio is 1 shown in intermediate and the formula (3): (1~3)] in the reactor, controlled temperature is between 20 ℃~70 ℃, reaction times was at least 8 hours, cooling, revolve to steam and remove an amount of normal hexane of back adding that desolvates, leave standstill, remove the impurity phase, get target product [compound shown in the formula (1)].
The silicoorganic compound that contain amino of the present invention's design and preparation can be as makeup (as lipstick) pigment dispersing agent, this compound is when improving pigment-dispersing, the granules of pigments particle diameter diminishes, thereby can make between the particle arrange tightr, improve refractive index, therefore can make makeup (as lipstick) have high glossiness.After tested, the refractive index that contains amino silicoorganic compound of the present invention's design and preparation is 1.45 (refractive index of used silicone oil is 1.41 in the general makeup).
The present invention is further illustrated below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention.
Embodiment 1
Structure is suc as formula the preparation of the silicoorganic compound shown in (1a):
(1) with the 120g glycidyl allyl ether; 193g toluene and 0.15g catalyzer: the aqueous isopropanol of Platinic chloride (massfraction is 1.0%) is put into there-necked flask; under nitrogen protection, be heated to 70 ℃; splash into the containing hydrogen silicone oil of 193g; react decompression afterwards in 6 hours and steam solvent and low-boiling-point substance; add an amount of methanol wash, leave standstill and remove the impurity phase, obtain epoxide modified silicone oil.
(2) 20g is added in the there-necked flask by epoxide modified silicone oil and the tetrahydrofuran (THF) that step (1) makes; under nitrogen protection, drip the N of 2.7g, N-dimethyl-1,3-propylene diamine; controlled temperature reacted 8 hours about 30 ℃, got amino-modified silicone [compound shown in the formula (1a)].n
1Be 10, n
2Be 20
IR (pressed disc method): 3358.19 (s, υ N-H), 2960~2863 (s, υ C-H), 1575 (w, δ N-H), 1468 (w, δ C-H), 1260 (s, δ Si-C), 1088~1022 (s, υ Si-O), 802 (s, υ Si-C).
1H-NMR (CDCl
3) (ppm): δ 0.08 (SiCH
3, aH), 0.14 (SiCH
3, bH), 1.3~1.5 (SiCH
2CH
2, cH and dH), 4.74~5.41 (SiCH2CH
2CH
2O, eH), 3.52 (OCH
2, fH), 3.78~4.01 (OCH
2CH, gH), 2.0 (OH, hH), 2.70~2.85 (OCH
2CHCH
2, iH), 1.96~2.00 (NH, jH), 2.51~3.77 (NHCH
2, kH), 1.51~1.57 (NHCH
2CH
2, lH), 2.36~3.35 (NHCH
2CH
2CH
2, mH), 2.27 (N (CH
3)
2, nH).
Embodiment 2
Structure is suc as formula the preparation of the silicoorganic compound shown in (1b):
(1) with the 120g glycidyl allyl ether; 193g toluene and 0.15g catalyzer: the aqueous isopropanol of Platinic chloride (massfraction is 1.0%) is put into there-necked flask; under nitrogen protection, be heated to 70 ℃; splash into the containing hydrogen silicone oil of 193g; react decompression afterwards in 6 hours and steam solvent and low-boiling-point substance; add an amount of methanol wash, leave standstill and remove the impurity phase, obtain epoxide modified silicone oil.
(2) 20g is added in the there-necked flask by epoxide modified silicone oil and the tetrahydrofuran (THF) that step (1) makes, drip the 1.8g diethylamine under nitrogen protection, controlled temperature reacted 8 hours about 30 ℃, got amino-modified silicone [compound shown in the formula (1b)].n
1Be 100, n
2Be 5
1H-NMR (CDCl
3) (ppm): δ 0.08 (SiCH
3, aH), 0.14 (SiCH
3, bH), 1.3~1.5 (SiCH
2CH
2, cH and dH), 3.37 (SiCH2CH
2CH
2O, eH), 3.52 (OCH
2, fH), 3.78 (OCH
2CH, gH), 2.0 (OH, hH), 2.51 (OCH
2CHCH
2, iH), 2.40 (NCH
2, jH), 1.00 (NCH
2CH
2, kH)
Embodiment 3
Structure is suc as formula the preparation of the silicoorganic compound shown in (1c):
(1) with the 120g glycidyl allyl ether; 193g toluene and 0.15g catalyzer: the aqueous isopropanol of Platinic chloride (massfraction is 1.0%) is put into there-necked flask; under nitrogen protection, be heated to 70 ℃; splash into the containing hydrogen silicone oil of 193g; react decompression afterwards in 6 hours and steam solvent and low-boiling-point substance; add an amount of methanol wash, leave standstill and remove the impurity phase, obtain epoxide modified silicone oil.
(2) 20g is added in the there-necked flask by epoxide modified silicone oil and the tetrahydrofuran (THF) that step (1) makes, drip the 2.6g di-alcohol under nitrogen protection, controlled temperature reacted 8 hours about 30 ℃, got amino-modified silicone [compound shown in the formula (1c)].n
1Be 200, n
2Be 1.
1H-NMR (CDCl
3) (ppm): δ 0.08 (SiCH
3, aH), 0.14 (SiCH
3, bH), 1.3~1.5 (SiCH
2CH
2, cH and dH), 3.37 (SiCH2CH
2CH
2O, eH), 3.52 (OCH
2, fH), 3.78 (OCH
2CH, gH), 2.0 (OH, hH), 2.51 (OCH
2CHCH
2, iH), 2.40 (NCH
2, jH), 1.00 (NCH
2CH
2, kH)
Embodiment 4
Structure is suc as formula the preparation of the silicoorganic compound shown in (1d):
(1) with the 120g glycidyl allyl ether; 193g toluene and 0.15g catalyzer: the aqueous isopropanol of Platinic chloride (massfraction is 1.0%) is put into there-necked flask; under nitrogen protection, be heated to 70 ℃; splash into the containing hydrogen silicone oil of 193g; react decompression afterwards in 6 hours and steam solvent and low-boiling-point substance; add an amount of methanol wash, leave standstill and remove the impurity phase, obtain epoxide modified silicone oil.
(2) 20g is added in the there-necked flask by epoxide modified silicone oil and the tetrahydrofuran (THF) that step (1) makes, drip the two stearylamines of 12.9g under nitrogen protection, controlled temperature reacted 8 hours about 30 ℃, got amino-modified silicone [compound shown in the formula (1d)].n
1Be 40, n
2Be 10.
1H-NMR (CDCl
3) (ppm): δ 0.08 (SiCH
3, aH), 0.14 (SiCH
3, bH), 1.3~1.5 (SiCH
2CH
2, cH and dH), 3.37 (SiCH2CH
2CH
2O, eH), 3.52 (OCH
2, fH), 3.78 (OCH
2CH, gH), 2.0 (OH, hH), 2.51 (OCH
2CHCH
2, iH), 2.40 (NCH
2, jH), 1.41 (NCH
2CH
2, kH), 1.29 (NCH
2CH
2CH
2, 1H), 1.33 (CH
2CH
3, mH), 0.96 (CH
3, nH)
Embodiment 5
Structure is suc as formula the preparation of the silicoorganic compound shown in (1e):
(1) with the 120g glycidyl allyl ether; 193g toluene and 0.15g catalyzer: the aqueous isopropanol of Platinic chloride (massfraction is 1.0%) is put into there-necked flask; under nitrogen protection, be heated to 70 ℃; splash into the containing hydrogen silicone oil of 193g; react decompression afterwards in 6 hours and steam solvent and low-boiling-point substance; add an amount of methanol wash, leave standstill and remove the impurity phase, obtain epoxide modified silicone oil.
(2) 20g is added in the there-necked flask by epoxide modified silicone oil and the tetrahydrofuran (THF) that step (1) makes; under nitrogen protection, drip 4.6g N; N-tetramethyl-dipropylenetriamine, controlled temperature reacted 8 hours about 30 ℃, got amino-modified silicone [compound shown in the formula (1e)].n
1Be 45, n
2Be 9.
1H-NMR (CDCl
3) (ppm): δ 0.08 (SiCH
3, aH), 0.14 (SiCH
3, bH), 1.3~1.5 (SiCH
2CH
2, cH and dH), 3.37 (SiCH2CH
2CH
2O, eH), 3.52 (OCH
2, fH), 3.78 (OCH
2CH, gH), 2.0 (OH, hH), 2.51 (OCH
2CHCH
2, iH), 2.40 (NCH
2, jH), 1.51 (NCH
2CH
2, kH), 2.36 (NCH
2CH
2CH
2, 1H), 2.27 (NCH
3, mH).
Embodiment 6
(1) dispersion stabilization experiment
Compound shown in 0.01 part of formula (1a), formula (1b), formula (1c), formula (1d) and the formula (1e) is dissolved in 10 parts of ethanol separately, under the violent stirring, add 0.1 part of PR57:1 (technical grade respectively, the Zhejiang lily chemical industry group that controls interest) dry powder, behind the ultrasonic 30min, left standstill 24 hours, 1cm place below liquid level separately, draw 0.5ml liquid respectively, be diluted to 5ml respectively, with UV 755B spectrophotometric determination transmitance T, with the transmitance numerical evaluation dispersion stabilization (DE%) of maximum absorption wave strong point, calculating formula is as follows:
DE%=(1-T) * 100% the results are shown in table 1.
Table 1
DD5562 is the makeup silicone oil (for commodity silicone oil) that DOW CORNING (DOWCORNING) provides in the table 1
(2) granules of pigments particle diameter test
Be dissolved in 10 parts of ethanol with 0.01 part separately by compound shown in formula (1a), formula (1b), formula (1c), formula (1d) and the formula (1e), under the violent stirring, add 0.1 part of PR57:1 (technical grade respectively, the Zhejiang lily chemical industry group that controls interest) dry powder, behind the ultrasonic 30min, dispersion particle diameters is measured with Mastersizer 2000 particle size analyzers.The result is as shown in Figure 1:
Embodiment 7~8
Lipstick in the present embodiment is made by following method.
Grease, wax class are added in the container that is provided with heating and mixing device, be heated between 85~95 ℃, make material dissolution and uniform mixing, in another container, pigment and dispersed grease dispersed with stirring are added in the grease wax after evenly again, after mixing, be filled in the lipstick mould and cooling fast, the demoulding then makes the finished product lipstick.The amido silicon oil and the commodity silicone oil of preparation are used for the lipstick prescription and compare.Concrete prescription is as shown in table 2:
Table 2
In the table 2: DC5562 and organosilicon wax are purchased the company in DOWCORNING; T.I.O, SALACOS DT-38, COSMOL222, COSMOL 168ARV, these greases of COSMOL 43V are purchased the company in KALIN; Grease FLORASUN 90 and 791 purchases the company in FLORATECH; Grease CORUM 5041 purchases the company in CORUM.
More as shown in table 3 according to lipstick outward appearance and performance that above two Example formulations are prepared:
Table 3
Claims (6)
1. silicoorganic compound, it has structure shown in the formula (1):
In the formula (1): R
1And R
2Be selected from H, alkyl or the substituted alkyl a kind ofly respectively, the substituting group in the wherein said substituted alkyl is a hydroxyl or/and group shown in the formula (2), n
1Be 10~200; n
2Be 1~50;
In the formula (2): R
3And R
4Be selected from H or C respectively
1~C
6A kind of in the alkyl.
2. silicoorganic compound as claimed in claim 1 is characterized in that, wherein R
1And R
2Be selected from C respectively
1~C
20The C of alkyl or replacement
1~C
6A kind of in the alkyl, the C of said replacement wherein
1~C
6Substituting group in the alkyl is a group shown in hydroxyl or the formula (2); R wherein
3And R
4Be selected from H or C respectively
1~C
6A kind of in the alkyl.
3. silicoorganic compound as claimed in claim 1 is characterized in that n
1Be 10~100.
4. silicoorganic compound as claimed in claim 1 is characterized in that n
2Be 3~20.
5. as any described silicoorganic compound in the claim 1~4, it is characterized in that, wherein R
1And R
2Be selected from respectively: CH
3CH
2-, HOCH
2CH
2-, CH
3(CH
2)
16CH
2-or (CH
3)
2NCH
2CH
2CH
2-in a kind of.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009101986159A CN101709063B (en) | 2009-11-11 | 2009-11-11 | Organosilicon compound containing amino groups |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009101986159A CN101709063B (en) | 2009-11-11 | 2009-11-11 | Organosilicon compound containing amino groups |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101709063A true CN101709063A (en) | 2010-05-19 |
CN101709063B CN101709063B (en) | 2011-11-30 |
Family
ID=42401874
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2009101986159A Active CN101709063B (en) | 2009-11-11 | 2009-11-11 | Organosilicon compound containing amino groups |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101709063B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102295771A (en) * | 2011-05-13 | 2011-12-28 | 华东理工大学 | Hyperbranched polymer as well as modified substance thereof and application of modified substance |
CN109796798A (en) * | 2019-01-25 | 2019-05-24 | 红河学院 | A kind of water-soluble etching pigment with mimeograph effect |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2726562B1 (en) * | 1994-11-08 | 1996-12-27 | Oreal | NOVEL SOLAR FILTERS, PHOTOPROTECTIVE COSMETIC COMPOSITIONS CONTAINING THEM AND USES THEREOF |
DE10320631A1 (en) * | 2003-05-08 | 2004-12-09 | Wacker-Chemie Gmbh | Organosilicon compounds containing polyalkoxy radicals |
CN100556909C (en) * | 2007-09-14 | 2009-11-04 | 华东理工大学 | Contain silica chain silicoorganic compound and uses thereof |
-
2009
- 2009-11-11 CN CN2009101986159A patent/CN101709063B/en active Active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102295771A (en) * | 2011-05-13 | 2011-12-28 | 华东理工大学 | Hyperbranched polymer as well as modified substance thereof and application of modified substance |
CN102295771B (en) * | 2011-05-13 | 2013-01-09 | 华东理工大学 | Hyperbranched polymer as well as modified substance thereof and application of modified substance |
CN109796798A (en) * | 2019-01-25 | 2019-05-24 | 红河学院 | A kind of water-soluble etching pigment with mimeograph effect |
Also Published As
Publication number | Publication date |
---|---|
CN101709063B (en) | 2011-11-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Shea et al. | Arylsilsesquioxane gels and related materials. New hybrids of organic and inorganic networks | |
Uhlig et al. | 29 Si NMR Some Practical Aspects | |
JP5983490B2 (en) | Method for producing silica particles | |
US6887518B2 (en) | Silica with homogeneous layer of silylating agent | |
KR101190923B1 (en) | Organofunctional silicone resin layers on metal oxides | |
CN101862620A (en) | The emulsifying agent that comprises the organopolysiloxane of glycerine-modification | |
TW201430013A (en) | Copolysilsesquioxane microspheres, the preparing method and the application thereof | |
CN103347889A (en) | Hydrosilylation catalyst | |
Cabrera-González et al. | Redox-Active Metallacarborane-Decorated Octasilsesquioxanes. Electrochemical and Thermal Properties | |
CN102286220A (en) | Method for preparing hydrophobic precipitated silicon dioxide | |
KR20130114157A (en) | Copolymers containing polysiloxane groups and having an epoxy/amine skeletal structure, and use thereof | |
CN101709063B (en) | Organosilicon compound containing amino groups | |
EP3237548A1 (en) | Multifunctional coated powders and high solids dispersions | |
CN109988311A (en) | A kind of poly- silicon oxygen silazane and preparation method thereof | |
Lu et al. | Preparation and characterization of organic–inorganic hybrid composites based on multiepoxy silsesquioxane and cyanate resin | |
EP3153518B1 (en) | Mono-functional branched organosiloxane compound and method for producing the same | |
Kawahara et al. | Dendritic, Nanosized Building Block for Siloxane‐Based Materials: A Spherosilicate Dendrimer | |
CN106633076A (en) | Organic silicone elastomer gel and preparation method thereof | |
CN109467095B (en) | Method for modifying surface of high-dispersion fumed silica by using substance with high carbon content | |
Zeng et al. | Poly (ethylene imine) hybrids containing polyhedral oligomeric silsesquioxanes: Preparation, structure and properties | |
CN106170872A (en) | High index of refraction Organic silicon nano composite material | |
JP2019183110A (en) | Composition for forming water-repellent film, and water-repellent film | |
WO2015118158A1 (en) | Surface treatment | |
Arkhireeva et al. | Preparation of Silsesquioxane Particles via a Nonhydrolytic Sol− Gel Route | |
Barczak et al. | Structure-adsorption properties of ethylene-bridged polysilsesquioxanes and polysiloxanes functionalized with different groups |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |