CN103435973A - Halogen-free epoxy resin composition as well as prepreg and laminate made from same - Google Patents
Halogen-free epoxy resin composition as well as prepreg and laminate made from same Download PDFInfo
- Publication number
- CN103435973A CN103435973A CN2013104040111A CN201310404011A CN103435973A CN 103435973 A CN103435973 A CN 103435973A CN 2013104040111 A CN2013104040111 A CN 2013104040111A CN 201310404011 A CN201310404011 A CN 201310404011A CN 103435973 A CN103435973 A CN 103435973A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- halogen
- resin composition
- free epoxy
- prepreg
- 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
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a halogen-free epoxy resin composition. The halogen-free epoxy resin composition comprises the following ingredients in parts by solid weight: (a) 50-97 parts of epoxy resin; (b) 3-50 parts of curing agent; (c) 1-45 parts of phosphorus-containing flame retardant; (d) 0.05-1 part of imidazole accelerator; and (e) 0.1-10 parts of phenylboronic acid. According to the halogen-free epoxy resin composition, a resin system not only has good flame retardance, but also inhibits the reaction of a system at low temperature (below 170 DEG C) and accelerates the reaction at high temperature during copper clad laminate production, so that the production efficiency can be increased remarkably, and the product cost is reduced.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to a kind of halogen-free epoxy resin composition and use prepreg and the veneer sheet of its making.
Background technology
The implementing in full on July 1st, 2006 along with European RoHS and WEEE instruction (about restriction some objectionable impurities instruction of use in electrical and electronic product with about scrapping the electrical and electronic product instruction), the non-halogen of electronic product has been trend of the times, as the copper-clad plate (being veneer sheet) of baseplate material, stands in the breach.Traditional copper-clad plate material generally adopts brominated flame retardant (as brominated epoxy resin, tetrabromo-bisphenol etc.) to guarantee that flame retardant resistance reaches UL94 V-0 grade.But correlative study shows, during the bromide burning, can generate carcinogenic dioxin, serious harm HUMAN HEALTH, and contaminate environment.Therefore, in order to meet non-halogen requirement, need to seek a kind of brand-new and effective fire-retardant approach.
For the problems referred to above, the method generally adopted in industry is to substitute bromide fire retardant in the past with phosphorous epoxy resin, but its goods exist, the wicking thermotolerance is not enough, the easily moisture absorption, the moist problem such as rear wicking thermotolerance deficiency of processing.
On the other hand, epoxy resin refers to a family macromolecule compound that contains 2 or 2 above epoxy group(ing) in molecular structure.Because it has good processing performance, mechanical property, electrical property, physicals and relative cheap cost, for a long time in the application of printed wiring plate substrate in occupation of dominant position.And the up-to-date classification of the UL of industrial security certification authority is defined as the epoxy resin ratio by the composition of copper-clad plate FR-4 in advising need to be greater than 50%, has more strengthened the dominant position of epoxy resin in the copper-clad plate base material.In the PCB in copper-clad plate production and downstream produces, all require the solidification value of prepreg in the process of pressing sheet material low, set time is short, to enhance productivity, reduces product cost.This just need to contain the more promotor of high-content in the composition epoxy resin of making prepreg.Regrettably, simple increase accelerator level, not only can not accurately control curing reaction, and understand initial ring epoxy resins premature reaction and hold back solvent in prepreg making processes, make dissolvent residual in final copper-clad plate sheet material, thereby final performance is had a negative impact.
Therefore, develop a kind of good flame retardant resistance that not only has, and can accelerate the halogen-free environment-friendly type composition epoxy resin of curing reaction, there are market outlook.
Summary of the invention
The object of the invention is to provide a kind of halogen-free epoxy resin composition and uses prepreg and the veneer sheet of its making.
For achieving the above object, the technical solution used in the present invention is: a kind of halogen-free epoxy resin composition, with solid weight meter, comprising:
(a) epoxy resin: 50 ~ 97 parts;
(b) solidifying agent: 3 ~ 50 parts;
(c) phosphonium flame retardant: 1 ~ 45 part;
(d) imidazoles promotor: 0.05 ~ 1 part;
(e) phenylo boric acid: 0.1 ~ 10 part.
Above, the content range of described phenylo boric acid is 0.1 ~ 10 part, if surpass 10 parts, there will be solidifying agent excessive, and if the problem of the degradation such as the second-order transition temperature of sheet material, thermotolerance, lower than 0.1 part, is not just accelerated curing effect.
Simultaneously, above-mentioned composition can need to add the filler of 0 ~ 100 part according to practical application, and described filler is selected from one or more of aluminium hydroxide, magnesium hydroxide, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, calcium carbonate, clay, kaolin, glass powder, mica powder, titanium dioxide.
In technique scheme, described epoxy resin is selected from one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin.
In technique scheme, described solidifying agent is selected from one or more in Dyhard RU 100, line style phenolic aldehyde, phosphorus-containing phenolic aldehyde, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, diaminodiphenylmethane.
In technique scheme, described phosphonium flame retardant is selected from phosphazene compound, phosphate compound, 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, 10-(2, and the 5-dihydroxy phenyl)-one or more in 10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, phosphorous cyanate, phosphorous bismaleimides.
In technique scheme, described curing catalyst is selected from one or more in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyanoethyl-2 Methylimidazole.
In technique scheme, described phenylo boric acid is selected from 4-fluorobenzoic boric acid, 4-(trifluoromethyl) phenylo boric acid, 4-cyanophenylboronic acid, 4-formylphenylboronic acid, to one or more in methylphenylboronic acid, 4-(4-pyridyl) phenylo boric acid.
In technique scheme, the mol ratio of described curing catalyst and phenylo boric acid is 1:2 ~ 5.
The present invention asks for protection the prepreg of making as above-mentioned halogen-free epoxy resin composition simultaneously, and above-mentioned halogen-free epoxy resin composition is made to glue by dissolution with solvents, then strongthener is immersed in above-mentioned glue; After the strongthener baking, can obtain described prepreg after flooding.
Described solvent can be selected one or more the mixture in acetone, butanone, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described strongthener can adopt natural fiber, organic synthetic fibers, organic fabric or without woven fabrics.
The present invention asks for protection a kind of veneer sheet that adopts above-mentioned halogen-free epoxy resin composition to make simultaneously; be covered with tinsel at a single or double by above-mentioned prepreg; after perhaps at least 2 being superposeed by above-mentioned prepreg; be covered with tinsel at its single or double; compacting, can obtain described veneer sheet.
The quantity of described prepreg is to determine according to the veneer sheet thickness of customer requirement, available one or more.Described tinsel, can be Copper Foil, can be also aluminium foil, and their thickness is not particularly limited.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention has designed a kind of new compositions of thermosetting resin, utilize phosphorus boron cooperative flame retardant, when having reduced the phosphorus content in the epoxy-resin systems, the flame retardant resistance that has guaranteed epoxy-resin systems reaches UL94 V-0 grade, improve product moisture-resistant and thermotolerance simultaneously, and improved toughness and the processibility of product.
2. resin system of the present invention not only has good flame retardant resistance, and in copper-clad plate production process, the reaction of low temperature (below 170 ℃) inhibition system, accelerated reaction during high temperature, significantly faster production efficiency, reduce product cost.
3. the present invention has adopted phenylo boric acid as the boron source, meet environmental requirement, and because phenylo boric acid contains certain crosslinked action, and the chemical structure phenyl ring that contains rigidity, Tg to cured article also has certain help, and the thermotolerance of quick-setting goods is also unaffected.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
A kind of halogen-free epoxy resin composition, with solid weight meter, comprise following component, shown in seeing table:
Table 1 resin composition formula
Wherein, phosphorous epoxy resin, XZ92530, Dow Chemical production; Bisphenol A type epoxy resin, YDB128, Guktoh Chemical Co., Ltd. produces; Biphenyl type epoxy resin, NC-3000, Nippon Kayaku K. K produces; The trifunctional phenol-type epoxy resin, KDB1065, Guktoh Chemical Co., Ltd. produces; Dyhard RU 100, converge and chemical industry company limited in Qingdao; Lacquer resins, TD2091, Dainippon Ink Chemicals produces; Phosphorus containing phenolic resin, phosphorus modification class phenolic compound, XZ9271, Dow Chemical production; Phosphate compound, Guangzhou Zhen Yuanyang company limited; 2-ethyl-4-methylimidazole, glyoxal ethyline, Japanese four countries change into production; The 4-cyanophenylboronic acid, 4-formylphenylboronic acid, the emerging bio tech ltd in the foot of a hill or mountain, Changsha.
Table 2 is respectively the performance test that embodiment mono-to three and Comparative Examples one to four are carried out, and result is as shown in the table:
The performance data of table 2 embodiment mono-to five and Comparative Examples one to four
In table, the testing method of characteristic is as follows:
(1) glue gelation time (second): the gelation tester is set to l71 ± 0.5 ℃, 0.5 to 0.7mL glue is dripped on the heating plate of gelation tester, open timing register, an end of toothpick point is aimed to the surface of heating plate, with the circumferential motion agitating resin of diameter 10-13mm.During stirring, circumferential motion should make the resin of middle portion stir outer each time, and the resin of outer part stirs centre.Toothpick should contact with resin and curing panel surface always.When the resin retrogradation, will be not easy to make external resin and internal resin to be exchanged, but must continue to stir, in the situation that do not make toothpick stir the disconnected resin that makes as far as possible, exchanged.When the resin mass stirred separates with curing dish, stop immediately timing, this time is gel time.
(2) flame resistivity: (flame retardancy): measure according to the UL94 method.
(3) heat decomposition temperature Td: measure according to IPC-TM-650 2.4.26 method.
(4) thermal expansivity Z axis CTE (TMA): measure according to IPC-TM-650 2.4.24 method.
(5) wicking thermotolerance (second): use the two sides band copper sample of 50 * 50mm, immerse in the soldering of 288 ℃, record the time that the sample layering is bubbled.
(6) humidity resistance: after (base material of 100 * 100cm) sample is kept to 1 hour in 121 ℃, the pressure cooking treatment unit of 105kpa, record is immersed in the soldering groove of 288 ℃ certain hour and observes whether layering of sample, foaming.
(7) glass transition temperature Tg (℃): according to dsc, according to the DSC method of IPC-TM-650 2.4.25 defined, tested.
As seen from the above table, the glue system that composition epoxy resin of the present invention is made can guarantee suitable gelation time, is applicable to the complete processing of prepreg.The pressing process can be accelerated again to solidify, and in the short period, can make sheet material fully curing, can faster production efficiency in copper-clad plate and PCB pressing process, reduce production costs.And, because phenylo boric acid contains certain crosslinked action, and the chemical structure phenyl ring that contains rigidity, the Tg of cured article is also had to certain help, and the thermotolerance of quick-setting goods is also unaffected.
Claims (9)
1. a halogen-free epoxy resin composition, is characterized in that, with solid weight meter, comprising:
(a) epoxy resin: 50 ~ 97 parts;
(b) solidifying agent: 3 ~ 50 parts;
(c) phosphonium flame retardant: 1 ~ 45 part;
(d) imidazoles promotor: 0.05 ~ 1 part;
(e) phenylo boric acid: 0.1 ~ 10 part.
2. halogen-free epoxy resin composition according to claim 1, it is characterized in that: described epoxy resin is selected from one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin.
3. halogen-free epoxy resin composition according to claim 1, it is characterized in that: described solidifying agent is selected from one or more in Dyhard RU 100, line style phenolic aldehyde, phosphorus-containing phenolic aldehyde, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, diaminodiphenylmethane.
4. halogen-free epoxy resin composition according to claim 1, it is characterized in that: described phosphonium flame retardant is selected from phosphazene compound, phosphate compound, 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, 10-(2, and the 5-dihydroxy phenyl)-one or more in 10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, phosphorous cyanate, phosphorous bismaleimides.
5. halogen-free epoxy resin composition according to claim 1, it is characterized in that: described curing catalyst is selected from one or more in glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyanoethyl-2 Methylimidazole.
6. halogen-free epoxy resin composition according to claim 1 is characterized in that: described phenylo boric acid is selected from 4-fluorobenzoic boric acid, 4-(trifluoromethyl) phenylo boric acid, 4-cyanophenylboronic acid, 4-formylphenylboronic acid, to one or more in methylphenylboronic acid, 4-(4-pyridyl) phenylo boric acid.
7. halogen-free epoxy resin composition according to claim 1, it is characterized in that: the mol ratio of described curing catalyst and phenylo boric acid is 1:2 ~ 5.
8. a prepreg that adopts halogen-free epoxy resin composition as claimed in claim 1 to make, is characterized in that: halogen-free epoxy resin composition claimed in claim 1 is made to glue by dissolution with solvents, then strongthener is immersed in above-mentioned glue; After the strongthener baking, can obtain described prepreg after flooding.
9. a veneer sheet that adopts halogen-free epoxy resin composition as claimed in claim 1 to make, it is characterized in that: at a single or double by prepreg claimed in claim 8, be covered with tinsel, after perhaps at least 2 being superposeed by prepreg claimed in claim 8, be covered with tinsel at its single or double, compacting, can obtain described veneer sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310404011.1A CN103435973B (en) | 2013-09-06 | 2013-09-06 | A kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310404011.1A CN103435973B (en) | 2013-09-06 | 2013-09-06 | A kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103435973A true CN103435973A (en) | 2013-12-11 |
| CN103435973B CN103435973B (en) | 2016-03-23 |
Family
ID=49689699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310404011.1A Active CN103435973B (en) | 2013-09-06 | 2013-09-06 | A kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435973B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497493A (en) * | 2015-01-15 | 2015-04-08 | 江苏恒神纤维材料有限公司 | Formula for pollution-free organic fertilizer and preparation method thereof |
| CN105237950A (en) * | 2015-09-24 | 2016-01-13 | 苏州宽温电子科技有限公司 | Environmental-friendly halogen-free flame-retardant epoxy resin used for copper-clad plates, and preparation method thereof |
| CN105316936A (en) * | 2014-06-06 | 2016-02-10 | 泉州红瑞兴纺织有限公司 | Flame-retardant finishing agent and use thereof |
| CN106146803A (en) * | 2015-04-02 | 2016-11-23 | 南亚塑胶工业股份有限公司 | Low dielectric phosphor-containing flame-proof curing agent and application thereof |
| CN106496950A (en) * | 2016-11-11 | 2017-03-15 | 惠柏新材料科技（上海）股份有限公司 | A kind of low smoke combustion-proof epoxide resin composition |
| CN106832781A (en) * | 2017-02-17 | 2017-06-13 | 南通苏源化纤有限公司 | Novel nano high fire-retardance thermosetting resin based composites |
| CN109810504A (en) * | 2019-01-24 | 2019-05-28 | 江苏澳盛复合材料科技有限公司 | A kind of bismaleimide resin composition and its solidfied material and composite material |
| GB2568727A (en) * | 2017-11-24 | 2019-05-29 | Gurit Uk Ltd | Fire-retardant composite material |
| DE102019121195A1 (en) * | 2019-08-06 | 2021-02-11 | Alzchem Trostberg Gmbh | Storage-stable epoxy resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040063870A1 (en) * | 2000-07-13 | 2004-04-01 | Loctite (R&D) Ltd. | Curable epoxy-based compositions |
| CN102276959A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
-
2013
- 2013-09-06 CN CN201310404011.1A patent/CN103435973B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040063870A1 (en) * | 2000-07-13 | 2004-04-01 | Loctite (R&D) Ltd. | Curable epoxy-based compositions |
| CN102276959A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105316936A (en) * | 2014-06-06 | 2016-02-10 | 泉州红瑞兴纺织有限公司 | Flame-retardant finishing agent and use thereof |
| CN104497493A (en) * | 2015-01-15 | 2015-04-08 | 江苏恒神纤维材料有限公司 | Formula for pollution-free organic fertilizer and preparation method thereof |
| CN106146803A (en) * | 2015-04-02 | 2016-11-23 | 南亚塑胶工业股份有限公司 | Low dielectric phosphor-containing flame-proof curing agent and application thereof |
| CN106146803B (en) * | 2015-04-02 | 2019-09-27 | 南亚塑胶工业股份有限公司 | Low dielectric phosphor-containing flame-proof curing agent and its application |
| CN105237950A (en) * | 2015-09-24 | 2016-01-13 | 苏州宽温电子科技有限公司 | Environmental-friendly halogen-free flame-retardant epoxy resin used for copper-clad plates, and preparation method thereof |
| CN106496950A (en) * | 2016-11-11 | 2017-03-15 | 惠柏新材料科技（上海）股份有限公司 | A kind of low smoke combustion-proof epoxide resin composition |
| CN106832781A (en) * | 2017-02-17 | 2017-06-13 | 南通苏源化纤有限公司 | Novel nano high fire-retardance thermosetting resin based composites |
| GB2568727A (en) * | 2017-11-24 | 2019-05-29 | Gurit Uk Ltd | Fire-retardant composite material |
| GB2568727B (en) * | 2017-11-24 | 2020-06-24 | Gurit Uk Ltd | Fire-retardant composite materials |
| US11149126B2 (en) | 2017-11-24 | 2021-10-19 | Gurit (Uk) Ltd. | Fire-retardant composite materials |
| CN109810504A (en) * | 2019-01-24 | 2019-05-28 | 江苏澳盛复合材料科技有限公司 | A kind of bismaleimide resin composition and its solidfied material and composite material |
| DE102019121195A1 (en) * | 2019-08-06 | 2021-02-11 | Alzchem Trostberg Gmbh | Storage-stable epoxy resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103435973B (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435973B (en) | A kind of halogen-free epoxy resin composition and the prepreg using it to make and veneer sheet | |
| JP6470400B2 (en) | High CTI halogen-free epoxy resin composition for copper clad plate and method of using the same | |
| US9650512B2 (en) | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same | |
| CN103540101B (en) | Non-halogen resin composition and apply its copper clad laminate and printed circuit board (PCB) | |
| CN102504532B (en) | Halogen-free low dielectric resin composition and prepreg and copper clad laminate made of same | |
| CN102174242B (en) | Halogen-free resin composition and prepreg and laminated board made of same | |
| CN104177809A (en) | Low-dielectric halogen-free resin composition and application thereof | |
| EP2896653B1 (en) | Epoxy resin composition, and, prepreg and copper clad laminate manufactured using the composition | |
| CN102181143A (en) | High-frequency thermosetting resin composition, prepreg and laminated sheet | |
| CN103980704B (en) | Halogen-free resin composition, prepreg and laminate for high-frequency high-speed substrate | |
| EP2977405A1 (en) | Halogen-free resin composition, and prepreg and laminate for printed circuits using the same | |
| CN104974520A (en) | Halogen-free resin composition and application thereof | |
| CN102732029A (en) | Halogen-free resin composition, bonding sheet and copper-clad laminate | |
| CN103980708A (en) | Halogen-free flame-retardant thermosetting resin composition of integrated circuit, prepreg and laminate | |
| CN103013046B (en) | Halogen-free flame retardant resin composition and use thereof | |
| CN103992622A (en) | Halogen-free resin composition, prepreg prepared from halogen-free resin composition and laminated board prepared from halogen-free resin composition and used for printed circuit | |
| CN104804377A (en) | Halogen-free resin composition, and prepreg and laminated boards which are prepared from halogen-free resin composition | |
| CN103788580A (en) | Halogen-free benzoxazine resin composition and prepreg and laminated board prepared from same | |
| CN103965624A (en) | Halogen-free resin composition, and prepreg and laminated board prepared from same | |
| CN104109347A (en) | Halogen-free thermosetting resin composition, prepreg and laminated plate | |
| CN102051024B (en) | Halogen-free flame-retardant epoxy resin composition and application thereof | |
| TWI548667B (en) | A halogen-free thermosetting resin composition, and a prepreg for use and a laminate for printed circuit | |
| CN102432836B (en) | Halogen-free thermosetting resin composition and prepreg and laminated board manufactured by same | |
| CN103965588A (en) | Halogen-free thermosetting resin composition, prepreg and laminated board | |
| EP3040358B1 (en) | Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using the same |
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 |