CN102492222A - Polypropylene/fiberglass composite material and preparation method thereof - Google Patents
Polypropylene/fiberglass composite material and preparation method thereof Download PDFInfo
- Publication number
- CN102492222A CN102492222A CN2011104030055A CN201110403005A CN102492222A CN 102492222 A CN102492222 A CN 102492222A CN 2011104030055 A CN2011104030055 A CN 2011104030055A CN 201110403005 A CN201110403005 A CN 201110403005A CN 102492222 A CN102492222 A CN 102492222A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- epoxy resin
- composite material
- fiberglass
- parts
- 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
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a polypropylene/fiberglass composite material and a preparation method thereof. The polypropylene/fiberglass composite material is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 15-50 parts of fiberglass, 5-15 parts of maleic anhydride grafted polypropylene, 0.2-0.5 part of peroxide initiator and 0.5-2 parts of epoxy resin. The preparation method of the polypropylene/fiberglass composite material comprises the steps of: uniformly mixing weighed polypropylene, maleic anhydride grafted polypropylene and the peroxide initiator according to the ratios, adding to the upstream feeding port of a screw extruder at the temperature of 160-230 DEG C and mixing; synchronously carrying out epoxy resin surface coating treatment on the fiberglass, weighing the fiberglass before and after coating, calculating the addition amount of epoxy resin according to the weight difference of the fiberglass before and after coating, introducing to the downstream fiberglass adding port of the screw extruder, and by virtue of the shearing action of the screw extruder, shearing the fiberglass into about 0.2-0.5 mm and uniformly dispersing the fiberglass in a base material; and extruding, drawing and granulating. The material is good in strength, rigidity and impact ductility, simple in process, low in cost and high in production efficiency.
Description
Technical field
The present invention relates to the material technology field, specifically come just to relate to a kind of polypropylene/glass fiber composite material, also relate to the preparation method of its this polypropylene/glass fiber composite material simultaneously.
Background technology
Vestolen PP 7052 is a kind of non-polar interchangeable heat thermoplastic plastic, has good processing properties, better comprehensive mechanical property and cheap relatively price, but hardness, rigidity and notched Izod impact strength are relatively low, have limited its application in many occasions.Fiber reinforcement normally polymer materials strengthens, increases firm effective means; Spun glass is owing to possess higher intensity and lower price; Application in the polymer composites preparation is very general; One of key that material property improves is to make good bonding of the interface generation of body material and fiber, and Vestolen PP 7052 is a kind of widely used thermoplastic, polymeric materials, although fiberglass surfacing generally all carries out surface treatment with coupling agent; But because Vestolen PP 7052 is the non-polar polymer material; Poor with the interfacial adhesion strength of spun glass, add the acid anhydride-grafted Vestolen PP 7052 raising interfacial adhesion strength of part even adopt usually, but the spun glass modification is still limited to the raising of Properties of Polypropylene.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming and provide a kind ofly have a good processing properties, well intensity, rigidity and impelling strength, and the polypropylene/glass fiber composite material that technology is simple, cost is low, production efficiency is high.
Another object of the present invention is to provide the preparation method of this polypropylene/glass fiber composite material.
A kind of polypropylene/glass fiber composite material of the present invention, its parts by weight of raw materials is following:
0.5～2 part of 100 parts of Vestolen PP 7052,15～50 parts in spun glass, 5～15 parts of maleic anhydride inoculated polypropylenes, 0.2～0.5 part of peroxide initiator and epoxy resin;
Wherein: peroxide initiator adopts 130～193 ℃ of decomposition temperatures, the kind of 1 minute transformation period.
Above-mentioned a kind of polypropylene/glass fiber composite material, wherein: Vestolen PP 7052 is common homopolymerization type or copolymerized type propene polymer.
Above-mentioned a kind of polypropylene/glass fiber composite material, wherein: spun glass is alkali-free or low alkali glass fiber.
Above-mentioned a kind of polypropylene/glass fiber composite material, wherein: epoxy resin is selected bisphenol-type epoxy resin, polyphenol type tetraglycidel ether epoxy resin or glycidyl ester type epoxy resin etc.
Above-mentioned a kind of polypropylene/glass fiber composite material, wherein: peroxide initiator is Di Cumyl Peroxide 99, tert-butyl peroxide or Lucidol etc.
A kind of preparation method of polypropylene/glass fiber composite material comprises the steps:
(1) mix by said ratio weighing Vestolen PP 7052, maleic anhydride inoculated polypropylene, peroxide initiator, under 160～230 ℃ of temperature, adding screw extrusion press upper reaches charging opening is mixing;
(2) spun glass is carried out the epoxy resin surface coating processing synchronously; Spun glass before and after weighing applies; Both differences are the add-on E of epoxy resin, and introducing screw extrusion press downstream spun glass adds inlet, the shearing action of screw extrusion press; Make spun glass cut off written treaty 0.2-0.5 millimeter, and be dispersed in the body material;
E=[(S
1-S
0)/S
0] G, wherein: the epoxy resin umber of E for adding; S
1For applying back unit length spun glass weight; S
0Be unit length spun glass weight before applying; The spun glass umber (can by calcination method confirm) of G for adding;
(3) promptly get polypropylene/glass fiber composite material through extruding check rod, granulation.
The present invention compared with prior art; Has tangible beneficial effect; Can know from above technical scheme: utilize the peroxide initiator that adds to decompose the generation radical at a certain temperature; Initiation makes the anhydride group of the maleic anhydride inoculated polypropylene of adding under these processing condition, produce chemical reaction with the epoxide group of epoxy resin molecule and combines, and improves the combination degree of Vestolen PP 7052 and epoxy resin.On the other hand, because epoxide group has good affinity with polar group through the fiberglass surfacing of coupling agent treatment, thereby the epoxy resin of many epoxy-functionals improves the bonding strength of Vestolen PP 7052 and fiberglass surfacing.As with 100 parts of Vestolen PP 7052,10 parts of maleic anhydride inoculated polypropylenes, 0.2 part of thorough mixing of Di Cumyl Peroxide 99 (initiator); Fiberglass surfacing is through bisphenol A epoxide resin (E-44) coating processing; Mixing compound in twin screw extruder by above-mentioned complete processing; This matrix material is carried out the infrared spectrum analysis revealed, at 1735 cm
-1A characteristic peak has appearred in the place; That this peak is corresponding is the stretching vibration ν of carbonyl in the ester compound, and the anhydride group of this explanation epoxy resin and maleic anhydride inoculated polypropylene produces chemical reaction, generates ester bond; Be that epoxy resin has been received on the Vestolen PP 7052 macromolecular chain; Test simultaneously shows, as not adding initiator, then under these processing condition, does not produce this reaction.
Through test; Utilize the present invention in common homopolymerization type Vestolen PP 7052, to add 50 parts spun glass; Compare with the matrix material that does not add epoxy resin, can make the tensile strength of material increase to 115MPa by 81MPa, modulus in flexure increases to 7.0GPa by 5.1 GPa; Flexural strength increases to 142MPa by 112MPa, and the normal temperature notched Izod impact strength is by 7.5KJ/m
2Increase to 10.2 KJ/m
2In copolymerized type propene polymer, add 43 parts spun glass; Compare with the matrix material that does not add epoxy resin; Can make the tensile strength of material increase to 105MPa by 83MPa; Modulus in flexure increases to 6.1GPa by 4.8GPa, and flexural strength increases to 129MPa by 105MPa, and the normal temperature notched Izod impact strength is by 9.2KJ/m
2Increase to 15.8KJ/m
2This shows, adopt surface-coated method and peroxide initiator, with relatively inexpensive epoxy resin modification polypropylene/glass fiber composite material; Obtained result preferably; Thereby improved intensity, rigidity and the impelling strength of blend, surface quality is good, has good processing properties.Employing directly is coated on fiberglass surfacing with epoxy resin, and the effect of improving of material property is significantly improved, and makes material have good intensity, rigidity and impelling strength; Technology is simple simultaneously, cost is low, production efficiency is high.
Embodiment
Embodiment 1
A kind of preparation method of polypropylene/glass fiber composite material comprises the steps:
(1) proportioning weighing Vestolen PP 7052, maleic anhydride inoculated polypropylene, the peroxide initiator by table 1-1 mixes, and under 160～230 ℃ of temperature, adding screw extrusion press upper reaches charging opening is mixing;
(2) spun glass is carried out the epoxy resin surface coating processing synchronously; Spun glass before and after weighing applies; Both differences calculate 2 parts of the add-ons of epoxy resin, and introduce screw extrusion press downstream spun glass and add inlet, the shearing action of screw extrusion press; Make spun glass cut off written treaty 0.2-0.5 millimeter, and be dispersed in the body material;
(3) promptly get polypropylene/glass fiber composite material through extruding check rod, granulation.
Get this material and be injection molded into batten, 23 ℃ place 24 hours after test performance, detected result is seen table 1-1.
The composite property detected result that does not add initiator and epoxy resin is seen table 1-2.
Table 1-2 does not add the composite property detected result of epoxy resin and initiator
Embodiment 2
A kind of preparation method of polypropylene/glass fiber composite material comprises the steps:
(1) proportioning weighing Vestolen PP 7052, maleic anhydride inoculated polypropylene, the peroxide initiator by table 2-1 mixes, and under 160～230 ℃ of temperature, adding screw extrusion press upper reaches charging opening is mixing;
(2) spun glass is carried out the epoxy resin surface coating processing synchronously; Spun glass before and after weighing applies; Both differences calculate 0.5 part of the add-on of epoxy resin, and introduce screw extrusion press downstream spun glass and add inlet, the shearing action of screw extrusion press; Make spun glass cut off written treaty 0.2-0.5 millimeter, and be dispersed in the body material;
(3) promptly get polypropylene/glass fiber composite material through extruding check rod, granulation.
Get this material and be injection molded into batten, 23 ℃ place 24 hours after test performance, the result who obtains is like table 2-1
Table 2-1 adds the composite property detected result of epoxy resin
The composite property detected result that does not add initiator and epoxy resin is seen table 2-2.
Table 2-2 does not add the composite property detected result of epoxy resin and initiator
Embodiment 3:
A kind of preparation method of polypropylene/glass fiber composite material comprises the steps:
(1) proportioning weighing Vestolen PP 7052, maleic anhydride inoculated polypropylene, the peroxide initiator by table 3-1 mixes, and under 160～210 ℃ of temperature, adding screw extrusion press upper reaches charging opening is mixing;
(2) spun glass is carried out the epoxy resin surface coating processing synchronously; Spun glass before and after weighing applies; Both differences calculate 1.1 parts of the add-ons of epoxy resin, and introduce screw extrusion press downstream spun glass and add inlet, the shearing action of screw extrusion press; Make spun glass cut off written treaty 0.2-0.5 millimeter, and be dispersed in the body material;
(3) promptly get polypropylene/glass fiber composite material through extruding check rod, granulation.
Get this material and be injection molded into batten, 23 ℃ place 24 hours after test performance, detected result is seen table 3-1.
Table 3-1 adds the composite property detected result of epoxy resin
The composite property detected result that does not add epoxy resin is seen table 3-2.
Table 3-2 does not add the composite property detected result of initiator and epoxy resin
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction; Anyly do not break away from technical scheme content of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (6)
1. polypropylene/glass fiber composite material, its parts by weight of raw materials is following:
0.5～2 part of 100 parts of Vestolen PP 7052,15～50 parts in spun glass, 5～15 parts of maleic anhydride inoculated polypropylenes, 0.2～0.5 part of peroxide initiator and epoxy resin;
Wherein: peroxide initiator adopts 130～193 ℃ of decomposition temperatures, the kind of 1 minute transformation period.
2. a kind of polypropylene/glass fiber composite material as claimed in claim 1, wherein: Vestolen PP 7052 is common homopolymerization type or copolymerized type propene polymer.
3. a kind of polypropylene/glass fiber composite material as claimed in claim 1, wherein: spun glass is alkali-free or low alkali glass fiber.
4. a kind of polypropylene/glass fiber composite material as claimed in claim 1, wherein: epoxy resin is selected bisphenol-type epoxy resin, polyphenol type tetraglycidel ether epoxy resin or glycidyl ester type epoxy resin.
5. a kind of polypropylene/glass fiber composite material as claimed in claim 1, wherein: peroxide initiator is Di Cumyl Peroxide 99, tert-butyl peroxide or Lucidol.
6. like the preparation method of one of claim 1-5 described polypropylene/glass fiber composite material, comprise the steps:
(1) mix by said ratio weighing Vestolen PP 7052, maleic anhydride inoculated polypropylene, peroxide initiator, under 160～230 ℃ of temperature, adding screw extrusion press upper reaches charging opening is mixing;
(2) spun glass is carried out the epoxy resin surface coating processing synchronously; Spun glass before and after weighing applies; Both differences can calculate the add-on E of epoxy resin, the spun glass after applying is introduced screw extrusion press downstream spun glass add inlet, the shearing action of screw extrusion press; Make spun glass cut off written treaty 0.2-0.5 millimeter, and be dispersed in the body material;
E=[(S
1-S
0)/S
0] G, wherein: the epoxy resin umber of E for adding; S
1For applying back unit length spun glass weight; S
0Be unit length spun glass weight before applying; The spun glass umber of G for adding;
(3) promptly get polypropylene/glass fiber composite material through extruding check rod, granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104030055A CN102492222A (en) | 2011-12-07 | 2011-12-07 | Polypropylene/fiberglass composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104030055A CN102492222A (en) | 2011-12-07 | 2011-12-07 | Polypropylene/fiberglass composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102492222A true CN102492222A (en) | 2012-06-13 |
Family
ID=46184086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104030055A Pending CN102492222A (en) | 2011-12-07 | 2011-12-07 | Polypropylene/fiberglass composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102492222A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275399A (en) * | 2013-06-21 | 2013-09-04 | 苏州新区特氟龙塑料制品厂 | Low-cost transparent plastic |
| CN106189098A (en) * | 2016-09-07 | 2016-12-07 | 安徽金生金世电子科技有限公司 | Polymer modification glass fibre and preparation method thereof |
| CN106400503A (en) * | 2016-09-07 | 2017-02-15 | 安徽金生金世电子科技有限公司 | Polymer-modified glass fibre and preparation method thereof |
| CN106433032A (en) * | 2016-09-07 | 2017-02-22 | 安徽金生金世电子科技有限公司 | Organic matter-modified glass fiber and preparation method thereof |
| CN106433031A (en) * | 2016-09-07 | 2017-02-22 | 安徽金生金世电子科技有限公司 | Modified glass fiber and preparation method thereof |
| CN107698878A (en) * | 2017-11-27 | 2018-02-16 | 谢彬彬 | A kind of ageing-resistant PP tubing of high rigidity and preparation method thereof |
| CN109096603A (en) * | 2018-07-10 | 2018-12-28 | 上海普利特复合材料股份有限公司 | The long glass fiber reinforced polypropylene composite material and its manufacturing method that a kind of overall plastic tail-gate is dedicated, adhesive effect is excellent |
| CN111635589A (en) * | 2020-07-15 | 2020-09-08 | 苏州润佳工程塑料股份有限公司 | Preparation method of high-modulus high-impact-resistance polypropylene composite material |
| CN114479283A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Long glass fiber reinforced polypropylene composite material and preparation method and application thereof |
| CN114616279A (en) * | 2019-09-05 | 2022-06-10 | 新加坡科技研究局 | Mechanically reinforced polyolefin composites |
| CN115335449A (en) * | 2020-03-31 | 2022-11-11 | 普瑞曼聚合物株式会社 | Fiber-reinforced polypropylene resin composition and process for producing the same |
| CN116554534A (en) * | 2023-07-04 | 2023-08-08 | 昆山巴鸣泡沫塑料制品有限公司 | Environment-friendly polypropylene flame-retardant foam material and preparation process thereof |
| CN116693977A (en) * | 2023-05-29 | 2023-09-05 | 江苏众成复合材料有限责任公司 | High-strength polypropylene pipe based on glass fiber and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181100A (en) * | 2011-03-18 | 2011-09-14 | 四川长虹电器股份有限公司 | Glass fiber reinforced co-polypropylene composite material and preparation method of the Glass fiber reinforced co-polypropylene composite material |
-
2011
- 2011-12-07 CN CN2011104030055A patent/CN102492222A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181100A (en) * | 2011-03-18 | 2011-09-14 | 四川长虹电器股份有限公司 | Glass fiber reinforced co-polypropylene composite material and preparation method of the Glass fiber reinforced co-polypropylene composite material |
Non-Patent Citations (2)
| Title |
|---|
| 《COMPOSITES.》 19941231 J.L.THOMASON et al "An investigation of glass fibre/ polypropylene interface strength and its effect on composite properties" 第197页摘要，第2栏第2段-第203页第1栏第2段 1-6 第25卷, 第3期 * |
| J.L.THOMASON ET AL: ""An investigation of glass fibre/ polypropylene interface strength and its effect on composite properties"", 《COMPOSITES.》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275399A (en) * | 2013-06-21 | 2013-09-04 | 苏州新区特氟龙塑料制品厂 | Low-cost transparent plastic |
| CN106189098A (en) * | 2016-09-07 | 2016-12-07 | 安徽金生金世电子科技有限公司 | Polymer modification glass fibre and preparation method thereof |
| CN106400503A (en) * | 2016-09-07 | 2017-02-15 | 安徽金生金世电子科技有限公司 | Polymer-modified glass fibre and preparation method thereof |
| CN106433032A (en) * | 2016-09-07 | 2017-02-22 | 安徽金生金世电子科技有限公司 | Organic matter-modified glass fiber and preparation method thereof |
| CN106433031A (en) * | 2016-09-07 | 2017-02-22 | 安徽金生金世电子科技有限公司 | Modified glass fiber and preparation method thereof |
| CN107698878A (en) * | 2017-11-27 | 2018-02-16 | 谢彬彬 | A kind of ageing-resistant PP tubing of high rigidity and preparation method thereof |
| CN109096603A (en) * | 2018-07-10 | 2018-12-28 | 上海普利特复合材料股份有限公司 | The long glass fiber reinforced polypropylene composite material and its manufacturing method that a kind of overall plastic tail-gate is dedicated, adhesive effect is excellent |
| CN114616279A (en) * | 2019-09-05 | 2022-06-10 | 新加坡科技研究局 | Mechanically reinforced polyolefin composites |
| CN115335449B (en) * | 2020-03-31 | 2024-05-31 | 普瑞曼聚合物株式会社 | Fiber reinforced polypropylene resin composition and method for producing same |
| CN115335449A (en) * | 2020-03-31 | 2022-11-11 | 普瑞曼聚合物株式会社 | Fiber-reinforced polypropylene resin composition and process for producing the same |
| CN111635589A (en) * | 2020-07-15 | 2020-09-08 | 苏州润佳工程塑料股份有限公司 | Preparation method of high-modulus high-impact-resistance polypropylene composite material |
| CN114479283A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Long glass fiber reinforced polypropylene composite material and preparation method and application thereof |
| CN114479283B (en) * | 2020-10-27 | 2023-07-21 | 中国石油化工股份有限公司 | Long glass fiber reinforced polypropylene composite material and preparation method and application thereof |
| CN116693977A (en) * | 2023-05-29 | 2023-09-05 | 江苏众成复合材料有限责任公司 | High-strength polypropylene pipe based on glass fiber and preparation method thereof |
| CN116693977B (en) * | 2023-05-29 | 2024-06-18 | 海伟石化有限公司 | High-strength polypropylene pipe based on glass fiber and preparation method thereof |
| CN116554534A (en) * | 2023-07-04 | 2023-08-08 | 昆山巴鸣泡沫塑料制品有限公司 | Environment-friendly polypropylene flame-retardant foam material and preparation process thereof |
| CN116554534B (en) * | 2023-07-04 | 2023-10-03 | 昆山巴鸣泡沫塑料制品有限公司 | Environment-friendly polypropylene flame-retardant foam material and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102492222A (en) | Polypropylene/fiberglass composite material and preparation method thereof | |
| US4003874A (en) | Producing glass-reinforced polyolefin compositions | |
| CN101613503B (en) | Water-resistant wood-plastic composite material and preparation method thereof | |
| CN105199404B (en) | A kind of composition for thermoplastic elastomer for covered with nylon material | |
| CN101704969B (en) | Wood plastic composite for injection and preparation method and application thereof | |
| CN1934183A (en) | Composite compositions comprising cellulose and polymeric components | |
| CN102417561B (en) | Ultrahigh-mobility propenyl elastomer grafting copolymer and preparation method thereof | |
| CN103525110A (en) | High-strength PE (polyethylene) wood-plastic composite material and preparation method thereof | |
| CN109081894B (en) | High-fluidity toughening agent and preparation method thereof | |
| CN106608996A (en) | Polyethylene composition and preparation method thereof, and modified crosslinked polyethylene | |
| CN101747600A (en) | Method for preparing polyethylene terephthalate (PET) blend | |
| CN101735398A (en) | Interfacial compatilizer for wood-plastic composite material and method for preparing same | |
| CN103571040A (en) | High-strength, high-toughness and high-rigidity polypropylene composite material and preparation method thereof | |
| CN102558679A (en) | Novel bamboo fiber/polypropylene composite material and method for preparing same | |
| CN102942790A (en) | High temperature-resistant high-strength polyphenylene sulfide-based reactively reinforced and toughened composite material | |
| CN109401643A (en) | One kind having high bonding force steel band reinforced polyethylene spiral ripple pipe special bonding resin material and preparation method thereof | |
| CN109456563A (en) | A kind of UHMWPE alloy compatibilization and toughening modified polypropene ripple pipe as special material and preparation method thereof | |
| CN104530739B (en) | A kind of polyolefin-based wood plastic composite of thermotropic high molecule liquid crystal activeness and quietness | |
| CN102127260A (en) | Tough long glass fiber-reinforced polypropylene composition plate material and preparation method thereof | |
| CN107090155A (en) | A kind of method that utilization printed circuit board (PCB) non-metal powder strengthens wood plastic composite | |
| CN106519556A (en) | Grafted modified polypropylene wood-plastic composite material and preparation method thereof | |
| CN105482254A (en) | High-surface-smoothness long-glass-fiber-reinforced polypropylene composite material and preparation method thereof | |
| CN111978641A (en) | High-modulus, high-fluidity and high-impact-resistance glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN103289183A (en) | Thermal enhancement polypropylene and preparation method thereof | |
| CN104163983A (en) | Ramie fiber-reinforced polypropylene composite material and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120613 |