CN103009639A - Production method of continuous glass fabric reinforced thermoplastic sheet - Google Patents
Production method of continuous glass fabric reinforced thermoplastic sheet Download PDFInfo
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- CN103009639A CN103009639A CN2012104901578A CN201210490157A CN103009639A CN 103009639 A CN103009639 A CN 103009639A CN 2012104901578 A CN2012104901578 A CN 2012104901578A CN 201210490157 A CN201210490157 A CN 201210490157A CN 103009639 A CN103009639 A CN 103009639A
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Abstract
The invention discloses a continuous glass fabric reinforced thermoplastic sheet, which uses a packaged continuous glass fabric as an initial material and thermoplastic plastic as a base stock. The production method comprises the following steps of unreeling, flattening, plastic dipping, finishing, thermosetting, molding processing and reeling, wherein the seven steps are continuously produced on a production line. The production method is reasonable and ensures high production efficiency and high finished product quality.
Description
Technical field
What the present invention relates to is a kind of production method of continuous glass-fiber cloth reinforced thermoplastics sheet material, belongs to the material technology field.
Background technology
Continuous glass-fiber cloth reinforced thermoplastics sheet material of the present invention, its thickness below 1mm, are a kind of synthetic thin materials of Sustainable Exploitation generally.
Described reinforced plastics sheet material can be directly used in the incrustation of entity product, also its MULTILAYER COMPOSITE can be bonded to one and form composite board, for the manufacture of panel of the product such as the entity such as floor, furniture and indoor partition etc.Thereby this described reinforced plastics sheet material is extensively adopted by every field institute.
At present, prior art adopts glass fibre or glass fiber bundle as the internal memory reinforcing material of plastic substrate mostly, by several different methods, produces described reinforced plastics sheet material or other goods.The prior art of producing described reinforced plastics sheet material has:
The disclosed application number 200580007180.5 of Chinese patent is to supply with cyclic oligomer at the MULTILAYER COMPOSITE reticular fiber structure, then via through type press and heating and make plastic plate.This patent application preparation method's main deficiency is that infiltration between plastics and the fiber is full closes not comprehensively, and the mechanical performance of manufactured goods is undesirable.
And Chinese patent application number is ZL97114543.1, is to adopt the extruder with cross die head, the continuous glass-fiber of multilayer pre-soaked resin is covered in the surface of plastic basis material or the base material and makes plastic plate.This patent application preparation method's main deficiency be that its glass does not really enter plastic substrate inside, thereby the humidification of glass is still unsatisfactory.
And Chinese patent application numbers 200810233396.9, be with fibre bundle by the abundant impregnated with molten plastics of pre-stain technique after, by the mould moulding and through cooling curing, and make the reinforced plastics sheet material or other has the product of planform.The production method of this reinforced plastics goods, because its reinforcing material that adopts is fibre bundle, rather than continuous tow, it more or not fabric, thereby the tensile strength of its manufactured goods transverse tensile strength especially, be obviously undesirable, be not enough to produce the high-strength plastic material products.
And Chinese patent application number is 200710025869.1, after pure glass polypropylene waste material is pulverized granulation, with again granulations of blend such as vinyons, thereafter manufacture again the reinforced plastics goods such as sheet material, although this patent application provides the waste material reutilization technology, but every mechanical performance of its manufactured goods is obviously paid no attention to, and is not enough to produce the high-strength plastic material products.
For widen to mould Dai Mu, to mould the use field of Dai Gang, research and develop a kind of glass reinforced plastics sheet material more advanced than prior art, be a present common heat subject of paying close attention in the industry.
Summary of the invention
It is reasonable that the present invention aims to provide a kind of production method, favorable quality of finished products, and the production method of the continuous glass-fiber cloth reinforced thermoplastics sheet material that production efficiency is high is to satisfy society's needs growing to described sheet material.
The present invention realizes the conception of its purpose, the one, adopting continuous glass-fiber cloth is thermoplastic matrix internal memory reinforcing material, with comprehensive raising manufactured goods sheet material multiaxis to tensile strength; The 2nd, adopt glass-fiber-fabric dipping hot melt plastics technology, make hot melting plastic infiltrate comprehensively, permeate, wrap up the fiber filament of glass-fiber-fabric, to give full play to internal memory glass-fiber-fabric multiaxis to the effect that strengthens matrix plastic comprehensively, improve the performance of manufactured goods sheet material; The 3rd, adopt tiling glass-fiber-fabric technology, soak the stress of weaving of eliminating glass-fiber-fabric before moulding at it, make fiberglass filament be in loosening and unfold state, effectively improve fiberglass filament and soak the condition of moulding matrix plastic, make matrix plastic fully enter the slit of glass-fiber-fabric and the inside of fiberglass filament, with the infiltration combination degree of Effective Raise matrix plastic and glass-fiber-fabric, strengthen the mechanical performance of manufactured goods sheet material; The 4th, behind glass-fiber-fabric impregnation matrix plastics, implement immediately thermal finalization processing and forming processes; Make plastics dipping glass-fiber-fabric under state is unfolded in tiling, loosen and naturally implement the thermal finalization processing, to eliminate its formed internal stress in front production process, to the negative effect of manufactured goods thin gauge sheet performance, with seasonal matrix plastic and the comprehensive combination of glass-fiber-fabric; Thereafter, but the more successively respectively rolloff of and cold roll pair secondary via the through type hot roll with the density of further raising matrix plastic and glass-fiber-fabric self and both adhesions, is produced high performance reinforced plastics sheet material of the present invention; The 5th, on a production line, produce continuously, increasing substantially production efficiency, thereby realize purpose of the present invention.
Based on the above technical though, the present invention realizes that the technical scheme of its purpose is:
A kind of production method of continuous glass-fiber cloth reinforced thermoplastics sheet material take thermoplastic as base-material, for the material that sets out, is characterized in that with package continuous glass-fiber cloth the production method of described sheet material is carried out successively according to the following steps:
A, unreel; In unreeling process, control glass-fiber-fabric motion drawing tension in 80 ~ 100NM scope, and realize centering by correction;
B, flattening; Described flattening is to import flattening device with unreeling glass-fiber-fabric, and is tiled on the belt conveying platform, makes footpath, the weft filament of glass-fiber-fabric unfold straight, elimination wrinkle;
C, soak and mould; Described soaking moulded, and is the glass-fiber-fabric that flattens through flattening step, imports and deposits in the dipping box of hot melt modified plastics, and the enforcement glass-fiber-fabric soaks to be moulded; The temperature of described hot melting plastic is controlled in 220 ~ 250 ℃ of scopes, soaks the time of moulding to be controlled in 1 ~ 2min scope;
D, soak and mould rear arrangement; Described soaking moulded post processing, is with through soaking the glass-fiber-fabric of moulding the saturated content of the described molten plastic of being in of processing, but through the secondary rolloff of the through type hot roll of surface temperature in 180 ~ 200 ℃ of scopes; Secondary via the scraping blade of the thickness setting spacing of pressing described sheet material again, wipe the described plastics that are present in the positive and negative surface of glass-fiber-fabric off; Thereafter the surface temperature that equals described sheet thickness via spacing again is the secondary rolloff of the cold roll of normal temperature, makes the described plastics in glass-fiber-fabric surface be in not roll banding state;
E, thermal finalization are processed; Described thermal finalization is processed, and is the material through the dipping post processing to be soaked mould glass-fiber-fabric and import in the heat-setting box, and is not tiled in sticking on the conveyer belt, makes described material soak moulding glass-fiber-fabric to be in free relaxation state and implements the thermal finalization processing; Described thermal finalization the temperature inside the box is controlled in 180 ~ 200 ℃ of scopes, and the thermal finalization processing time is controlled in 1 ~ 1.5min scope;
F, forming processes; Described forming processes is that the material that will process through thermal finalization soaks and moulds glass-fiber-fabric, imports the secondary enforcement of the hot roll of surface temperature 180 ~ 200 ℃ of scopes in hot rolling; Then then import surface temperature and be the roll of normal temperature secondary implement cold rolling; Thereafter make again the continuous glass-fiber-fabric reinforced thermoplastics of the moulding of thickness in 0.4 ~ 1mm scope sheet material through naturally cooling off;
G, rolling; Described rolling is with through the prepared described formed sheet of heat treatment, and coiling is namely finished the production process of described continuous glass-fiber cloth reinforced thermoplastics sheet material;
Describedly unreel, flatten, soak and mould, soak and mould post processing, thermal finalization processing, forming processes, seven steps of rolling, on a production line, carry out continuously; And the travel line speed of described production line is controlled in 3 ~ 4m/min scope.
By above given purport technical scheme, be combined in front described technical though and can understand that the present invention has realized its purpose that will realize.
In technique scheme, the present invention advocates that also described base-material thermoplastic is modified polypropylene plastic.But being not limited to this, also can be other thermoplastics such as polyethylene or poly-the third ethene.
In technique scheme, the present invention advocates that also described glass-fiber-fabric is that grammes per square metre is at 150 ~ 450g/m
2Plain weave glass-fiber-fabric or twill glass-fiber-fabric or satin weave glass-fiber-fabric; Its fabric construction be twin shaft to or the multi-axial fabric structure; The warp of described glass-fiber-fabric, weft filament be alkali-free without wax without twisting filament.And described glass-fiber-fabric can be woven cloths, also can be non-weaving cloth.
In technique scheme, the present invention also advocates, the described glass-fiber-fabric of moulding step that soaks is the fabric guide roll of arranging via a plurality of upper and lower dislocation in dipping box, soaks and moulds and be the motion of serpentine route.Its purpose obviously is, makes glass-fiber-fabric and hot melting plastic fully flood, and hot melting plastic is goed deep in the gap of glass-fiber-fabric and the weaving in the long filament of glass-fiber-fabric, with further raising dipping effect.
In technique scheme, the present invention also advocates, in described modified polypropylene plastic, also contains a kind of in fire retardant, UV resistant agent and the antioxidant or two kinds or three kinds.
In technique scheme, the present invention also advocates, described glass-fiber-fabric is to import hot melting plastic to extrude in the case after flattening step, and by the described case discharging opening of extruding, and the dipping box that enters impregnation steps with hot melting plastic curtain coating waterfall is implemented dipping.
After technique scheme was implemented in full, the production method that the present invention has was reasonable, and production efficiency is high, and the characteristics such as favorable quality of finished products are apparent.
Description of drawings
Fig. 1 is the manufactured goods structural representation of a kind of specific embodiment of the present invention.Glass-fiber-fabric shown in the figure 8 is that twin shaft is to woven cloths or non-weaving cloth;
Fig. 2 is production line schematic diagram of the present invention; 1 for unreeling section shown in the figure, and 2 for flattening section, and 3 mould section for soaking, and 4 mould the post processing section for soaking, 5 thermal finalization sections, and 6 is the moulding section, 7 is the rolling section.
The specific embodiment
Below in conjunction with accompanying drawing, by the description of the specific embodiment, the invention will be further described.
A kind of typical specific embodiment please be joined and be read attached Fig. 1 and 2.
A kind of production method of continuous glass-fiber cloth reinforced thermoplastics sheet material, take thermoplastic as base-material, for the material that sets out, and the production method of described sheet material is carried out successively according to the following steps with package continuous glass-fiber cloth 1-1:
A, unreel; In unreeling process, control glass-fiber-fabric motion drawing tension in 80 ~ 100NM scope by electronic tensile controller 1-3, and realize centering by olive roller 1-2 correction;
B, flattening; Described flattening is to import flattening device with unreeling glass-fiber-fabric 1-1, and is tiled on the belt conveying platform 2-1, makes footpath, the weft filament of glass-fiber-fabric 1-1 unfold straight, elimination wrinkle;
C, soak and mould; Described soaking moulded, and is the glass-fiber-fabric 1-1 that flattens through flattening step, imports and deposits in the dipping box 3-2 of hot melt modified plastics, and the enforcement glass-fiber-fabric soaks to be moulded; The temperature of described hot melting plastic is controlled in 220 ~ 250 ℃ of scopes, soaks the time of moulding to be controlled in 1 ~ 2min scope;
D, soak and mould rear arrangement; Described soaking moulded post processing, is with through soaking the glass-fiber-fabric of moulding the saturated content of the described molten plastic of being in of processing, but through the through type hot roll secondary 4-1 rolloff of surface temperature in 180 ~ 200 ℃ of scopes; Via the secondary 4-2 of scraping blade of the thickness setting spacing of pressing described sheet material, wipe the described plastics that are present in the positive and negative surface of glass-fiber-fabric off again; Thereafter the surface temperature that equals described sheet thickness via spacing again is secondary 4-3 of the cold roll rolloff of normal temperature, makes the described plastics in glass-fiber-fabric surface be in not roll banding state;
E, thermal finalization are processed; Described thermal finalization is processed, and is the material through the dipping post processing to be soaked mould glass-fiber-fabric and import in the heat-setting box 5-1, and is not tiled in sticking on the foraminous conveyer 5-2, makes described material soak moulding glass-fiber-fabric to be in free relaxation state and implements the thermal finalization processing; Temperature is controlled in 180 ~ 200 ℃ of scopes in the described heat-setting box 5-1, and the thermal finalization processing time is controlled in 1 ~ 1.5min scope;
F, forming processes; Described forming processes is that the material that will process through thermal finalization soaks and moulds glass-fiber-fabric, imports the hot roll secondary 6-1 enforcement hot rolling of surface temperature 180 ~ 200 ℃ of scopes in; Then the secondary 6-2 of roll that then imports surface temperature and be normal temperature implements cold rolling; Thereafter make again the continuous glass-fiber-fabric reinforced thermoplastics of the moulding of thickness in 0.4 ~ 1mm scope sheet material through naturally cooling off;
G, rolling; Described rolling is with through the prepared described formed sheet of heat treatment, and coiling 7-1 namely finishes the production process of described continuous glass-fiber cloth reinforced thermoplastics sheet material;
Describedly unreel, flatten, soak and mould, soak and mould post processing, thermal finalization processing, forming processes, seven steps of rolling, on a production line, carry out continuously; And the travel line speed of described production line is controlled in 3 ~ 4m/min scope.
And described base-material thermoplastic is modified polypropylene plastic.
And described glass-fiber-fabric is that grammes per square metre is at 150 ~ 450g/m
2Plain weave glass-fiber-fabric or twill glass-fiber-fabric or satin weave glass-fiber-fabric; Its fabric construction be twin shaft to or the multi-axial fabric structure; The warp of described glass-fiber-fabric, weft filament be alkali-free without wax without twisting filament.
And the described glass-fiber-fabric of moulding step that soaks is the fabric guide roll 3-3 that arranges via a plurality of upper and lower dislocation in modified polypropylene plastic dipping box 3-2, soaks and moulds and be serpentine route motion.
And in described modified polypropylene plastic, also contain a kind of in the UV resistant agents such as fire retardant, the titanium dioxide such as APP and the antioxidant or two kinds or three kinds.
And described glass-fiber-fabric is to import hot melting plastic to extrude in the case 3-1 after flattening step, and by the described case 3-1 discharging opening of extruding, and the dipping box 3-2 that enters impregnation steps with hot melting plastic curtain coating waterfall implements dipping.
And described soaking moulded the temperature that soaking of step moulded the heat-setting box 5-1 of case 3-2 and thermal finalization step, provides and keeps by electrical heating; And the described secondary 4-1 of hot roll that moulds rear arrangement step and both temperature of secondary 6-1 of hot roll of forming processes step of soaking provides and keeps by circulating heat conduction oil in the roller.
The test result of the manufactured goods first sample of the present invention of the specific embodiment described above is: glass weight percentage 30%, proportion 1.2, tensile strength 130Mpa, bending strength 110 Mpa, bending modulus 4000 Mpa, impact strength 80 Mpa, case hardness 88.6HR, 156.6 ℃ of heat distortion temperatures, 142.5 ℃ on dimension card, flame retardant rating V
O, described test result shows that the present invention has obtained very significantly technical economic benefit, has realized original intention of the present invention.
Claims (6)
1. the production method of a continuous glass-fiber cloth reinforced thermoplastics sheet material take thermoplastic as base-material, for the material that sets out, is characterized in that with package continuous glass-fiber cloth the production method of described sheet material is carried out successively according to the following steps:
A, unreel; In unreeling process, control glass-fiber-fabric motion drawing tension in 80 ~ 100NM scope, and realize centering by correction;
B, flattening; Described flattening is to import flattening device with unreeling glass-fiber-fabric, and is tiled on the belt conveying platform, makes footpath, the weft filament of glass-fiber-fabric unfold straight, elimination wrinkle;
C, soak and mould; Described soaking moulded, and is the glass-fiber-fabric that flattens through flattening step, imports and deposits in the dipping box of hot melt modified plastics, and the enforcement glass-fiber-fabric soaks to be moulded; The temperature of described hot melting plastic is controlled in 220 ~ 250 ℃ of scopes, soaks the time of moulding to be controlled in 1 ~ 2min scope;
D, soak and mould rear arrangement; Described soaking moulded post processing, is with through soaking the glass-fiber-fabric of moulding the saturated content of the described molten plastic of being in of processing, but through the secondary rolloff of the through type hot roll of surface temperature in 180 ~ 200 ℃ of scopes; Secondary via the scraping blade of the thickness setting spacing of pressing described sheet material again, wipe the described plastics that are present in the positive and negative surface of glass-fiber-fabric off; Thereafter the surface temperature that equals described sheet thickness via spacing again is the secondary rolloff of the cold roll of normal temperature, makes the described plastics in glass-fiber-fabric surface be in not roll banding state;
E, thermal finalization are processed; Described thermal finalization is processed, and is the material through the dipping post processing to be soaked mould glass-fiber-fabric and import in the heat-setting box, and is not tiled in sticking on the conveyer belt, makes described material soak moulding glass-fiber-fabric to be in free relaxation state and implements the thermal finalization processing; Described thermal finalization the temperature inside the box is controlled in 180 ~ 200 ℃ of scopes, and the thermal finalization processing time is controlled in 1 ~ 1.5min scope;
F, forming processes; Described forming processes is that the material that will process through thermal finalization soaks and moulds glass-fiber-fabric, imports the secondary enforcement of the hot roll of surface temperature 180 ~ 200 ℃ of scopes in hot rolling; Then then import surface temperature and be the roll of normal temperature secondary implement cold rolling; Thereafter make again the continuous glass-fiber-fabric reinforced thermoplastics of the moulding of thickness in 0.4 ~ 1mm scope sheet material through naturally cooling off;
G, rolling; Described rolling is with through the prepared described formed sheet of heat treatment, and coiling is namely finished the production process of described continuous glass-fiber cloth reinforced thermoplastics sheet material;
Describedly unreel, flatten, soak and mould, soak and mould post processing, thermal finalization processing, forming processes, seven steps of rolling, on a production line, carry out continuously; And the travel line speed of described production line is controlled in 3 ~ 4m/min scope.
2. the production method of continuous glass-fiber cloth reinforced thermoplastics sheet material according to claim 1 is characterized in that, described base-material thermoplastic is modified polypropylene plastic.
3. the production method of continuous glass-fiber cloth reinforced thermoplastics sheet material according to claim 1 is characterized in that, described glass-fiber-fabric is that grammes per square metre is at 150 ~ 450g/m
2Plain weave glass-fiber-fabric or twill glass-fiber-fabric or satin weave glass-fiber-fabric; Its fabric construction be twin shaft to or the multi-axial fabric structure; The warp of described glass-fiber-fabric, weft filament be alkali-free without wax without twisting filament.
4. the production method of continuous glass-fiber cloth reinforced thermoplastics sheet material according to claim 1, it is characterized in that, the described glass-fiber-fabric of moulding step that soaks is the fabric guide roll of arranging via a plurality of upper and lower dislocation in dipping box, soaks and moulds and be the motion of serpentine route.
5. the production method of continuous glass-fiber cloth reinforced thermoplastics sheet material according to claim 2 is characterized in that, in described modified polypropylene plastic, also contains a kind of in fire retardant, UV resistant agent and the antioxidant or two kinds or three kinds.
6. the production method of continuous glass-fiber cloth reinforced thermoplastics sheet material according to claim 1, it is characterized in that, described glass-fiber-fabric is to import hot melting plastic to extrude in the case after flattening step, and by the described case discharging opening of extruding, the dipping box that enters impregnation steps with hot melting plastic curtain coating waterfall is implemented dipping.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210490157.8A CN103009639B (en) | 2012-11-27 | 2012-11-27 | Production method of continuous glass fabric reinforced thermoplastic sheet |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210490157.8A CN103009639B (en) | 2012-11-27 | 2012-11-27 | Production method of continuous glass fabric reinforced thermoplastic sheet |
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| CN103009639A true CN103009639A (en) | 2013-04-03 |
| CN103009639B CN103009639B (en) | 2014-12-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104552985A (en) * | 2014-12-24 | 2015-04-29 | 广东生益科技股份有限公司 | Process and device for producing thin prepreg |
| CN105109142A (en) * | 2015-09-09 | 2015-12-02 | 郑州翎羽新材料有限公司 | Composite sheet used for compartment door and method for preparing compartment door by using same |
| CN109454879A (en) * | 2018-12-18 | 2019-03-12 | 振石集团华美新材料有限公司 | The production equipment and its technique of wide door width continuous glass-fiber enhancing thermoplasticity preimpregnation sheet material |
| TWI713814B (en) * | 2018-01-26 | 2020-12-21 | 金財興股份有限公司 | Method and device for manufacturing fiber reinforcement composite |
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| GB825004A (en) * | 1954-09-09 | 1959-12-09 | Minnesota Mining & Mfg | Reinforced resinous structural material |
| JP3997252B1 (en) * | 2006-06-12 | 2007-10-24 | 株式会社神戸製鋼所 | Long fiber reinforced resin strand production equipment |
| CN102218828A (en) * | 2011-05-27 | 2011-10-19 | 常州市宏发纵横新材料科技股份有限公司 | Method for preparing continuous fiber multiaxial fabric reinforced thermoplastic composite material |
| CN202186057U (en) * | 2011-04-15 | 2012-04-11 | 王浩 | Continuous forming production line for FRP (Fiber Reinforce Plastic) glass fibre reinforced plastic boards |
| CN202242003U (en) * | 2011-09-30 | 2012-05-30 | 台州市家得宝日用品有限公司 | Manufacturing equipment for continuous fiber reinforced thermoplastic composite material pre-impregnation band |
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- 2012-11-27 CN CN201210490157.8A patent/CN103009639B/en not_active Expired - Fee Related
Patent Citations (5)
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| GB825004A (en) * | 1954-09-09 | 1959-12-09 | Minnesota Mining & Mfg | Reinforced resinous structural material |
| JP3997252B1 (en) * | 2006-06-12 | 2007-10-24 | 株式会社神戸製鋼所 | Long fiber reinforced resin strand production equipment |
| CN202186057U (en) * | 2011-04-15 | 2012-04-11 | 王浩 | Continuous forming production line for FRP (Fiber Reinforce Plastic) glass fibre reinforced plastic boards |
| CN102218828A (en) * | 2011-05-27 | 2011-10-19 | 常州市宏发纵横新材料科技股份有限公司 | Method for preparing continuous fiber multiaxial fabric reinforced thermoplastic composite material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104552985A (en) * | 2014-12-24 | 2015-04-29 | 广东生益科技股份有限公司 | Process and device for producing thin prepreg |
| CN105109142A (en) * | 2015-09-09 | 2015-12-02 | 郑州翎羽新材料有限公司 | Composite sheet used for compartment door and method for preparing compartment door by using same |
| CN105109142B (en) * | 2015-09-09 | 2017-11-14 | 郑州翎羽新材料有限公司 | A kind of method that hatch door prepares hatch door with composite sheet and using the sheet material |
| TWI713814B (en) * | 2018-01-26 | 2020-12-21 | 金財興股份有限公司 | Method and device for manufacturing fiber reinforcement composite |
| CN109454879A (en) * | 2018-12-18 | 2019-03-12 | 振石集团华美新材料有限公司 | The production equipment and its technique of wide door width continuous glass-fiber enhancing thermoplasticity preimpregnation sheet material |
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| CN103009639B (en) | 2014-12-17 |
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Address after: 213164, building B802, building 1, Changzhou science and Education City, No. 18 middle Wu Road, Wujin District, Jiangsu, Changzhou Patentee after: TRUST NEW MATERIAL TECHNOLOGY Inc. Address before: 213164, building B802, building 1, Changzhou science and Education City, No. 18 middle Wu Road, Wujin District, Jiangsu, Changzhou Patentee before: TRUST NEW MATERIAL TECHNOLOGY Co.,Ltd. |
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Granted publication date: 20141217 Termination date: 20211127 |
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| CF01 | Termination of patent right due to non-payment of annual fee |