CN100534786C - Paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film and its preparation method - Google Patents
Paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film and its preparation method Download PDFInfo
- Publication number
- CN100534786C CN100534786C CNB2007101817306A CN200710181730A CN100534786C CN 100534786 C CN100534786 C CN 100534786C CN B2007101817306 A CNB2007101817306 A CN B2007101817306A CN 200710181730 A CN200710181730 A CN 200710181730A CN 100534786 C CN100534786 C CN 100534786C
- Authority
- CN
- China
- Prior art keywords
- film
- ethylene
- layer
- top layer
- bidirectional stretching
- 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.)
- Active
Links
Images
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention discloses one kind of biaxially stretched polypropylene film with on-line leached layer for no-adhesive paper-plastic combination and its preparation process. The film includes one base film comprising one or two biaxially stretched upper surface layers, one core layer and one or two biaxially stretched lower surface layers, and one functional film layer for direct combination with paper material. The film is prepared through forming melt with the material in an extruder, flow casting the melt to form co-extruded thick sheet, biaxially stretching to form film, corona treatment or flame treatment to form mother film, ageing treatment and cutting into the film product. The biaxially stretched polypropylene film with on-line leached layer for no-adhesive paper-plastic combination has low power consumption, environment friendship, high heat sealing strength and high stripping strength.
Description
Technical field
The present invention relates to a kind of paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film and preparation method thereof.
Background technology
Common bidirectional stretching polypropylene film production technology comprises flat embrane method and bubble pipe method, and especially based on flat embrane method, and flat embrane method is divided into progressively biaxial tension and synchronous bidirectional stretches two kinds, and progressively biaxial tension is a vertically back cross directional stretch of elder generation based on twice stretching; This patent relates to the interior method again of drenching of line in the bidirectional stretching polypropylene film processing method.
At present, the industrial paper composite methods that is applied to mainly contains following several: first glue method (dry method is compound and wet method is compound), yet thereby this method can give off more toxic solvent or fugitive constituent contaminated environment; It two is solvent-free composite algorithms, and the initial bonding strength of this method gained joint product is extremely low; It three is precoating methods, though this method can be without solvent, but belongs to the secondary operations technology of biaxially oriented film, increases cost.In addition, the particularly solvent-free composite algorithm gained of said method joint product adhesive linkage peel strength time dependence is more obvious.Therefore, for overcoming the shortcoming of existing paper complex technique, Chinese patent ZL03226653.7 discloses a kind of paper composite construction, the described paper composite construction of this patent comprises that papery layer and hot pressing are compounded in the plastic film layers on the papery layer, can not have the surface that the glue composite membrane directly is compounded in the papery layer by biaxial stretch-formed polypropylene and realizes.Though this patent discloses a kind of paper plastic glue-free composite construction, but do not disclose concrete composition of described thin layer and preparation method thereof, in actual use, people are difficult to produce accurately reproduction, in the applying in paper complex technique field, has certain degree of difficulty.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and realize that paper plastic glue-free is compound, simplify paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of combination process, energy savings, environmentally-friendly sanitary and good product performance and preparation method thereof.
Goal of the invention of the present invention is achieved in that a kind of paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film, it is characterized in that: this film comprises the following top layer that is provided with in turn, next top layer, sandwich layer, last time the top layer, upper epidermis and by online pouring arrive upper epidermis again can be directly and paper wood, preprint paper wood or contain the compound functional layer of another film hot-pressing of this layer, functional layer is an ethylene-butene copolymer, ethylene-octene copolymer, ethene-butylene-octene copolymer, the modified by maleic acid anhydride graft thing of ethylene-butene copolymer, the modified by maleic acid anhydride graft thing of ethylene-octene copolymer, the modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer or their blend, or above copolymer, modifier, any composition of blend respectively with the blend again of hydrogenated petroleum resin.Wherein, the weight content of the butylene in the ethylene-butene copolymer is 10～30%, the weight content of the octene in the ethylene-octene copolymer is 5～20%, the weight content of the weight content of butylene, octene is respectively 1～30%, 1～20% in ethene-butylene-octene copolymer, and the percent grafting of the modified by maleic acid anhydride graft thing of the modified by maleic acid anhydride graft thing of ethylene-butene copolymer, the modified by maleic acid anhydride graft thing of ethylene-octene copolymer and ethene-butylene-octene copolymer is 0.5～2%.The weight ratio that described functional layer accounts for film is 10～50%.
Described hydrogenated petroleum resin accounts for 1～30% of functional layer gross weight.
Described top layer down is to contain the blend of polypropylene and antiblocking agent or is the blend that contains polypropylene, high density polyethylene (HDPE), antioxidant.
Next top layer, sandwich layer and last time the top layer be and contain isotactic polypropylene or by one or more mixtures formed among isotactic polypropylene and hydrogenated petroleum resin, antistatic additive, the slipping agent.
In described next top layer, sandwich layer and the last time top layer one or more layers contains titanium dioxide.
In described next top layer, sandwich layer and the last time top layer one or more layers contains calcium carbonate and/or polybutylene terephthalate.
In the present invention, described functional layer is through sided corona treatment or flame treatment.
The preparation method of paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of the present invention, its technological process is:
Will be through the main material of screening, masterbatch is pressed the component design premix, stir, resin after metering, send into extruder and be processed into plasticizing, the melt of homogenizing, melt passes through pipeline transmission, filter filters, through the runner distributor to the die head coextrusion, become sheet by curtain coating casting sheet Quench, sheet is earlier through the longitudinal stretching flakiness, thin slice through one group by extruder, die head, the pouring apparatus for coating that deflector roll constitutes, entering becomes film after the cross directional stretch unit stretches again, the thickness of film adopts automatic measuring thickness device control, to improve surface tension, through traction harvest parent roll, parent roll is through Ageing Treatment and cut into finished film with the film after handling through sided corona treatment or flame treatment for film.
The drawing process of described film is the flat embrane method of coextrusion biaxial tension, the temperature of extruder, filter, die head is controlled at 220～270 ℃, curtain coating casting sheet temperature is controlled at 15～40 ℃, the longitudinal stretching cell temperature is controlled at 50～150 ℃, the temperature of the multiple unit of online pouring extruder, filter, die head is controlled at 180～260 ℃, the cross directional stretch cell temperature is controlled at 80～180 ℃, is respectively 4.5～6.5 and 7～10 to draw ratio in length and breadth, and surface treatment intensity is 35～45mN/m.
Adopt paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of said structure and preparation method thereof, its advantage is:
Paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of the present invention and preparation method thereof, it comprises base membrane layer and functional layer, wherein, the upper epidermis that base membrane layer can be common bidirectional stretching polypropylene film or is prepared into by the technical program composition, sandwich layer, following top layer or upper epidermis, last time the top layer, sandwich layer, next top layer, following top layer constitutes, the repeated spraying bidirectional stretching polypropylene film that the described material of the technical program constitutes, its functional layer can be directly and paper wood, preprint paper wood or contain another film hot-pressing of this layer compound, realized the no gel that paper is compound, save coating process, simplify combination process, saved the energy.And compound tense can not produce toxic gas, environmental protection, safety, health.Simultaneously, with the bidirectional stretching polypropylene film that this structure, composition manufacturing form, its heat seal strength is big, with paper wood, preprint paper wood or contain the product that another film hot-pressing of this layer is composited, and the peel strength height, the manufacturing that is beneficial to product is promoted.
Description of drawings
Accompanying drawing 1 is the cross-section structure of an embodiment of the present invention.
Accompanying drawing 2 is the cross-section structure of the another kind of embodiment of the present invention.
Accompanying drawing 3 is the technological process of method for manufacturing thin film of the present invention.
The specific embodiment
The invention will be further described below in conjunction with accompanying drawing.
According to illustrated in figures 1 and 2, paper plastic glue-free composite bidirectional stretching polypropylene film of the present invention, it comprises in turn the following top layer 1 that is provided with, sandwich layer 3, upper epidermis 5 and can be directly and paper wood, preprint paper wood or contain the compound functional layer 6 of another film hot-pressing of this layer.When making this film, top layer 1 was the coextrusion structure through biaxial tension under upper epidermis 5, sandwich layer 3 reached, and had constituted four the most basic layered structures of film of the present invention with this trilamellar membrane body and the multiple functional layer 6 of online pouring, as shown in Figure 1.In addition, be to improve the performance of film, be provided with top layer 4 last time between upper epidermis 5 and the sandwich layer 3, be provided with next top layer 2 between sandwich layer 3 and the following top layer 1, constituted another kind of embodiment of the present invention with this five tunics body and the multiple functional layer 6 of online pouring: six layers of structure, as shown in Figure 2.And functional layer 6 of the present invention, this functional layer 6 is to drench again to upper epidermis 5 on the thin slice of the three-layer co-extruded of longitudinal stretching or five-layer co-squeezing structure.In the present invention, functional layer 6 is an ethylene-butene copolymer, ethylene-octene copolymer, ethene-butylene-octene copolymer, the modified by maleic acid anhydride graft thing of ethylene-butene copolymer, the modified by maleic acid anhydride graft thing of ethylene-octene copolymer, the modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer or above copolymer, modifier, any composition of blend respectively with the blend again of hydrogenated petroleum resin, wherein, butene content in the ethylene-butene copolymer is 10～30%, octene content in the ethylene-octene copolymer is 5～20%, butene content is 1～30% in ethene-butylene-octene copolymer, octene content is 1～20%, the modified by maleic acid anhydride graft thing of ethylene-butene copolymer, the percent grafting of the modified by maleic acid anhydride graft thing of ethylene-octene copolymer and the modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer is 0.5～2%, wherein, when functional layer 6 contained hydrogenated petroleum resin, hydrogenated petroleum resin accounted for 1～30% of functional layer 6 gross weights.And following top layer 1 is to contain the blend of polypropylene and antiblocking agent or is the blend that contains polypropylene, high density polyethylene (HDPE), antioxidant.Polypropylene is that polypropylene is isotactic polypropylene, co-polypropylene (as ethylene-propylene copolymer, ethylene-propylene-butylene copolymer).No matter film of the present invention is four-layer structure or six layers of structure, and functional layer 6 all accounts for 10～50% of film weight.Above-mentioned antistatic additive can be glycerin monostearate, two (beta-hydroxyethyl) octadecylamine, and slipping agent can be erucyl amide, oleamide, di-2-ethylhexylphosphine oxide stearmide (EBS); Hydrogenated petroleum resin can be carbon-5 series products or carbon-9 series products, the CLEARON board product P-125 of the latter such as Japanese YAKUHARA company, the former is as the effective ingredient among the firm agent PA609 of increasing of EXXON-MOBIL company (being designated as EM609 for ease of the statement this patent); Antiblocking agent is silica (SiO2), polymethyl methacrylate (PMMA) etc.; Antioxidant is 1010,1076 etc.
In addition, according to different manufacturing requirements, next top layer 2, sandwich layer 3 and last time top layer 4 be contain isotactic polypropylene or by one or more compositions among isotactic polypropylene and hydrogenated petroleum resin, antistatic additive, the slipping agent according to the identical or hyaline layer formed of different proportion separately; The second, one or more layers in next top layer 2, sandwich layer 3 and the last time top layer 4 contains titanium dioxide; The 3rd, one or more layers in next top layer 2, sandwich layer 3 and the last time top layer 4 contains calcium carbonate and/or polybutylene terephthalate.
As shown in Figure 3, method for manufacturing thin film of the present invention, its technological process is:
Among the figure: A is raw material (comprising main material, modified materials, additive masterbatch), B is a melt, C is a sheet, and D is a film, and E is a finished product, F is that extruder is extruded operation, G be die head, curtain coating casting sheet chilling device to the melt forming operation, H is the longitudinal stretching operation, I is that return to work preface, J of online pouring is that cross directional stretch operation, K are sided corona treatment or flame treatment operation, L is a winding process, and M is Ageing Treatment, branch cutting process.
To press the component design premix through the raw material A (comprising main material, additive masterbatch) of screening, stir, resin is sent into the melt B that extruder processing F becomes plasticizing, homogenizing after metering, melt B is filtered by pipeline transmission, filter, be assigned to the die head coextrusion through runner,, the melt B Quench become sheet C by curtain coating casting sheet Quench molding procedure G, sheet C is through longitudinal stretching H, the multiple I of online pouring is to thin slice upper epidermis 5, and then, film body is drawn into film D through cross directional stretch operation J.The thickness of film D adopts automatic measuring thickness device control, and film D to improve surface tension, becomes parent roll with the film after handling through traction rolling L through sided corona treatment or flame treatment K, and parent roll is through Ageing Treatment and cut M and become finished film E.Wherein:
The drawing process of film is co-extruding biaxial stretched flat embrane method, the temperature of extruder, filter, die head is controlled at 220～270 ℃, curtain coating casting sheet temperature is controlled at 15～40 ℃, the longitudinal stretching cell temperature is controlled at 50～150 ℃, the temperature of the multiple unit of online pouring extruder, filter, die head is controlled at 180～260 ℃, the cross directional stretch cell temperature is controlled at 80～180 ℃, is respectively 4.5～6.5 and 7～10 to draw ratio in length and breadth, and surface treatment intensity is 35～45mN/m.
Illustrate 1: the standard of properties of product test institute foundation sees the following form in following examples:
| Physical property | Unit | Testing standard |
| Thickness | μm | ASTM D892 |
| Density | g/cm 3 | ASTM D792 |
| Mist degree | ％ | ASTM D1003 |
| Whiteness | ％ | ASTM E313 |
| Light transmittance | ％ | ASTM D1003 |
| Glossiness | ％ | ASTM D2457 |
| Hot strength | MPa | ASTM D882 |
| Elongation at break | ％ | ASTM D882 |
| Wetting tension | dyne/cm | ASTM D2578 |
| Heat seal strength | N/15mm | ASTM F2029 |
| Percent thermal shrinkage (120 ℃, 2 minutes) | ％ | ASTM D1204 |
| Peel strength (film/paper material) | N/15mm | With reference to ASTM D903 * |
*Annotate: under 23 ℃/50% humidity environment, allow film function face and wide 15mm, grammes per square metre 300g/cm
3The front of ash end art post paperboard (" Foshan Hua Feng paper industry " produces) batten is at 115 ℃, and involution is 60 seconds under the 0.30MPa condition, cools off after 3 minutes, presses ASTM D903 standard testing.
Illustrate 2: percentage of filling a prescription described in following examples or percentage composition all refer to percetage by weight.
Illustrate 3: in following examples, the melt index of functional layer 6 described compositions (2.16 kilograms, 190 ℃) is respectively: ethylene-butene copolymer: 4.5 grams/10 minutes; Ethylene-octene copolymer: 7 grams/10 minutes; Ethene-butylene-octene copolymer: 5 grams/10 minutes; The modified by maleic acid anhydride graft thing of ethylene-butene copolymer: 3.5 grams/10 minutes; The modified by maleic acid anhydride graft thing of ethylene-octene copolymer: 5.5 grams/10 minutes; The modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer: 4 grams/10 minutes.
Embodiment 1:
The composition of functional layer 6 is: the modified by maleic acid anhydride graft thing of 70% ethylene-butene copolymer, 30% ethylene-butene copolymer, wherein, the content of butylene is 30% in the ethylene-butene copolymer, and the percent grafting of the modified by maleic acid anhydride graft thing of ethylene-butene copolymer is 0.5%.
The composition of upper epidermis 5 is: 100% isotactic polypropylene (isotacticity is 95%, melt index is 3 grams/10 minutes);
The composition of sandwich layer 3 is: 99.75% isotactic polypropylene (isotacticity is 97%, melt index is 3 grams/10 minutes), 2500ppm glycerin monostearate;
The composition on following top layer 1 is: by the high density polyethylene (HDPE) that accounts for top layer 99.2% (melt index is 0.05 gram/10 minutes) and the blend of ethylene-propylene copolymer (melt index is 7 grams/10 minutes), the antioxidant 1010 of 8000ppm of configuration in 9: 11.
The gross thickness of prepared product is 20 μ m, functional layer 6 thick 6 μ m, and functional layer 6 accounts for 30% of film gross weight.
The preparation method is: will press the component design premix through the raw material A (comprising main material, additive masterbatch) of screening, stir, resin after metering, send into the melt B that extruder processing F becomes plasticizing, homogenizing, melt filters by pipeline transmission, filter, is assigned to the die head coextrusion through runner, G becomes sheet C by curtain coating casting sheet, sheet is through longitudinal stretching H, and the multiple I of online pouring is to thin slice upper epidermis 5, and cross directional stretch J becomes film D.The thickness of film D adopts automatic measuring thickness device control, and to improve surface tension, through traction harvest L parent roll, parent roll is through Ageing Treatment and cut M and become finished film E with the film after handling through sided corona treatment or flame treatment K for film.Wherein, the flat embrane method bidirectional stretching polypropylene film production line that equipment provides for German Brueckner company, the main extruder screw diameter is 150mm, draw ratio is 33: 1 a single screw extrusion machine, auxiliary extruder screw diameter is 90mm, and draw ratio is 30: 1 a single screw extrusion machine.Extruder temperature is 100 ℃ except that the feeding section, and other each section is 245 ℃, filter and respectively distinguishes temperature and be 250 ℃, die head and respectively distinguish temperature and be 235 ℃; Quenching (curtain coating casting sheet) temperature is 25 ℃; The longitudinal stretching preheating is respectively distinguished temperature and is 130 ℃, stretches and respectively to distinguish temperature and be 135 ℃ of 110 ℃, setting temperature, and draw ratio is 4.9; The multiple extruder screw diameter of online pouring is 120mm, and draw ratio is 35: 1 a single screw extrusion machine, and extruder temperature is 200 ℃ except that the feeding section, and other each section is 250 ℃, filter and respectively distinguishes temperature and be 260 ℃, die head and respectively distinguish temperature and be 245 ℃; The cross directional stretch temperature: respectively the district is 175 ℃, each district that stretches is 160 ℃, each district of finalizing the design is 165 ℃ in preheating, and draw ratio is 9; Sided corona treatment power is 22wmin./m
2
The properties of product of manufacturing are as follows:
(1) thickness: 20 μ m
(2) density (extinction type): 0.83g/cm
3
(3) hot strength (vertically/laterally): 90MPa/130MPa
(4) heat seal strength: 7.0N/15mm
(5) peel strength (film-paper wood): 3.5N/15mm
(6) mist degree: 76.2%
(7) glossiness: 8.5%
(8) percent thermal shrinkage (vertically/laterally): 3.5%/1.5%
(9) surface tension: 40mN/m
Embodiment 2:
The composition of functional layer 6 is: the modified by maleic acid anhydride graft thing of 50% ethylene-butene copolymer, 20% ethylene-butene copolymer, 30% P-125, wherein, the content of butylene is 10% in the ethylene-butene copolymer, and the percent grafting of the modified by maleic acid anhydride graft thing of ethylene-butene copolymer is 1.2%.
The composition of upper epidermis 5 is: 100% isotactic polypropylene (isotacticity is 95%, melt index is 3 grams/10 minutes);
Next time top layer 2, last time, top layer 4 composition was: the glycerin monostearate of 99.8% isotactic polypropylene (isotacticity is 96%, melt index be 2.5 grams/10 minutes), 2000ppm;
The composition of sandwich layer 3 is: 99.7% isotactic polypropylene (isotacticity is 96%, melt index is 2.5 grams/10 minutes), the glycerin monostearate of 2000ppm, the di-2-ethylhexylphosphine oxide stearmide of 1000ppm;
The composition on following top layer 1 is: the antiblocking agent SiO2 of 99.8% isotactic polypropylene (isotacticity is 95%, and melt index restrains/10 minutes 3), 2000ppm.
The gross thickness of prepared product is 18 μ m, functional layer 6 thick 5 μ m, and functional layer 6 accounts for 27.8% of film gross weight.
Identical with embodiment 1 with other content except that the extruder of coextrusion among the preparation method, the extruder parameter of coextrusion is respectively:
Main extruder is the tandem single screw extrusion machine:
Screw diameter: melt extrude machine 160mm, metering extruder 160mm
Draw ratio: melt extruded machine 20: 1, metering extruder 20: 1
Auxiliary extruder is a single screw extrusion machine:
Screw diameter: 65mm
Draw ratio: 30: 1
The properties of product of manufacturing are as follows:
(1) thickness: 18 μ m
(2) density (brightening type): 0.9g/cm
3
(3) hot strength (vertically/laterally): 110MPa/200MPa
(4) heat seal strength: 6.0N/15mm
(5) peel strength (film-paper wood): 3.2N/15mm
(6) mist degree: 1.2%
(7) percent thermal shrinkage (vertically/laterally): 2.0%/1.2%
(8) surface tension: 40mN/m
Embodiment 3:
The composition of functional layer 6 is: the modified by maleic acid anhydride graft thing of 80% ethylene-octene copolymer, 19% ethylene-butene copolymer, 1% P-125, wherein, octene content is 20% in the ethylene-octene copolymer, and the percent grafting of the modified by maleic acid anhydride graft thing of ethylene-butene copolymer is 2%.
The composition of upper epidermis 5 is: 100% isotactic polypropylene (isotacticity is 95%, melt index is 3 grams/10 minutes);
Next time top layer 2, last time, top layer 4 composition was: the glycerin monostearate of 99.8% isotactic polypropylene (isotacticity is 95%, melt index be 2 grams/10 minutes), 2000ppm;
The composition of sandwich layer 3 is: 99.75% isotactic polypropylene (isotacticity is 95%, melt index is 2 grams/10 minutes), the glycerin monostearate of 2000ppm, the erucyl amide of 500ppm;
The composition on following top layer 1 is: the antiblocking agent SiO2 of 99.8% isotactic polypropylene (isotacticity is 95%, and melt index restrains/10 minutes 3), 2000ppm.
The gross thickness of prepared product is 18 μ m, functional layer 6 thick 5.4 μ m, and functional layer 6 accounts for 30% of film gross weight.
Identical with embodiment 1 with other content except that the extruder of coextrusion among the preparation method, the extruder parameter of coextrusion is respectively:
Main extruder is the tandem single screw extrusion machine:
Screw diameter: melt extrude machine 230mm, metering extruder 275mm
Draw ratio: melt extruded machine 20: 1, metering extruder 20: 1
Auxiliary extruder is a single screw extrusion machine:
Screw diameter: 90mm
Draw ratio: 33: 1
The properties of product of manufacturing are as follows:
(1) thickness: 18 μ m
(2) density (brightening type): 0.9g/cm
3
(3) hot strength (vertically/laterally): 100MPa/180MPa
(4) heat seal strength: 6.3N/15mm
(5) peel strength (film-paper wood): 3.8N/15mm
(6) mist degree: 1.5%
(7) percent thermal shrinkage (vertically/laterally): 3.0%/1.0%
(8) surface tension: 40mN/m
Embodiment 4:
The composition of functional layer 6 is: the modified by maleic acid anhydride graft thing of 20% ethylene-butene copolymer, 45% ethylene-octene copolymer, 20% ethylene-octene copolymer, 15% P-125, wherein, butene content is 25% in the ethylene-butene copolymer, octene content is 5% in the ethylene-octene copolymer, and the percent grafting of the modified by maleic acid anhydride graft thing of ethylene-octene copolymer is 0.5%.
The composition of upper epidermis 5 is: 100% isotactic polypropylene (isotacticity is 95%, melt index is 3 grams/10 minutes);
Next time top layer 2, last time, top layer 4 composition was: 100% isotactic polypropylene (isotacticity is 94%, and melt index is 3.5 grams/10 minutes);
The composition of sandwich layer 3 is: 80% isotactic polypropylene (isotacticity is 94%, and melt index is 3.5 grams/10 minutes), 19.8% P-125, the glycerin monostearate of 2000ppm;
The composition on following top layer 1 is: by the polyethylene that accounts for top layer 99.1% of configuration in 9: 11 and the antioxidant 1010 of polypropylene blend, 9000ppm.
The gross thickness of prepared product is 18 μ m, functional layer 6 thick 7.2 μ m, and functional layer 6 accounts for 40% of film gross weight.
Identical with embodiment 1 with other content except that the extruder of coextrusion among the preparation method, the extruder parameter of coextrusion is respectively:
Main extruder is a double screw extruder:
Screw diameter: 169mm, 169mm
Draw ratio: 32: 1,32: 1
Auxiliary extruder is a single screw extrusion machine:
Screw diameter: 120mm
Draw ratio: 33: 1
The properties of product of manufacturing are as follows:
(1) thickness: 18 μ m
(2) density (extinction type): 0.83g/cm
3
(3) hot strength (vertically/laterally): 90MPa/170MPa
(4) heat seal strength: 5.5N/15mm
(5) peel strength (film-paper wood): 4.7N/15mm
(6) mist degree: 1.8%
(7) percent thermal shrinkage (vertically/laterally): 3.0%/1.5%
(8) surface tension: 40mN/m
Embodiment 5:
The composition of upper epidermis 5, functional layer 6 is: the modified by maleic acid anhydride graft thing of 60% ethylene-octene copolymer, ethene-butylene of 20%-octene copolymer, 10% ethylene-octene copolymer, 10% P-125, wherein, octene content is 10% in the ethylene-octene copolymer, butene content is 1% in ethene-butylene-octene copolymer, octene content is 20%, and the percent grafting of the modified by maleic acid anhydride graft thing of ethylene-octene copolymer is 1.2%.
Next time top layer 2, last time, top layer 4 composition was: 100% isotactic polypropylene (isotacticity is 96.5%, melt index be 2.8 grams/10 minutes);
The composition of sandwich layer 3 is: 100% isotactic polypropylene (isotacticity is 96.5%, melt index is 2.8 grams/10 minutes);
The composition on following top layer 1 is: the antiblocking agent PMMA of 99.8% isotactic polypropylene (isotacticity is 96.5%, melt index is 2.8 grams/10 minutes), 2000ppm.
The gross thickness of prepared product is 40 μ m, functional layer 6 thick 20 μ m, and functional layer 6 accounts for 50% of film gross weight.
Except that flat embrane method bidirectional stretching polypropylene film production line supplier, extruder type and parameter, miscellaneous equipment and control parameter are identical with embodiment 1 among the preparation method.Production line supplier is Mitsubishi heavy industry (MHI) Co., Ltd., and main extruder and auxiliary extruder parameter are respectively:
Main extruder is the tandem single screw extrusion machine, and the screw rod parameter is:
Melt extrude machine: diameter is 115mm, and draw ratio is 20: 1
The metering extruder: diameter is 115mm, and draw ratio is 20: 1
Auxiliary extruder is that screw diameter is 120mm, and draw ratio is 30: 1 a single screw extrusion machine.
The specific performance of prepared product is:
(1) thickness: 40 μ m
(2) density (brightening type): 0.9g/cm
3
(3) hot strength (vertically/laterally): 90MPa/170MPa
(4) heat seal strength: 12.0N/15mm
(5) peel strength (film-paper wood): 5.8N/15mm
(6) mist degree: 3.5%
(7) percent thermal shrinkage (vertically/laterally): 3.8%/1.4%
(8) surface tension: 40mN/m
Embodiment 6:
The composition of functional layer 6 is: the modified by maleic acid anhydride graft thing of 20% ethylene-butene copolymer, 20% ethylene-octene copolymer, 30% ethylene-octene copolymer, the modified by maleic acid anhydride graft thing of ethene-Ding-octene copolymer of 10%, 20% EM609, wherein, butene content is 20% in the ethylene-butene copolymer, octene content is 15% in the ethylene-octene copolymer, the percent grafting of the modified by maleic acid anhydride graft thing of ethylene-octene copolymer is 2%, and the percent grafting of the modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer is 0.5%.
The composition of upper epidermis 5 is: 100% isotactic polypropylene (isotacticity is 97.5%, melt index is 3.2 grams/10 minutes);
Next time top layer 2, last time, the top layer 4 was 99.85% isotactic polypropylene (isotacticity is 97.5%, and melt index is 3.2 grams/10 minutes), two (beta-hydroxyethyl) octadecylamine of 500ppm, the oleamide of 1000ppm;
The composition of sandwich layer 3 is: 99.85% isotactic polypropylene (isotacticity is 97.5%, and melt index is 3.2 grams/10 minutes), the glycerin monostearate of 500ppm, the oleamide of 1000ppm;
The composition on following top layer 1 is: the antiblocking agent SiO2 of 99.8% isotactic polypropylene (isotacticity is 97.5%, and melt index is 3.2 grams/10 minutes), 2000ppm.
The gross thickness of prepared product is 18 μ m, functional layer 6 thick 5 μ m, and functional layer 6 accounts for 27.8% of film gross weight.
The preparation method is identical with embodiment 2, and the properties of product of manufacturing are as follows:
(1) thickness: 18 μ m
(2) density (brightening type): 0.9g/cm
3
(3) hot strength (vertically/laterally): 105MPa/190MPa
(4) heat seal strength: 5.0N/15mm
(5) peel strength (film-paper wood): 3.4N/15mm
(6) mist degree: 1.4%
(7) percent thermal shrinkage (vertically/laterally): 2.5%/1.1%
(8) surface tension: 40mN/m
Bidirectional stretching polypropylene film by the foregoing description 1 to 6 described structure, composition and preparation method's production, it is simple in structure, and heat seal strength is big, with paper wood, preprint paper wood or contain the product that another film hot-pressing of this layer is composited, the peel strength height, the manufacturing that is beneficial to product is promoted.
Embodiment 7:
The composition of functional layer 6 is: the modified by maleic acid anhydride graft thing of ethene-butylene of 60%-octene copolymer, ethene-butylene-octene copolymer of 15%, 25% EM609, wherein, the content of butylene is 30% in ethene-butylene-octene copolymer, octene content is 1%, and the percent grafting of the modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer is 1.2%.
The composition of upper epidermis 5 is: 100% isotactic polypropylene (isotacticity is 95%, melt index is 3 grams/10 minutes);
Next time top layer 2, last time, top layer 4 composition was: 70% isotactic polypropylene (isotacticity is 95.5%, and melt index is 2.8 grams/10 minutes), 14% EM609,14% calcium carbonate, 2% titanium dioxide;
The composition of sandwich layer 3 is: 70% isotactic polypropylene (isotacticity is 95.5%, and melt index is 2.8 grams/10 minutes), 12% EM609,14% calcium carbonate, 4% titanium dioxide;
The composition on following top layer 1 is: the antiblocking agent SiO2 of 99.8% isotactic polypropylene (isotacticity is 95%, and melt index is 3 grams/10 minutes), 2000ppm.
The gross thickness of prepared product is 47 μ m, functional layer 6 thick 7 μ m, and functional layer 6 accounts for 21.5% of film gross weight.
The preparation method is: will press the component design premix through the raw material A (comprising main material, modified materials, additive masterbatch) of screening, stir, resin after metering, send into the melt B that extruder is processed into plasticizing, homogenizing F, melt filters by pipeline transmission, filter, be assigned to the die head coextrusion through runner, become sheet C by quenching (curtain coating casting sheet) G, sheet becomes film D through two-way (earlier vertically more laterally or in length and breadth to synchronously) stretching H.The thickness of film D adopts automatic measuring thickness device control, and to improve surface tension, through traction harvest parent roll, cut I at last and become finished film E through Ageing Treatment with the film after handling by parent roll through sided corona treatment or flame treatment for film.Wherein, the flat embrane method bidirectional stretching polypropylene film production line that equipment provides for German Brueckner company, the main extruder screw diameter is 150mm, draw ratio is 33: 1 a single screw extrusion machine, auxiliary extruder screw diameter is 90mm, and draw ratio is 30: 1 a single screw extrusion machine.Extruder temperature is 180 ℃ except that the feeding section, and other each section is 245 ℃, filter and respectively distinguishes temperature and be 250 ℃, die head and respectively distinguish temperature and be 230 ℃; Quenching (curtain coating casting sheet) temperature is 23 ℃; The longitudinal stretching preheating is respectively distinguished temperature and is 130 ℃, stretches and respectively to distinguish temperature and be 135 ℃ of 110 ℃, setting temperature, and draw ratio is 5.6; The multiple extruder screw diameter of online pouring is 120mm, and draw ratio is 35: 1 a single screw extrusion machine, and extruder temperature is 200 ℃ except that the feeding section, and other each section is 250 ℃, filter and respectively distinguishes temperature and be 260 ℃, die head and respectively distinguish temperature and be 250 ℃; The cross directional stretch temperature: respectively the district is 175 ℃, each district that stretches is 161 ℃, each district of finalizing the design is 170 ℃ in preheating, and draw ratio is 9; Sided corona treatment power is 30wmin./m
2
The properties of product of manufacturing are as follows:
(1) thickness: 47 μ m
(2) density: 0.65g/cm
3
(3) hot strength (vertically/laterally): 90MPa/160MPa
(4) heat seal strength: 9.0N/15mm
(5) peel strength (film-paper wood): 5.1N/15mm
(6) light transmittance: 20%
(7) whiteness: 90%
(8) percent thermal shrinkage (vertically/laterally): 2.2%/0.5%
(9) surface tension: 41mN/m
Embodiment 8:
The composition of functional layer 6 is: the modified by maleic acid anhydride graft thing of ethene-butylene of 80%-octene copolymer, 20% ethene-butylene-octene copolymer, wherein, the content of butylene is 15% in ethene-butylene-octene copolymer, octene content is 10%, and the percent grafting of the modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer is 2%.
The composition of upper epidermis 5 is: 100% isotactic polypropylene (isotacticity is 95%, melt index is 3 grams/10 minutes);
Next time top layer 2, last time, top layer 4 composition was: 92% isotactic polypropylene (isotacticity is 94.5%, and melt index is 2.2 grams/10 minutes), 4% polybutylene terephthalate, 4% titanium dioxide;
The composition of sandwich layer 3 is: 60% isotactic polypropylene (isotacticity is 94.5%, and melt index is 2.2 grams/10 minutes), 20% EM609,12% calcium carbonate, 8% polybutylene terephthalate;
The composition on following top layer 1 is: by the high density polyethylene (HDPE) that accounts for top layer 99.1% (melt index is 0.05 gram/10 minutes) and the blend of ethylene-propylene-butylene copolymer (melt index is 7.5 grams/10 minutes), the antioxidant 1010 of 6000ppm, the antioxidant 1076 of 3000ppm of configuration in 9: 11.
The gross thickness of prepared product is 60 μ m, functional layer 6 thick 5.3 μ m, and functional layer 6 accounts for 10% of film gross weight.
The preparation method is: will press the component design premix through the raw material A (comprising main material, modified materials, additive masterbatch) of screening, stir, resin after metering, send into the melt B that extruder is processed into plasticizing, homogenizing F, melt filters by pipeline transmission, filter, be assigned to the die head coextrusion through runner, become sheet C by quenching (curtain coating casting sheet) G, sheet becomes film D through two-way (earlier vertically more laterally or in length and breadth to synchronously) stretching H.The thickness of film D adopts automatic measuring thickness device control, and to improve surface tension, through traction harvest parent roll, cut I at last and become finished film E through Ageing Treatment with the film after handling by parent roll through sided corona treatment or flame treatment for film.Wherein, the flat embrane method bidirectional stretching polypropylene film production line that equipment provides for German Brueckner company, the main extruder screw diameter is 150mm, draw ratio is 33: 1 a single screw extrusion machine, auxiliary extruder screw diameter is 90mm, and draw ratio is 30: 1 a single screw extrusion machine.Extruder temperature is 180 ℃ except that the feeding section, and other each section is 245 ℃, filter and respectively distinguishes temperature and be 250 ℃, die head and respectively distinguish temperature and be 235 ℃; Quenching (curtain coating casting sheet) temperature is 25 ℃; The longitudinal stretching preheating is respectively distinguished temperature and is 135 ℃, stretches and respectively to distinguish temperature and be 140 ℃ of 110 ℃, setting temperature, and draw ratio is 5.5; The multiple extruder screw diameter of online pouring is 120mm, and draw ratio is 35: 1 a single screw extrusion machine, and extruder temperature is 200 ℃ except that the feeding section, and other each section is 250 ℃, filter and respectively distinguishes temperature and be 260 ℃, die head and respectively distinguish temperature and be 250 ℃; The cross directional stretch temperature: respectively the district is 175 ℃, each district that stretches is 162 ℃, each district of finalizing the design is 168 ℃ in preheating, and draw ratio is 9; Sided corona treatment power is
28w·min.
2。
The properties of product of manufacturing are as follows:
(1) thickness: 60 μ m
(2) density: 0.62g/cm
3
(3) hot strength (vertically/laterally): 90MPa/180MPa
(4) heat seal strength: 5.5N/15mm
(5) peel strength (film-paper wood): 4.1N/15mm
(6) light transmittance: 17%
(7) whiteness: 90%
(8) percent thermal shrinkage (vertically/laterally): 2.8%/1.3%
(9) surface tension: 41mN/m
By the bidirectional stretching polypropylene film that the foregoing description 7 to 8 described structures, composition and preparation method produce, its heat seal strength is big, is used for the packing of seed, feed, plastic pellet after compound with paper wood hot pressing such as brown paper; With the product that another film hot-pressing that contains this functional layer 6 is composited, whiteness height, light-proofness is good, and the peel strength height can be used as synthetic paper, is widely used in label, handbag, packages printing base material.
Claims (10)
1. paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film, it is characterized in that: this film comprises the following top layer (1) that is provided with in turn, next top layer (2), sandwich layer (3), top layer last time (4), upper epidermis (5) and by online pouring arrive upper epidermis (5) again can be directly and paper wood, preprint paper wood or contain the compound functional layer (6) of another film hot-pressing of this layer, functional layer (6) is an ethylene-butene copolymer, ethylene-octene copolymer, ethene-butylene-octene copolymer, the modified by maleic acid anhydride graft thing of ethylene-butene copolymer, the modified by maleic acid anhydride graft thing of ethylene-octene copolymer, the modified by maleic acid anhydride graft thing of ethene-butylene-octene copolymer or their blend, or above copolymer, modifier, any composition of blend respectively with the blend again of hydrogenated petroleum resin, and its feature is as follows:
(i) weight content of butylene is 10～30% in the ethylene-butene copolymer, and the weight content of octene is 5～20% in the ethylene-octene copolymer; The weight content of butylene is 1～30% in ethene-butylene-octene copolymer, the weight content of octene is 1～20%;
(ii). the percent grafting of the modified by maleic acid anhydride graft thing of the modified by maleic acid anhydride graft thing of ethylene-butene copolymer, the modified by maleic acid anhydride graft thing of ethylene-octene copolymer, ethene-butylene-octene is 0.5～2%;
The weight ratio that (iii) described functional layer accounts for film is 10～50%.
2. according to the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 1, it is characterized in that: described hydrogenated petroleum resin accounts for 1～30% of functional layer (6) gross weight.
3. according to the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 1, it is characterized in that: described top layer (1) down is to contain the blend of polypropylene and antiblocking agent or is the blend that contains polypropylene, high density polyethylene (HDPE), antioxidant.
4. according to the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 1, it is characterized in that: sandwich layer (3) is for isotactic polypropylene or for by one or more mixtures formed among isotactic polypropylene and hydrogenated petroleum resin, antistatic additive, the slipping agent.
5. according to the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 1, it is characterized in that: described next top layer (2) and top layer last time (4) are for isotactic polypropylene or for by one or more mixtures formed among isotactic polypropylene and hydrogenated petroleum resin, antistatic additive, the slipping agent.
6. according to the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 1, it is characterized in that: one or more layers in described next top layer (2), described sandwich layer (3) and top layer last time (4) contains titanium dioxide.
7. according to the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 2, it is characterized in that: one or more layers in described next top layer (2), described sandwich layer (3) and top layer last time (4) contains calcium carbonate and/or polybutylene terephthalate.
8. according to the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 1, it is characterized in that: described functional layer (6) is through sided corona treatment or flame treatment.
9. preparation method according to the paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 1, its technological process is:
Will be through the main material of screening, masterbatch is pressed the component design premix, stir, resin after metering, send into extruder and be processed into plasticizing, the melt of homogenizing, melt passes through pipeline transmission, filter filters, through the runner distributor to the die head coextrusion, become sheet by curtain coating casting sheet Quench, sheet is earlier through the longitudinal stretching flakiness, thin slice through one group by extruder, die head, the pouring film device that deflector roll constitutes, entering becomes film after the cross directional stretch unit stretches again, the thickness of film adopts automatic measuring thickness device control, through traction harvest parent roll, parent roll cuts into finished film at last through Ageing Treatment with film.
10, according to the preparation method of the described paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film of claim 9, it is characterized in that: described film must be handled through sided corona treatment or flame treatment operation before the harvest parent roll.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101817306A CN100534786C (en) | 2007-08-16 | 2007-10-23 | Paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film and its preparation method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710029806.3 | 2007-08-16 | ||
| CN200710029806 | 2007-08-16 | ||
| CNB2007101817306A CN100534786C (en) | 2007-08-16 | 2007-10-23 | Paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101148105A CN101148105A (en) | 2008-03-26 |
| CN100534786C true CN100534786C (en) | 2009-09-02 |
Family
ID=39248854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101817306A Active CN100534786C (en) | 2007-08-16 | 2007-10-23 | Paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100534786C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11123964B2 (en) | 2013-03-18 | 2021-09-21 | Dow Global Technologies Llc | Film composition for paper thermal lamination application |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101396892B (en) * | 2008-10-22 | 2013-05-01 | 北京康得新复合材料股份有限公司 | Metallization biaxial stretching polyester (BOPET) pre-coating film using chemical treatment |
| CN102732174B (en) * | 2012-06-26 | 2013-12-18 | 北京康得新复合材料股份有限公司 | Pre-coating film and preparation method for same |
| CN102806735A (en) * | 2012-08-30 | 2012-12-05 | 江苏奔多新材料有限公司 | High-fastness aluminum plating polypropylene (PP) film and production process thereof |
| CN102873953B (en) * | 2012-09-13 | 2016-02-03 | 北京康得新复合材料股份有限公司 | Without the preparation method of silane coupling agent pre-coating film and bidirectional stretching polypropylene film thereof and this polypropylene film |
| CN103172987A (en) * | 2013-03-11 | 2013-06-26 | 常州百佳薄膜科技有限公司 | Antiblocking parent stock for optical base film, and preparation method thereof |
| CN105985576A (en) * | 2015-02-15 | 2016-10-05 | 江苏朗博高新科技材料有限公司 | Smooth master batch used for BOPP films |
| CN106003995A (en) * | 2016-05-20 | 2016-10-12 | 合肥徽宝包装有限公司 | Making process of plastic thin film |
| CN106003981A (en) * | 2016-05-20 | 2016-10-12 | 合肥徽宝包装有限公司 | Plastic thin film making method |
| CN113752585A (en) * | 2021-08-23 | 2021-12-07 | 苏州市和好塑业有限公司 | Direct-spraying PP (propene Polymer) process for reducing glue layer of plastic box |
| CN114148065B (en) * | 2021-12-01 | 2022-08-26 | 广东德冠包装材料有限公司 | Moisture-resistant double-pulled polypropylene pearl label base film and preparation method thereof |
| CN114379183B (en) * | 2022-01-13 | 2024-04-23 | 广东德冠包装材料有限公司 | Repeatedly-usable polyurethane transfer film and preparation method thereof |
| CN114454581A (en) * | 2022-02-11 | 2022-05-10 | 云阳金田塑业有限公司 | Environment-friendly mail-order express delivery film and preparation method thereof |
-
2007
- 2007-10-23 CN CNB2007101817306A patent/CN100534786C/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11123964B2 (en) | 2013-03-18 | 2021-09-21 | Dow Global Technologies Llc | Film composition for paper thermal lamination application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101148105A (en) | 2008-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100534786C (en) | Paper plastic glue-free composite on line repeated spraying bidirectional stretching polypropylene film and its preparation method | |
| CN100534787C (en) | Paper plastic glue-free composite bidirectional stretching polypropylene film and preparation method thereof | |
| CN100566994C (en) | A kind of paper plastic glue-free composite bidirectional stretching polypropylene film and preparation method thereof | |
| RU2426651C2 (en) | Biaxially-oriented polypropylene film for direct-bonding lamination on paper and method of its production | |
| US6423420B1 (en) | Oriented coextruded films | |
| DE69426490T2 (en) | Chlorine-free composite film material, process for its production and its use | |
| US20220402252A1 (en) | Multilayer structure | |
| EP1885558B2 (en) | Coextruded multi-layer barrier film having at least one film ply of ethylene-vinyl alcohol copolymer (evoh), method of producing it, and its use | |
| EP0963408B1 (en) | Oriented coextruded films | |
| JP3350872B2 (en) | Matte biaxially stretched polypropylene film and method for producing the same | |
| US7799418B2 (en) | Transverse-direction, elastomeric, breathable film | |
| CN106183292A (en) | Three-layer co-extruded quick biaxial tension wide cut polyethylene co-extruded film and preparation method thereof | |
| CN1232475A (en) | High density polyethylene film with high biaxial orientation | |
| CN108463347A (en) | The cavitation linea low density film of double orientation with good seal performance | |
| US6749948B2 (en) | Polyolefin film with peelable outer layer | |
| EP2528737B2 (en) | Matt polyolefin film having release properties | |
| CN100548670C (en) | A kind of paper plastic glue-free composite off line repeated spraying bidirectional stretching polypropylene film | |
| EP4209331A1 (en) | Biaxially oriented polyethylene sheets for thermoforming, process for their manufacture, their use, a thermoforming process and products thereof | |
| CN101298202A (en) | Stretching film for low temperature heat sealing between paper and plastic film or between plastic films and manufacturing method thereof | |
| EP0983142B1 (en) | Polypropylene/polystyrene multilayer film structures | |
| US6451446B1 (en) | Polypropylene/polystyrene multilayer film structures | |
| CN113146993A (en) | Method for producing stretched label film | |
| CN107031156B (en) | A kind of multilayer complex films and its preparation method and application having XAYBX structure | |
| DE102009005137A1 (en) | Label film for thermoforming | |
| DE3626809A1 (en) | Biaxially oriented polypropylene film - includes gas barrier and sealing layers, for packaging foodstuffs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20090410 Address after: C, Guangdong science and Technology Industrial Park, Shunde, zip code: 528325 Applicant after: Guangdong De Guan packing material Co., Ltd. Co-applicant after: Guangdong Decro BOPP Co., Ltd. Address before: Post encoding Shunde Xingtan Town Industrial Zone Xin Yong Qi Xin Lu Guangdong decro packing material Co., Ltd. Guangdong city in Foshan Province: 528333 Applicant before: Guangdong Decro Package Films Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 528325 Guangdong Shunde science and Technology Industrial Park C District Co-patentee after: Gaungdong Decro Film New Material Co.,Ltd. Patentee after: Guangdong Decro Package Films Co., Ltd. Address before: 528325 Guangdong Shunde science and Technology Industrial Park C District Co-patentee before: Guangdong Decro BOPP Co., Ltd. Patentee before: Guangdong Decro Package Films Co., Ltd. |