CN104672607A - Biaxially oriented polypropylene high-modulus film master batch and production process thereof - Google Patents
Biaxially oriented polypropylene high-modulus film master batch and production process thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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Abstract
The invention discloses biaxially oriented polypropylene high-modulus film master batch and a production process thereof. The biaxially oriented polypropylene high-modulus film master batch comprises the following components in percentage by mass: 50-60% of homo-polypropylene, 0-50% of an erectness enhancer, 0.2-1.0 of an antioxidant, 0.5-5% of cage-shaped polyhedral oligomeric silsesquioxane with a grain size of 0.5-10nm. According to the biaxially oriented polypropylene high-modulus film master batch disclosed by the invention, hydrogenated petroleum resin and the cage-shaped polyhedral oligomeric silsesquioxane cooperatively enhance the erectness, so that the erectness of the BOPP film is effectively improved; meanwhile, the BOPP film has the characteristics of low haze and high glossiness, can meet the using requirements of high-speed automatic packaging equipment, and is positive in practical significance.
Description
Technical field
The present invention relates to a kind of Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch and production technique thereof.
Background technology
BiOriented Polypropylene Films (BOPP) is generally multi-layer co-extruded film, is formed after sheet material through co-extrusion by polypropylene GRANULES, more obtained through the stretching of both direction in length and breadth.BiOriented Polypropylene Films has light weight, nontoxic, odorless, protection against the tide, physical strength are high, the advantages such as good stability of the dimension, printing performance are good, the transparency is good, be widely used in the packaging of food, candy, cigarette, tealeaves, fruit juice, milk, textiles etc., have the laudatory title of " packaging queen ".Wide, the pollution of BOPP film application low and the protection to forest natural resources, become than paper and the more welcome wrapping material of polyvinyl chloride (PVC).Its manufacturing process is simple and easy reliably, reasonable price makes again it become the wrapping material more generally used than biaxial stretching polyester (BOPET) film and biaxial tension nylon (BOPA) film.
In the production process of Biaxially oriented polypropylene film (BOPP) (BOPP) film, in order to improve some performance of polypropylene film, often need in resin, add the auxiliary agent with partial function.But because pure additive is generally liquid, mashed prod or powder, and general addition is less, therefore directly adds auxiliary agent in the process of producing polypropylene film and is difficult to mix, thus causes the polypropylene film quality of production unstable.
For the problems referred to above, at present conventional way is made " masterbatch " with polypropylene bulk material Homogeneous phase mixing in advance by the functional agent compared with multiple types, before polypropylene film is produced again by masterbatch and starting material by a certain percentage Homogeneous phase mixing carry out extrusion.
More BOPP masterbatch is in the market antistatic master batch, antiblocking masterbatch, pearly-lustre masterbatch, anti-aging master batch, delustring masterbatch etc., and less for the BOPP masterbatch of height well-pressed degree cigarette film, electrical membrane, high transmittance film.The BOPP film masterbatch of the well-pressed degree of this height needs to add rigidity auxiliary agent, thus the modulus of raising film, heat-shrinkable and glossiness, with the performance requriements of satisfied high-grade packaging film.And existing BOPP stiffness of thin film is less, glossiness, heat-shrinkable are poor.Endure masterbatch and production technique thereof as Chinese invention patent application CN102321303A discloses a kind of antistatic increasing, the concrete component of masterbatch very that can antistaticly can increase again mentioned in literary composition comprises: polypropylene 55 ~ 65 parts, glass microballon 1 ~ 5 part, 20 ~ 25 parts, hydrogenated petroleum resin alkene, 17 ~ 25 parts, static inhibitor.The masterbatch that this formula is produced has the effect that antistatic increasing is endured, but its glass microballon used is mineral filler, without surface treatment, bad with body material consistency, easily disperses inequality, cause masterbatch quality fluctuation larger in the process of extruding pelletization.Chinese invention patent application CN102382360A discloses a kind of 15 microns of firm masterbatch of the special increasing of BOPP retraction tobacco film, by selecting C5 and C9 petroleum resin mix and add a certain proportion of compatilizer, makes the firm masterbatch of increasing produced reach the quality of efficient stable.The firm masterbatch of increasing that the method is produced can keep high transparent at short notice, but in the process of stretching film forming and as thermo-oxidative ageing variable color easy in the later stage use procedure of cigarette film, affects product appearance.Chinese invention patent application CN102153810A discloses a kind of PP film intensity strengthening agent, the PP film intensity strengthening agent that the method is produced is extruded after mixing by polypropylene 50%, C5 petroleum resin 49.5%, oxidation inhibitor 0.5% and is formed, wherein C5 petroleum resin mainly give the good thermal stability of film and smooth performance, impact is increased on the deflection of film little, and need again to add several functions auxiliary agent when stretching film forming, add secondary production technique, increase production cost.
On the other hand, for Biaxially oriented polypropylene film (BOPP) high-modulus film, especially cigarette packaging film, because it adopts high-speed automated packaging facilities, film is had to the requirement of high-modulus, low-friction coefficient, high-clarity (i.e. low haze).
Therefore, develop a kind of Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch, make film prepared therefrom have the features such as high-modulus, high percent thermal shrinkage, low haze, meet the service requirements of high-speed automated packaging facilities, there is positive realistic meaning.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch and production technique thereof.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch, in mass, comprises following component:
Homo-polypropylene 50 ~ 60%;
Intensity strengthening agent 40 ~ 50%;
Oxidation inhibitor 0.2 ~ 1.0%;
Cage modle polysilsesquioxane 0.5 ~ 5%;
The melt flow rate (MFR) of described homo-polypropylene is 1 ~ 10 g/10min;
Described intensity strengthening agent be selected from C5 hydrogenated petroleum resin, C9 hydrogenated petroleum resin one or both;
The particle diameter of described cage modle polysilsesquioxane is 0.5 ~ 10 nm.
Above, described cage modle polysilsesquioxane is prior art, its English name polyhedral oligomeric silsesquioxane, and be called for short POSS, general formula is (RSiO
3/2)
n.
Above-mentioned masterbatch is mainly used in the sandwich layer of BOPP film.
Preferably, the melt flow rate (MFR) of described homo-polypropylene is 2 ~ 5 g/10min.
In technique scheme, described oxidation inhibitor is selected from the one in antioxidant 1010, antioxidant 1076, antioxidant 264, oxidation inhibitor 164, oxidation inhibitor DNP.
Mechanism of the present invention is as follows: cage modle polysilsesquioxane has three-dimensional inorganic-organic hybridization structure, and has higher oxidation-resistance and water resisting property, coordinates oxidation inhibitor to use and can improve polyacrylic resist oxygen aging ability.In addition, cage modle polysilsesquioxane has very high modulus and hardness, synergy is had with intensity strengthening agent, add cage modle polysilsesquioxane, BOPP film can be made to have high well-pressed degree when reducing hydrogenated petroleum resin consumption, simultaneously because the mist degree of hydrogenated petroleum resin on BOPP film has impact, decrease the consumption of hydrogenated petroleum resin, effectively reduce the mist degree of BOPP film.
In addition, because cage modle polysilsesquioxane is with organic group, with matrix resin, there is good compatibility, can be uniformly dispersed in polymer melt, therefore do not need to carry out surface treatment to cage modle polysilsesquioxane, save production technique.Meanwhile, nanometer cage modle polysilsesquioxane has the quantum size effect of typical nanoparticle, has stronger over-all properties; The silica skeleton of cage modle polysilsesquioxane forms inorganic kernel, can give the performances such as the good thermostability of body material, antioxidant.
The present invention asks the production technique protecting a kind of Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch simultaneously, comprises the steps: above-mentioned each component thing fully to mix; The material mixed is put in the twin screw extruder being preheating to 170 ~ 210 DEG C, cooling, pelletizing, drying after melt extrusion, described Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch can be obtained.
In technique scheme, the screw speed of described twin screw extruder is 100 ~ 150 r/min.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention is configured with a kind of Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch, endure by using hydrogenated petroleum resin and collaborative increasing of cage modle polysilsesquioxane, effectively raise the well-pressed degree of BOPP film, make BOPP film have the feature of low haze, high gloss simultaneously, the service requirements of high-speed automated packaging facilities can be met, there is positive realistic meaning;
2. the present invention adopts oxidation inhibitor and cage modle polysilsesquioxane jointly to serve resist oxygen aging effect, compared to being used alone oxidation inhibitor, has the advantages that timeliness is long, effective;
3. the present invention adopts cage modle polysilsesquioxane, not only can improve the resistance to elevated temperatures of film, reduces the high temperature friction coefficient of film; And be uniformly dispersed in melt polypropylene due to nanometer cage modle polysilsesquioxane, the effect of inorganic nano-filler can be played, the viscosity of melt polypropylene can be reduced, improve processing characteristics, solve conventional nano filler in prior art because volume is little, specific surface area large, with polymer melt poor compatibility and the polymer melt that causes in easily reunites and causes disperseing the problem of inequality;
4. experiment proves, adopts the film of master batch processing of the present invention to have the characteristic of high-stiffness, high percent thermal shrinkage, low haze, high gloss, is applicable to high-grade packaging industry;
5. production technique of the present invention is easy, is easy to realize, and is suitable for applying.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment one
Weigh the 2020S that homo-polypropylene 55wt%(platform moulds Ningbo production, melt flow rate (MFR) is 3g/10min, Vicat softening point 150 DEG C), the R-1125 that C9 hydrogenated petroleum resin 40wt%(U.S. Yi Shiman produces, ring and ball softening point 125 DEG C), the antioxidant 1010 of 0.2wt%, cage modle polysilsesquioxane 4.8wt% is put in mixing machine and stirs 10min, then compound is put in the hopper of forcing machine, forcing machine each section of temperature is between 170 ~ 210 DEG C, screw speed 150 r/min, melt after extruding in tank cooling forming, be drawn in dicing machine dry after pelletizing.
The physicochemical property of the masterbatch prepared is in table 1.
Embodiment two
Weigh the 2020S that polypropylene 55wt%(platform moulds Ningbo production, melt flow rate (MFR) is 3g/10min, Vicat softening point 150 DEG C), the R-1125 that C9 hydrogenated petroleum resin 44.3wt%(U.S. Yi Shiman produces, ring and ball softening point 125 DEG C), the antioxidant 1010 of 0.2wt%, cage modle polysilsesquioxane 0.5wt% is put in mixing machine and stirs 10min, then compound is put in the hopper of forcing machine, forcing machine each section of temperature is between 170 ~ 210 DEG C, screw speed 150r/min, melt after extruding in tank cooling forming, be drawn in dicing machine dry after pelletizing.
The physicochemical property of the masterbatch prepared is in table 1.
Embodiment three
Weigh the 2020S that polypropylene 55wt%(platform moulds Ningbo production; melt flow rate (MFR) is 3g/10min; Vicat softening point 150 DEG C); the R-1125 that C9 hydrogenated petroleum resin 42wt%(U.S. Yi Shiman produces; ring and ball softening point 125 DEG C); the antioxidant 1010 of 0.2wt%; cage modle polysilsesquioxane 2.8wt% is put in mixing machine and stirs 10min; then compound is put in the hopper of forcing machine; forcing machine each section of temperature is between 170 ~ 210 DEG C; screw speed 150r/min, melt after extruding in tank cooling forming, to be drawn in dicing machine after pelletizing dry.
The physicochemical property of the masterbatch prepared is in table 1.
Table 1 increases very masterbatch physicochemical property
Masterbatch embodiment prepared adds in polypropylene prepares BOPP film, this film has three-decker, upper epidermis and layer all adopt the formula of BOPP film commercially available at present: upper epidermis is Co-polypropylene 99wt% and antiblocking agent 1wt%, and layer is Co-polypropylene 90wt% and high temperature slipping agent 10%; Core film layer formula is: homo-polypropylene 75wt%(platform moulds the 2020S that Ningbo produces, melt flow rate (MFR) is 3g/10min, Vicat softening point 150 DEG C), the masterbatch 22wt% produced in this technical em-bodiments, the efficient DS126 increasing sliding antistatic master batch 3wt%(Beijing Ducheng New Material Co., Ltd. and produce).The concrete Production Flow Chart of film is:
1) core layer raw material homo-polypropylene, masterbatch, efficient increase sliding antistatic master batch and to put in main extruder through blanking device by formula rate and be heated into viscous state; Upper epidermis material copolymerization polypropylene and antiblocking agent, layer material copolymerization polypropylene and high temperature slipping agent put into melting in two subsidiary extruder according to formula rate respectively through blanking device.Three kinds of melts converge after filtering in three layers of die head to be extruded, and melt temperature controls at 220 ~ 230 DEG C;
2) melt extruded forms slab by water coolant (16 ~ 22 DEG C) cooling;
3) first slab carries out longitudinal stretching, and preheating temperature maintains 125 ~ 155 DEG C, and draft temperature maintains 80 ~ 90 DEG C, stretch ratio 5.7 times, and setting temperature maintains 90 ~ 95 DEG C; Then carry out cross directional stretch, preheating temperature maintains 160 ~ 180 DEG C, and draft temperature maintains 150 ~ 160 DEG C, draw ratio 6.5 times, and setting temperature maintains 100 ~ 120 DEG C;
4) film enters tractor, and take off roll temperature maintains 20 ~ 40 DEG C, carries out rolling after flattening, and the film obtained carries out performance measurement through overaging after one week.
Obtained BOPP film performance and the contrast of commercially available BOPP product performance refer to table 2.
The master batch formulation of the employing of described commercially available BOPP product is: homo-polypropylene 50wt%, C9 hydrogenated petroleum resin 49.5wt%, the antioxidant 1010 of 0.5wt%; The upper epidermis of its film is all identical with the present invention with the preparation method of layer and film.
Table 2 BOPP film performance (timeliness is after 1 week)
| Project | Commercially available prod | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Percent thermal shrinkage/% | 7.7 | 8.5 | 8.0 | 8.3 |
| Mist degree/% | 1.0 | 0.9 | 1.0 | 0.95 |
| Young's modulus/N/mm 2 | 2600 | 2890 | 2800 | 2830 |
| Kinetic friction coefficient (80 DEG C) | 0.24 | 0.20 | 0.22 | 0.21 |
As seen from the above table, compared with prior art, the BOPP film adopting master batch processing of the present invention to obtain has the feature of high well-pressed degree, high percent thermal shrinkage, low haze, high gloss, the service requirements of high-speed automated packaging facilities can be met, a kind of outstanding high-modulus film, can as cigarette packaging film.
Claims (5)
1. a Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch, is characterized in that, in mass, comprises following component:
Homo-polypropylene 50 ~ 60%;
Intensity strengthening agent 40 ~ 50%;
Oxidation inhibitor 0.2 ~ 1.0%;
Cage modle polysilsesquioxane 0.5 ~ 5%;
The melt flow rate (MFR) of described homo-polypropylene is 1 ~ 10 g/10min;
Described intensity strengthening agent be selected from C5 hydrogenated petroleum resin, C9 hydrogenated petroleum resin one or both;
The particle diameter of described cage modle polysilsesquioxane is 0.5 ~ 10 nm.
2. Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch according to claim 1, is characterized in that: the melt flow rate (MFR) of described homo-polypropylene is 2 ~ 5 g/10min.
3. Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch according to claim 1, is characterized in that: described oxidation inhibitor is selected from the one in antioxidant 1010, antioxidant 1076, antioxidant 264, oxidation inhibitor 164, oxidation inhibitor DNP.
4. a production technique for Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch, is characterized in that, comprises the steps: each component thing according to claim 1 fully to mix; The material mixed is put in the twin screw extruder being preheating to 170 ~ 210 DEG C, cooling, pelletizing, drying after melt extrusion, described Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch can be obtained.
5. the production technique of Biaxially oriented polypropylene film (BOPP) high-modulus film masterbatch according to claim 4, is characterized in that: the screw speed of described twin screw extruder is 100 ~ 150 r/min.
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| CN106432914A (en) * | 2016-09-30 | 2017-02-22 | 武汉惠强新能源材料科技有限公司 | Masterbatch for high-stiffness polypropylene film and preparation method thereof |
| CN106519455A (en) * | 2016-10-13 | 2017-03-22 | 汕头市贝斯特科技有限公司 | Low-friction coefficient anti-bonding master batch special for metallized base film and preparation method thereof |
| CN106565961A (en) * | 2016-11-10 | 2017-04-19 | 河南惠强新能源材料科技股份有限公司 | Stiffness increasing agent for polypropylene lithium ion battery diaphragm and battery diaphragm prepared by using same |
| CN109679216A (en) * | 2018-12-28 | 2019-04-26 | 重庆普利特新材料有限公司 | A kind of high rigid-tough balance, resistance to stress whiten, halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN109867861A (en) * | 2019-02-12 | 2019-06-11 | 优矿塑新材料科技(芜湖)有限公司 | A kind of dust-protection type polypropylene agglomerate |
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| CN111040296A (en) * | 2019-12-25 | 2020-04-21 | 苏州度辰新材料有限公司 | Polyolefin composition with high mechanical property and preparation method thereof |
| CN111117077A (en) * | 2020-01-06 | 2020-05-08 | 广东德冠包装材料有限公司 | Extinction material for BOPP extinction film, preparation method of extinction material and BOPP extinction film |
| CN115926294A (en) * | 2022-12-29 | 2023-04-07 | 苏州度辰新材料有限公司 | Polyolefin film master batch with high stiffness and preparation method thereof |
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| CN106565961A (en) * | 2016-11-10 | 2017-04-19 | 河南惠强新能源材料科技股份有限公司 | Stiffness increasing agent for polypropylene lithium ion battery diaphragm and battery diaphragm prepared by using same |
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| CN109679216A (en) * | 2018-12-28 | 2019-04-26 | 重庆普利特新材料有限公司 | A kind of high rigid-tough balance, resistance to stress whiten, halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN109867861A (en) * | 2019-02-12 | 2019-06-11 | 优矿塑新材料科技(芜湖)有限公司 | A kind of dust-protection type polypropylene agglomerate |
| CN110746717A (en) * | 2019-10-24 | 2020-02-04 | 青华科教仪器有限公司 | Slush molding PVC material and preparation method thereof |
| CN111040296A (en) * | 2019-12-25 | 2020-04-21 | 苏州度辰新材料有限公司 | Polyolefin composition with high mechanical property and preparation method thereof |
| CN111117077A (en) * | 2020-01-06 | 2020-05-08 | 广东德冠包装材料有限公司 | Extinction material for BOPP extinction film, preparation method of extinction material and BOPP extinction film |
| CN115926294A (en) * | 2022-12-29 | 2023-04-07 | 苏州度辰新材料有限公司 | Polyolefin film master batch with high stiffness and preparation method thereof |
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