CN103435911A - Anti-adhesion BOPP (Biaxially-oriented Polypropylene) master batch and preparation method thereof - Google Patents
Anti-adhesion BOPP (Biaxially-oriented Polypropylene) master batch and preparation method thereof Download PDFInfo
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- CN103435911A CN103435911A CN2013103813254A CN201310381325A CN103435911A CN 103435911 A CN103435911 A CN 103435911A CN 2013103813254 A CN2013103813254 A CN 2013103813254A CN 201310381325 A CN201310381325 A CN 201310381325A CN 103435911 A CN103435911 A CN 103435911A
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- antiblocking
- bopp
- adhesion
- film
- polypropylene
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- 229920006378 biaxially oriented polypropylene Polymers 0.000 title claims abstract description 54
- 239000011127 biaxially oriented polypropylene Substances 0.000 title claims abstract description 54
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- -1 polypropylene Polymers 0.000 claims abstract description 47
- 239000004743 Polypropylene Substances 0.000 claims abstract description 43
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000004005 microsphere Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000005453 pelletization Methods 0.000 claims abstract description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 35
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000155 melt Substances 0.000 abstract description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000005484 gravity Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000013538 functional additive Substances 0.000 abstract 1
- 239000002985 plastic film Substances 0.000 abstract 1
- 229920006255 plastic film Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 60
- 239000007822 coupling agent Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000006748 scratching Methods 0.000 description 4
- 230000002393 scratching effect Effects 0.000 description 4
- 229920002554 vinyl polymer Chemical group 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OYUMYJKDVNCXAX-UHFFFAOYSA-N 2-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O OYUMYJKDVNCXAX-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
An anti-adhesion BOPP (Biaxially-oriented Polypropylene) master batch belongs to a functional additive of a plastic film and particularly relates to an anti-adhesion master batch for a BOPP film (namely, a biaxially-oriented polypropylene film). The invention aims at obtaining the anti-adhesion BOPP master batch so as to overcome the defects of poor effect and large specific gravity existing in a conventional anti-adhesion agent. Meanwhile, the invention also provides a preparation method of the anti-adhesion BOPP master batch so as to improve the anti-adhesion effect of anti-adhesion particles. The anti-adhesion BOPP master batch comprises the following components in parts by weight: 100 parts of polypropylene and 0.5-4 parts of methyl methacrylate microspheres. The preparation method comprises the following steps of: fully mixing the precisely weighted anti-adhesion agent and the polypropylene, extruding a melt by using a double-screw extruder, controlling the production temperature of the extruder at 210-240 DEG C, electric currents at 440-460 A, the rotational speed of the extruder at 420-430r/min, the pressure of a machine head at 18-20MPa/h and the temperature of the melt a 210-250 DEG C, drying and cooling the extruded melt, and pelletizing so as to obtain the master batch finished product.
Description
Technical field
The invention belongs to the functional agent of plastics film, specifically refer to the antibock Masterbatch of a kind of BOPP film (that is: BiOriented Polypropylene Films) use.
Background technology
The BOPP film is a kind of very important flexible packing material, owing to thering is colourless, odorless, tasteless, nontoxic characteristics and high tensile, high impact, obdurability is high, the good characteristics such as optical property, so at packaging field, application is very widely arranged, its market is also in continuous expansion, China's BOPP film yield in 2007 reaches 2,000,000 ton/years, will have the end of the year 2008 twenties BOPP film lines to put into production, and the annual production of following BOPP film will reach 250～3,000,000 ton/years.The rolling in process of production of BOPP film, cut and other operation, and packing can many problems occur due to inter-adhesive between film in using, even can't produce or use.
Solving the common way of film blocking problem is, add a certain proportion of antiblocking agent of people on the top layer of BOPP film, its mechanism is, because antiblocking agent and pp material are incompatible, and higher than polypropylene fusing point, can guarantee like this to melt extrude Shi Buhui and be melted in the film production process.The particle diameter of antiblocking agent is generally at 3-5 μ m, and the skin depth of film is about 1 μ m, like this after film forming, these antiblocking agents form many projections on the surface of film, or the different lax shapes of appearance is concavo-convex, make the surface of film become coarse, can retain a certain amount of air between layers, thereby play the inter-adhesive between layers effect that prevents.
In prior art, the antiblocking agent in BOPP need to have following characteristics:
1, with acrylic resin, close refractive index is arranged;
2, fusing point is higher than polypropylene, and incompatible with pp material; 3, the size of antiblocking agent should be applicable to the film skin depth; 4, can be scattered in equably in polypropylene, surface is round and smooth, and hardness is lower, avoids scratching face.
As the antiblocking agent used on the BOPP film, can be divided into inorganic antiblocking agent and the large class of organic antiblocking agent two at present.
Inorganic antiblocking agent applies at most in the BOPP film product, the widest.The present inorganic antiblocking agent be applied in the BOPP film product mainly contains diatomite, talcum powder, calcium carbonate, synthetic silica or the glass microballon etc. of independent use.Wherein, talcum powder and calcium carbonate are larger to BOPP Film Optics performance impact, can obviously increase mist degree; The diatomite much higher hard, easily scratch the film face, and application also is restricted, and generally is applied to the polyolefin film of other low side.Common BOPP film antiblocking agent masterbatch is generally used the gel method synthetic silica for antiblocking agent, because synthetic silica low price, light specific gravity (specific surface area is large) anti-adhesion effects is splendid, but the shortcoming of synthetic silica is the mist degree that can affect film, the hardness of silicon-dioxide is very high simultaneously, and machine and film surface are made a big impact.Therefore be not suitable for producing glossiness, the exigent high-end BOPP film of transparency.
The optical property of organic antiblocking agent is fine, and can not produce and scratch film surface, but as easy as rolling off a log degraded under hot environment, control to production and complete processing requires very high, most importantly the price of organic antiblocking agent is generally 3～6 times of left and right of inorganic antiblocking agent, and price is very expensive, and practical value is not high, so limited the application of organic antiblocking agent on the BOPP film, used seldom.
Inorganic antiblocking agent has impact in various degree to the optical property of film, it should be noted that simultaneously, after having added inorganic antiblocking agent, equal to add the grinding impurity that produces wearing and tearing for mechanical means, just directly can produce wearing and tearing to the equipment on high-speed production lines and wrapping mechanism etc.As the screw rod of forcing machine, cylinder barrel, film interlabial gap etc., accumulate over a long period, will on the precision stability of equipment, cause thousand to determine the impact of degree.
And organic antiblocking agent has relatively low softening temperature or fusing point, and smooth performance is arranged, less to the Film Optics performance impact, but easily degrade on the high temperature die head, be accumulated in die head, can affect film quality in the course of time.
The special-purpose antiblocking agent masterbatch of BOPP film develops at present, also there is no truly can reach the product of ideal effect.So it is good to pursue a kind of service performance, price is lower antiblocking agent masterbatch again, is the problem that current BOPP film functional agent industry is constantly explored.
Summary of the invention
The objective of the invention is to obtain a kind of antiblocking BOPP masterbatch, to overcome existing antiblocking agent poor effect, heavy defect.
The present invention also provides a kind of antiblocking BOPP master batch method, to improve the antiblocking effect of antiblocking particle.
A kind of antiblocking BOPP masterbatch comprises following component and content (weight part):
Polypropylene 100
Poly (methyl methacrylate) micro-sphere 2-4
Described poly (methyl methacrylate) micro-sphere particle diameter is the 5-10 micron.
Described a kind of antiblocking BOPP masterbatch also comprises transparent base, and described transparent base is selected from aliphatics or aromatic carboxylic acid metallic soap, sorbyl alcohol Bian fork derivative, organophosphate and rosin nucleator.
Described a kind of antiblocking BOPP masterbatch also comprises antioxidant, and described antioxidant is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid etc.
Described a kind of antiblocking agent BOPP masterbatch also comprises dispersion agent, and described dispersion agent is selected from ethylene bis stearamide (that is: EBS)-I, II, III or IV etc.
Described antiblocking BOPP masterbatch preparation process be by the antiblocking agent after precision weighing and polypropylene after sufficiently mixing through twin screw extruder by melt extrusion, forcing machine production temperature is controlled at 210-240 ℃, current control is at 440-460A, the forcing machine rotating speed is controlled at 420-430r/min, head pressure is controlled at 18-20MPa/h, melt temperature is controlled at 210-250 ℃, and melt extrusion forms the masterbatch finished product by dry, cooling, pelletizing.
Adopt the poly (methyl methacrylate) micro-sphere of uniform particle diameter can not scratch film surface, refraction coefficient is 1.50 simultaneously, can not affect the transparency of film, and the polymethylmethacrylate melt temperature is higher than polypropylene simultaneously.Spherical polymethylmethacrylate is difficult for scratching film surface, in preparation process, also can not cause wearing and tearing to machine.
Embodiment
Below, the embodiment the present invention relates to is described.In addition, the present invention, the embodiment do not the following describes, the restriction of embodiment.
polypropylene
The polypropylene that the present invention uses, be selected from a kind of or several mixing in isotactic PP, a rule PP and random PP, the mixture of preferred isotactic PP and random PP, the weight ratio of isotactic PP and random PP is 15-30:1, degree of isotacticity is larger, crystallization rate is faster, the yield strength of film product and surface hardness can obviously increase, and in order to improve the optical property of film, add a small amount of random PP, random PP plays internal lubricant in polymkeric substance, and is conducive to polymer directional.
The PP that preferably melt flow rate (MFR) is 2～4g/ (10min) simultaneously.
?
antiblocking agent
The preferred organic antiblocking agent of the antiblocking agent that the present invention selects, as poly (methyl methacrylate) micro-sphere, the more preferably poly (methyl methacrylate) micro-sphere of narrow size distribution, preferably microspherulite diameter 5 or 10 microns.Poly (methyl methacrylate) micro-sphere can not scratch film surface, and refraction coefficient is 1.50 simultaneously, can not affect the transparency of film, and the polymethylmethacrylate melt temperature is higher than polypropylene simultaneously.Spherical polymethylmethacrylate is difficult for scratching film surface, in preparation process, also can not cause wearing and tearing to machine.The microballoon of narrow size distribution can make antiblocking agent can better be dispersed in film surface, can give play to more fully the effect of antiblocking agent.At thickness, in minimum film, be even more important, the microballoon of uniform particle diameter can be prepared thinner film.
The preparation method of poly (methyl methacrylate) micro-sphere has letex polymerization (0.01～0.5 μ m), emulsifier-free emulsion polymerization (0.2～0.8 μ m), seeding polymerization (0.5～1 μ m), dispersion polymerization (0.8～6 μ m), seed swelling (1～10 μ m), suspension polymerization (100～1000 μ m) method.In order to prepare the poly (methyl methacrylate) micro-sphere of the present invention's 5-10 micron used, the present invention can adopt the method for dispersion polymerization or seed swelling.
In the situation that polypropylene is 100 weight parts, the consumption of poly (methyl methacrylate) micro-sphere is the 0.5-4 weight part.
The poly (methyl methacrylate) micro-sphere that poly (methyl methacrylate) micro-sphere is narrow size distribution, described microspherulite diameter is 5 or 10 microns, and rate of small round spheres is 95%, and narrow size distribution refers to that the particle diameter of most of microballoon concentrates near a certain particle diameter.
Organic antiblocking agent can also be selected the mixture of polysiloxane or polymethylmethacrylate and polysiloxane, preferably is prepared into the microballoon of 5 or 10 microns.In polysiloxane, Siliciumatom mainly plays smooth effect.
The preparation method of the mixture microballoon of polymethylmethacrylate and polysiloxane has organosilicon and methyl methacrylate to utilize the monomer emulsion emulsion to drip continuously copolymerization to prepare after microballoon, organosilicon and methyl methacrylate are prepared into respectively microballoon and carry out even blend.
Organopolysiloxane (abbreviation polysiloxane), be a class to take the Si-O key repeated be main chain, the direct polymkeric substance of connection organic group on Siliciumatom, its general formula is:
Wherein, R represents organic group, as methyl, and phenyl etc.; N is the organic group number connected on Siliciumatom; M is the polymerization degree.
Polymethylmethacrylate and polysiloxane parts by weights, ratio is 1:1-1.5
In order to obtain better antiblocking effect, antiblocking agent of the present invention can also comprise inorganic antiblocking agent, and described inorganic antiblocking agent comprises one or several in diatomite, calcium carbonate, synthetic silica and glass microballon.The 1.5-10 that the particle diameter of described organic antiblocking agent is inorganic antiblocking agent doubly.By using organic antiblocking agent of greater particle size, can reduce the scuffing of inorganic antiblocking agent to film surface.Because inorganic antiblocking agent all has higher density, be difficult for being dispersed among film.Mixed by the two, can effectively solve shortcoming that the density of the shortcoming of easy degraded of organic antiblocking agent and inorganic antiblocking agent is higher and to the shortcoming of the wearing and tearing of machine.Especially in thin film.
In the situation that polypropylene is 100 weight parts, the consumption of organic antiblocking agent is 0.5～4 mass parts
Antiblocking agent of the present invention can also comprise the coupling agent for the treatment of inorganic antiblocking agent.
The general formula of silane coupling agent is RSiX
3, in formula, R represents the groups such as amino, sulfydryl, vinyl, epoxy group(ing), cyano group and methacryloxy, these groups and different matrix resins all have stronger response capacity, the alkoxyl group (as methoxyl group, oxyethyl group etc.) that the X representative can be hydrolyzed.
The preferred cross-linking type coupling agent of described coupling agent, preferably have the silane coupling agent of vinyl or sulfydryl.Silane coupling agent with vinyl or sulfydryl can produce good chemical b ` with inorganic antiblocking agent, organic antiblocking agent.With respect to common hydrogen bond action or van der Waals interaction, coupling effect is better.
In the situation that polypropylene is 100 weight parts, the consumption of silane coupling agent is 0.5～2 mass parts.
other auxiliary agents
Antiblocking BOPP masterbatch of the present invention also comprises antioxidant, transparent base, dispersion agent.
Antioxidant is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid etc.In the situation that polypropylene is 100 weight parts, the consumption of antioxidant is 0.1～0.4 weight part.
Transparent base is selected from aliphatics or aromatic carboxylic acid metallic soap, sorbyl alcohol Bian fork derivative, organophosphate and rosin nucleator.In the situation that polypropylene is 100 weight parts, the consumption of transparent base is 0.1～0.3 weight part.
Transparent base refers to fusible organic compound, mainly contains aliphatics or aromatic carboxylic acid metallic soap, sorbyl alcohol Bian fork derivative, organophosphate and rosin nucleator.
Dispersion agent is selected from ethylene bis stearamide (that is: EBS)-I, II, III or IV etc.In the situation that polypropylene is 100 weight parts, the consumption of dispersion agent is 0.5～2 weight part.
Antiblocking BOPP masterbatch preparation process be by the antiblocking agent after precision weighing and polypropylene after sufficiently mixing through twin screw extruder by melt extrusion, forcing machine production temperature is controlled at 210-240 ℃, current control is at 440-460A, the forcing machine rotating speed is controlled at 420-430r/min, head pressure is controlled at 18-20MPa/h, melt temperature is controlled at 210-250 ℃, and melt extrusion forms the masterbatch finished product by dry, cooling, pelletizing.
The BOPP performance test adopts following standard:
Mist degree adopts the ASTMD1003 test, and glossiness adopts the ASTMD2457 test.
embodiment 1～3:
| ? | Isotatic polypropylene | Atactic Polypropelene | The PMMA microballoon |
| Embodiment 1 | 100 | -— | 0.5 |
| Embodiment 2 | 94 | 6 | 2 |
| Embodiment 3 | 97 | 3 | 4 |
In embodiment 1, the melt flow rate (MFR) of isotatic polypropylene is 4g/ (10min), the microballoon that the PMMA microballoon is particle diameter 1-20 micron.
In embodiment 2, the melt flow rate (MFR) of isotatic polypropylene is 2g/ (10min), and the melt flow rate (MFR) of Atactic Polypropelene is 4g/ (10min),, the microballoon that the PMMA microballoon is particle diameter 1-20 micron.
In embodiment 2, the melt flow rate (MFR) of isotatic polypropylene is 3g/ (10min), and the melt flow rate (MFR) of Atactic Polypropelene is 2g/ (10min),, the microballoon that the PMMA microballoon is particle diameter 1-20 micron.
The preparation method of embodiment 1～3 be by the PMMA microballoon after precision weighing and isotactic or/and Atactic Polypropelene after sufficiently mixing through twin screw extruder by melt extrusion, wherein, melt flow rate (MFR) is 3g/ (10min), forcing machine production temperature is controlled at 210-240 ℃, current control is at 440-460A, the forcing machine rotating speed is controlled at 420-430r/min, head pressure is controlled at 18-20MPa/h, melt temperature is controlled at 210-250 ℃, and melt extrusion forms the masterbatch finished product by dry, cooling, pelletizing.
The BOPP film of producing thickness 28 μ m of take is benchmark, adds respectively the antiblocking agent masterbatch, under identical proportioning, same process condition, produces film, and its test result is as follows, measures the correlated performance of film, as following table:
| ? | Mist degree/% | Glossiness/% |
| Embodiment 1 | 78 | 91.4 |
| Embodiment 2 | 71 | 95.2 |
| Embodiment 3 | 72 | 94.8 |
embodiment 4～10
| ? | PP | The PMMA microballoon | Polysiloxane | Calcium carbonate | Silicon-dioxide | Coupling agent |
| Embodiment 4 | 100 | 0.5 | ? | 2 | ? | ? |
| Embodiment 5 | 100 | 0.5 | 0.5 | ? | 2 | ? |
| Embodiment 6 | 100 | 2 | 3 | 1 | 1 | ? |
| Embodiment 7 | 100 | 2 | 2.5 | 1 | 0.5 | ? |
| Embodiment 8 | 100 | 2 | ? | ? | 2 | 1 |
| Embodiment 9 | 100 | 2 | ? | ? | 2 | 1 |
| Embodiment 10 | 100 | 2 | ? | ? | 2 | 1 |
In embodiment 4, the polyacrylic melt flow rate (MFR) of selecting is 4g/ (10min), the microballoon that the particle diameter that the PMMA microballoon is narrow particle diameter is 10 microns.Calcium carbonate is that particle diameter is the 1-5 micron.
In embodiment 5-10, the polyacrylic melt flow rate (MFR) of selecting is 4g/ (10min), the microballoon that the particle diameter that the PMMA microballoon is narrow particle diameter is 5 microns.Silicon-dioxide is selected aerosil.
Embodiment 9 with the difference of embodiment 10 is, the particle diameter of the aerosil of embodiment 9 is 8 microns, and the median size of the aerosil of embodiment 10 is 2.5 microns.
The coupling agent of embodiment 8 adopts KH-550.Embodiment 9 and embodiment 10 adopt has vinyl silicane coupling agent.
The preparation method of embodiment 4～10 be by the PMMA microballoon after precision weighing and polypropylene and other components after sufficiently mixing through twin screw extruder by melt extrusion, wherein, melt flow rate (MFR) is 3g/ (10min), forcing machine production temperature is controlled at 210-240 ℃, current control is at 440-460A, the forcing machine rotating speed is controlled at 420-430r/min, head pressure is controlled at 18-20MPa/h, melt temperature is controlled at 210-250 ℃, and melt extrusion forms the masterbatch finished product by dry, cooling, pelletizing.
The BOPP film of producing thickness 28 μ m of take is benchmark, adds respectively the antiblocking agent masterbatch, under identical proportioning, same process condition, produces film, and its test result is as follows, measures the correlated performance of film, as following table:
| ? | Mist degree/% | Glossiness/% |
| Embodiment 4 | 78 | 93.4 |
| Embodiment 5 | 71 | 95.2 |
| Embodiment 6 | 72 | 94.5 |
| Embodiment 7 | 74 | 94.3 |
| Embodiment 8 | 72 | 94.8 |
| Embodiment 9 | 73 | 94.2 |
| Embodiment 10 | 70 | 95.8 |
After tested, adopt the poly (methyl methacrylate) micro-sphere of narrow size distribution microballoon also can not scratch film surface when guaranteeing the antiblocking performance, can not affect the transparency of film.Spherical polymethylmethacrylate is difficult for scratching film surface, in preparation process, also can not cause wearing and tearing to machine.In test, find, large organic particle diameter has prevented the wearing and tearing of little inorganic particle diameter to machine effectively.
The mixture of organic antiblocking agent and polysiloxane is discovery afterwards after tested, and smooth function when described organic antiblocking agent is compared the organic antiblocking agent of independent use with the mixture antiblocking agent of polysiloxane is significantly increased.
It is more effective that employing has the coupling agent of crosslinked group.Dispersion effect is better.Smoothness containing the film of polysiloxane is better.
The antiblocking agent that organic antiblocking agent combines with inorganic antiblocking agent after tested, by using with of the two, efficiently solve shortcoming that the density of the shortcoming of easy degraded of organic antiblocking agent and inorganic antiblocking agent is higher and to the shortcoming of the wearing and tearing of machine, because organic antiblocking agent forms higher projection, effectively prevent inorganic antiblocking agent to the wearing and tearing of machine and to the scratch of film simultaneously, also guaranteed glossiness and the transparency of film.
Claims (10)
1. antiblocking BOPP masterbatch, is characterized in that, described antiblocking BOPP masterbatch comprises following component and weight part:
Polypropylene 100;
Poly (methyl methacrylate) micro-sphere 0.5-4.
2. antiblocking BOPP masterbatch according to claim 1, is characterized in that, described poly (methyl methacrylate) micro-sphere is narrow size distribution poly (methyl methacrylate) micro-sphere.
3. antiblocking BOPP masterbatch according to claim 1, is characterized in that, the particle diameter that described poly (methyl methacrylate) micro-sphere is is 5 or 10 microns.
4. antiblocking BOPP masterbatch according to claim 1, is characterized in that, described polypropylene is selected from a kind of or several mixing in isotactic PP, a rule PP and random PP.
5. antiblocking BOPP masterbatch according to claim 1, is characterized in that, the weight ratio of described polypropylene isotactic PP and random PP is 15-30:1.
6. antiblocking BOPP masterbatch according to claim 1, is characterized in that, described polyacrylic melt flow rate (MFR) is 2～4g/ (10min).
7. antiblocking BOPP masterbatch according to claim 1, is characterized in that, described antiblocking BOPP masterbatch also comprises polysiloxane, and by weight, ratio is 1-5:1 for described poly (methyl methacrylate) micro-sphere and described polysiloxane.
8. antiblocking BOPP masterbatch according to claim 1, it is characterized in that, described antiblocking BOPP masterbatch also comprises inorganic antiblocking agent, described inorganic antiblocking agent is selected from one or several in diatomite, calcium carbonate, glass microballon, and the particle diameter 1.5-10 that the particle diameter of described poly (methyl methacrylate) micro-sphere is inorganic antiblocking agent doubly.
9. antiblocking BOPP masterbatch according to claim 8, is characterized in that, described antiblocking BOPP masterbatch also comprises the silane coupling agent for the treatment of inorganic antiblocking agent.
10. the preparation method as the described antiblocking BOPP masterbatch of any one claim in claim 1-9, is characterized in that, comprises the following steps:
By antiblocking BOPP masterbatch after sufficiently mixing through twin screw extruder by melt extrusion, forcing machine production temperature is controlled at 210-240 ℃, current control is at 440-460A, the forcing machine rotating speed is controlled at 420-430r/min, head pressure is controlled at 18-20MPa/h, melt temperature is controlled at 210-250 ℃, and melt extrusion forms the masterbatch finished product by dry, cooling, pelletizing.
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