CN1966561A - Antistatic biaxially oriented polypropylene composition and its preparation method - Google Patents
Antistatic biaxially oriented polypropylene composition and its preparation method Download PDFInfo
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Abstract
This invention relates to antistatic biaxially oriented polypropylene (BOPP) combination, using polypropylene as material and including opening agent, smoothness agent, antistatic agent, antioxidant, processing and heat stabilizer, wherein the antistatic agent is glycerin fatty acid ester or two ester, polyethylene glycol ester, amides and/or ethyl amines, the anti-adhesion agent is a series of silicon dioxide inorganic matters or crosslinked polysiloxane particles, the opening agent is the synthesized silicon dioxide or silicates, calcium stearate, the smoothness agent is oleic acid amide, erucic acid amide and/or silicone, and the primary and secondary antioxidants are phosphite stabilizing agent and hindered amine antioxidant. The preparation method includes adding antistatic agent, etc. additives in granulation part, and adding them into PP, mixing, and melting and granulating to obtain the BOPP antistatic resin, or pre-preparing antistatic anti-adhesion smoothness masterbatch by various components. This invention keeps the original performances of BOPP with a lower volume of auxiliaries, and obtain good performances of antistatic property, anti-adhesion, and smoothness.
Description
Technical field
The present invention relates to a kind of plastics composite, be specifically related to a kind of antistatic biaxially oriented polypropylene (BOPP) composition, and the preparation method of this antistatic biaxially oriented polypropylene composition.
Background technology
Advantage such as Biaxially oriented polypropylene film (BOPP) (PP) film has light weight, nontoxic, odorless, protection against the tide, physical strength height, dimensional stabilizing is good, printing is good.Be widely used in packaging field, there is the laudatory title of " packing queen " particularly food product pack aspect.Along with Chinese economic development, domestic many producers introduce the BOPP production line in succession, and manufacturing enterprise spreads all over various places.In the production process of film, because film and the high speed rolling or the friction of drawing between nip rolls, deflector roll, bridle rolls, the baffle plate etc. make film surface have the high potential static charge.When film batches, produce intensive there is a natural attraction between the sexes effect, make film that volume wrinkle or dislocation take place.Because electrostatic exists, as food product pack, making-up etc., plastics film is dust stratification pollution easily in use, and easy cleaning does not influence light transmission.Therefore, the electrostatic existence is the harm greatly that film production is used.Owing to the singularity of film article, its good opening is essential crucial performance simultaneously.
BOPP is generally used for unitary film, also is used for the top layer film of composite membrane, is used for the packing of food and medicine etc., and directly contacts with materials such as powdery, granular, bulks, is the adhesion packed article, and then the smooth performance of the opening of BOPP is also particularly important.
Present goods producer, for the goods that make production possess the antistatic or smooth performance of antiblocking, have to before production, in the BOPP resin, add various master batches, this makes goods producer increase cost, and the adding of inappropriate composition, directly has influence on the performance and the outward appearance of coating materials, as the transparency variation of coating materials, processing stability variation etc.Therefore, should add various suitable species after deliberation, the processing and the functional agent of consumption in the production of BOPP resin polymerization, BOPP be possessed satisfy the antiblocking of general operational requirement, antistatic, smooth PP Pipe Compound.
The volume specific resistance of BOPP is up to 10
16Ω cm, BOPP film production process all needs to add antistatic master batch at present.If the BOPP PP Pipe Compound has added static inhibitor, just can reduce this problem of BOPP products factory, the kind of static inhibitor is a lot, distinguishes by chemical structure, and 4 kinds in cationic static inhibitor, anionic antistatic agent, non-ionic antistatic agent and conductive polymer type static inhibitor arranged.The principal item of non-ionic antistatic agent has fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, alkyl ethoxy compound, hydroxyethyl alkylamine, glycerol fatty acid ester etc.Ionic anti-static agent is to the macromolecular material strong adhesion, and antistatic property is good, but its poor heat stability, high temperature processing down easily decomposes and variable color, reduces the transparency and the glossiness of film greatly.And non-ionic antistatic agent is difficult for causing plastic ageing degraded etc., and the advantage that has ionic anti-static agent not possess is an ideal BOPP film static inhibitor.It has the uncharged surface active molecules of low polarity, and adsorbed water molecule forms solvated compounds and forms the static that conductive layer is eliminated film surface.What we studied is based on nonionogenic tenside, and in order to improve anlistatig effect, we also adopt non-ionic antistatic agent and ionic anti-static agent compound mode under study for action.
" plastic wrapping " the 4th phase in 2002,39～41 pages, in " functional aid in the BOPP film " literary composition, needed various functional aids in the BOPP film production process have been set forth, mainly comprise static inhibitor, slipping agent, anti, toughner, pearling agent etc., analyzed their mechanism of action etc.Wherein adding 0.1～2% static inhibitor is stearic acid glycerols, amides, ethyl amine etc.; Adding 0.1～0.5% slipping agent is erucicamide, silicone etc.; Adding 0.1～0.5% anti is silicon-dioxide or polysiloxane; The toughner of interpolation 5～20% is C
5Or C
9Petroleum resin are main petroleum spirit converted products mixture; Adding 5～20% pearling agent % is CaCO
3, TiO
2, mica etc.In this article, auxiliary agent that the BOPP PP Pipe Compound may use and range of application roughly only are provided, for the use of toughner, pearling agent etc., must be at a certain specific product, and do not possess ubiquity; The scope of the recommendation of static inhibitor, slipping agent, anti is also bigger, and lower limit content and upper limit content have bigger influence to the performance and the cost of product, obviously improper as BOPP production firm to the auxiliary agent kind in the base resin or use consumption.
What publication number CN 1476969A related to is that a kind of Biaxially oriented polypropylene film (BOPP) shrinks monofilm and preparation method thereof, monofilm divides the upper, middle and lower-ranking structure, skin is the smooth surface layer of film anti, the middle level is the film sandwich layer, lower floor is the smooth surface layer of film anti, described upper strata is that homo-polypropylene, weight content are that 0.2～6% adhesion-resistant slippery agent constitutes, and homo-polypropylene is contained in the middle layer, and homo-polypropylene is contained in lower floor, weight content is 0.2～6% adhesion-resistant slippery agent.Wherein the per-cent that each component is put this layer gross weight in the monofilm is respectively: the adhesion-resistant slippery agent in the upper strata is any one or more combination of silicon-dioxide, organosilicon, silica, silicone, antiblocking agent silicon-dioxide 0.1～0.5%, silicone 0.2～3.5%; Homo-polypropylene 79.5～96.95% in the middle layer, static inhibitor 0.05～0.5%, high molecular weight amines 0～0.3%, ethoxylated amine 0～0.5%, Zerol 0～0.5%, C
5Or/and C
9Hydrogenated resin 3～20%; Middle layer by layer down homo-polypropylene 97.2～99.9%, silicon-dioxide antiblocking agent 0.1～0.3%, silicone 0～2.5%.This patent has provided a kind of production method of BOPP thermal contraction coated thin film and the auxiliary formula of PP Pipe Compound, prescription in the upper, middle and lower-ranking film is all different, particularly in mesopelagic layer, for mist degree that lowers product and glossiness and the shrinking percentage that improves product, improve the deflection of product, the hydrogenated resin that adds preferable consumption nearly 10～17.5%, factory for resin, the factory that the BOPP PP Pipe Compound that manufacturing contains high-load hydrogenated resin offers film is infeasible, and the BOPP of this performance does not have general suitability yet.
Summary of the invention
Order of the present invention provides a kind of prescription of antistatic biaxially oriented polypropylene composition, the consumption of opening agent, slipping agent, static inhibitor and auxiliary agents such as other oxidation inhibitor, processing and thermo-stabilizer in the said composition prescription, all adopt lower consumption, and can keep original performance of BOPP (Biaxially oriented polypropylene film (BOPP)) resin simultaneously: the kinetic friction coefficient of BOPP resin reaches 0.18～0.22, and surface resistivity reduces to 10
12～14Ω satisfies normal the production and application requiring of general coating materials production of articles factory.Because preparation technology is to the performance important influence of antistatic biaxially oriented polypropylene composition, so the present invention also will provide the preparation method of this antistatic biaxially oriented polypropylene composition simultaneously.
The scheme of finishing above-mentioned first invention task is: a kind of antistatic biaxially oriented polypropylene composition is a base-material with PP (polypropylene), includes opening agent, slipping agent, static inhibitor, oxidation inhibitor, processing and thermo-stabilizer etc., it is characterized in that,
Described static inhibitor is selected from: fatty mono glyceride or diester (non-ionic antistatic agent), fatty acid polyglycol ester (non-ionic antistatic agent), amides (non-ionic type or amphoteric static inhibitor) and/or ethylamine (non-ionic antistatic agent) class; Its amount ranges is between 0.1～0.4%.Preferably scope is 0.15～0.3%.
In order to improve anlistatig effect, can adopt the two or more materials in non-ionic antistatic agent and the ionic anti-static agent simultaneously.
Anti can adopt the inorganics or the particulate state crosslinked polysiloxane of silicon-dioxide series, and its particle diameter is less than 8 μ m; Synthetic silicon-dioxide or silicate are adopted in described opening agent; Wherein, the granularity of synthetic silicon-dioxide is asking of 2 μ m～4 μ m, best 1 μ m～3 μ m, and consumption is between 0.05～0.2%; The consumption of described synthetic silicate is between 0.05～0.3%.
Should adopt different amounts during the different preventing adhesion agent, can use two or more simultaneously, but between always consumption can not exceed 0.05～0.2% or between 0.05～0.3%;
Calcium stearate is adopted in described opening agent, between its amount ranges 0.05～0.2%;
Described slipping agent is selected from amine hydroxybenzene, erucicamide or silicone.Can adopt two or more material wherein simultaneously, but consumption addition during employing, but the described below scope of overall control: wherein the addition of erucicamide is preferably in 0.05～0.3%; Wherein the content of silicone slipping agent is generally 0.2～1.5%;
Can adopt two or more slipping agent wherein simultaneously, total amount can not exceed desired scope when adopting simultaneously.
Major-minor oxidation inhibitor adopts phosphite stablizer and suffocated amine antioxidant to be used, two kinds of oxidation inhibitor add and consumption between 0.05～0.2%.
Above-described base-material can adopt the density of PP to be: 0.90～0.91g/cm
3PP is main raw material with the high-purity propylene, and can add ethene is comonomer, and ethene and ethylene content what add, and does not influence the basic material as the present invention's research.
Described static inhibitor comprises non-ionic antistatic agent and ionic anti-static agent, and the present invention is with non-ionic antistatic agent and the compound use of ionic anti-static agent.Because these two kinds of ingredient compatibilitys can be good, do not influence the physicals of PP resin again, its antistatic effect single variety separately is effective, and surface resistivity can lower 1～2 order of magnitude.When anionic fatty group sulfonate consumption reach the composite antistatic agent total mass 10% after, every performance is significantly increased.The add-on of anionic fatty group sulfonate is that 15%～20% of composite antistatic agent total mass is advisable.
Different with ionic anti-static agent, non-ionic antistatic agent does not have ionization, thus can't come leak charge by self-conductive, so the non-ionic antistatic agent Heat stability is good, generally plastics composite is not produced injurious effects, the nontoxic or low toxicity of most products.It is not decompose, never degenerate in processes such as resin high temperature process such as mixing, granulation that the present invention selects the requirement of static inhibitor; Good with other auxiliary agent consistency, plasticizing is good; Health, nontoxic.After the forming process.When the static inhibitor molecular layer that moves out when film surface was damaged, inner static inhibitor should be able in time ooze out, and recovered the surface resistivity of film, and just goods can secular maintenance antistatic property.
The something in common of ionic and the antistatic principle of non-ionic type is: all be to precipitate into behind the specimen surface moisture content in the absorbed air by the static inhibitor molecule to form conductive channel and make the loss of static nuclear.But ionic anti-static agent just can go out ion formation conductive channel by autodissociation after adsorbing certain moisture, and non-ionic antistatic agent only is to reach anlistatig purpose by the moisture content in the absorbed air.So, when the static inhibitor of ionic after the surface of sample precipitate into certain concentration, the ion that certain moisture content just can make the static inhibitor molecule breaking go out in its absorbed air forms conductive channel, increase its antistatic effect, so it is faster that the resistance value on Duan Liqi surface sometime descends, and shows the feature different with non-ionic antistatic agent.Static inhibitor has transport property, and after static inhibitor joined polymkeric substance, its can to move to content little or add layer from adding layer.Therefore after after a while, the static inhibitor molecule of plastics inner is constantly to surface transport, and the surface resistivity of plastics descends.In processing, use, owing to reasons such as stretching, friction, washings, cause frosting static inhibitor unimolecular layer damaged, make antistatic property reduce like this.Because the migration of static inhibitor is replenished the unimolecular layer of surface damage internally, continue the performance antistatic property.Replenish if defect layer can not get the migration of static inhibitor, the surface resistivity of plastics will rise.Therefore investigating a kind of static inhibitor should consider its fugitive property, also to investigate its long-acting performance in resin, the present invention is during usually to the week of a kind of static inhibitor in resin, two weeks, one month, two months, three months and half a year, at relative air humidity is the test of carrying out surface resistivity under (50 ± 3) %, its surface resistivity that records is taken the logarithm and the time mapping, can estimate out the quality that this static inhibitor shows in BOPP.
One group of its curve of sample all be tending towards downtrending and after January downtrending tend towards stability, show after the sample moulding prolongation along with the time, static inhibitor constantly from sample inside to surface transport.The static inhibitor of specimen surface is assembled many more, and its sheet resistance value is just low more.But the static inhibitor molecular arrangement of specimen surface has a degree of saturation, so its sheet resistance value also has a stationary value.
The static inhibitor that short run effect is good, its performance are that static inhibitor all tends towards stability from the inner speed of separating out rear surface resistance value in very fast January of sample, and in 3 months, the antistatic property of this material is fine.
Long-acting well behaved static inhibitor, though in the time of one month, its surface resistivity is not the most excellent, in the time of three months, its surface resistivity reaches than low value but As time goes on,, and in the time of 6 months or the longer time, surface resistivity remains on than low value always.
Certainly, a kind of static inhibitor or composite antistatic agent possess short-term and secular static resistance simultaneously, that is optimal.
Therefore, understood the long and short effect of separating out principle and the performance of its antistatic property of static inhibitor, the consumption that increases static inhibitor in order to increase static resistance simply is worthless.In fact, satisfying actual application is exactly suitable PP Pipe Compound, and low excessively ρ
SValue is a kind of waste.
The inorganics of silicon-dioxide series of the present invention or particulate state crosslinked polysiloxane anti form the particulate that all distributes at film surface, make the film surface roughening, the solid particulate of projection makes air be easy between each layer of person who lives in exile's film, anti particulate size is wanted suitably, little then anti-adhesion effects is not obvious, and is big then influence the surface luster and the transparency of film, therefore, the size of its particulate must be complementary with the thickness of film, and general particle diameter is less than 8 μ m;
Because can be used as the silicon dioxide microparticle of opening agent has a variety of, quality great disparity, native silicon dioxide are natural mineral matters, and transparence and purity are all not high, because natural mineral matter is " heavy " structure, concerning the opening agent of identical weight, effectively the particulate sum is few.Therefore, the agent of natural mineral opening not only influences film clarity, and usefulness is also low simultaneously.Therefore we adopt lightweight to synthesize silicide.Because it has light structures, therefore under the situation of identical weight, the particulate sum is many more than all kinds of heavy natural mineral.Therefore, the effective vent composition is far above natural mineral.In order to reduce the disadvantageous effect that organic silicon-dioxide brings, very important to the selection of silicon-dioxide granularity, the synthetic silica granularity that the present invention adopts is between 2 μ m～4 μ m, best 1 μ m～3 μ m, and consumption is between 0.05～0.2%.
Synthetic silicate also is the effective vent agent among a kind of BOPP, the PP refractive index is 1.463, the refractive index of silicate also is 1.50, approaching refractive index is arranged between the two, it is less when then light is by film to the transparency influence of fading of coating materials, because when directing light passes through the contact interface of two kinds of different substancess, if two kinds of different substancess have identical specific refractory power, the directing light that then passes through is in the alignment scope internal loss minimum of former input angle; If it is big more that the specific refractory power of two kinds of different substancess differs, the directing light that then passes through is big more in the alignment scope internal loss of former input angle.Therefore silicate has good transparency, and consumption of the present invention is between 0.05～0.3%.
Add antiblocking agent and slipping agent is exactly for coating materials overcomes adhesion aborning at PP, when extraneous weather and storage condition change, be exuded to film surface.Though make the film produced through the extruding of pressure roller and can not bond, even or the part film surface bond mutually, after the regular hour, have the opening agent to ooze out, the adherent pellicular front is dissociated, reach the purpose of opening.
Ideal BOPP film slipping agent should have good continuous lubrication of following characteristics: a. and high temperature lubricating.B. with polymkeric substance suitable consistency is arranged, because except that paraffins, all lubricants also all are surfactants, are close with static inhibitor, and slipping agent is with antiseized and antistatic property, so slipping agent also can be processed into the complex function masterbatch according to certain ratio with static inhibitor.The slipping agent kind that the BOPP film is commonly used has amides, soap class and silicone based.Amides such as amine hydroxybenzene and erucicamide, soap class such as calcium stearate, silicone based as silicone, the latter is aqueous, adds and uses inconvenience; Though the soap series products is cheap, effect is undesirable, and addition is big, and the performance to film produces detrimentally affect easily; These two kinds of slipping agents of amine hydroxybenzene and erucicamide, moderate cost, effect is obvious, and addition is moderate.
The silicone slipping agent, this slipping agent has good hot sliding, and frictional coefficient is very low at a certain temperature, does not have bloom shape material to move out, this is with regard to not producing the problem of the heat sealability decline that is brought owing to migration, and is also little than erucicamide class to the influence of mist degree.If excessive use can make the printing variation of film.The content of such surface slip agent is generally 0.2～1.5% in the present invention.
Major-minor oxidation inhibitor is used hindered amines and phosphoric acid ester usually, can select plastic working industry used various components usually.Owing to use single suffocated amine antioxidant not reach antioxidant effect well, for this reason, add phosphite stablizer and hindered amines again and be used.Like this, hindered amines plays a part to stop and reduce free radical activity, and the phosphite stablizer plays the effect of hydroperoxide decomposition, and the two synergy constitutes effective stabiliser system.In the present invention, two kinds of oxidation inhibitor add and consumption between 0.05～0.2%.
The technical scheme of finishing the 2nd invention task of the application is: the preparation method of antistatic biaxially oriented polypropylene composition, and step is as follows:
In the granulation section of producing BOPP (Biaxially oriented polypropylene film (BOPP)), with static inhibitor, opening agent, slipping agent, oxidation inhibitor, hot-work stablizer etc. join mixing in the poor jar of airtight mixing by proportioning, in being metered into PP, melting mixing is a granulated into antistatic BOPP PP Pipe Compound again;
Described static inhibitor is selected from: fatty mono glyceride or diester, fatty acid polyglycol ester, amides and/or ethyl amine; Its amount ranges is between 0.1～0.4%.Preferably scope is between 0.15～0.3%;
In order to improve anlistatig effect, can adopt the two or more materials in above non-ionic antistatic agent and the ionic anti-static agent simultaneously.
Anti adopts the inorganics or the particulate state crosslinked polysiloxane of silicon-dioxide series, and its particle diameter is less than 8 μ m; Synthetic silicon-dioxide or silicate are adopted in described opening agent; Wherein, the granularity of synthetic silicon-dioxide is asking of 2 μ m～4 μ m, best 1 μ m～3 μ m, and consumption is between 0.05～0.2%; The consumption of described synthetic silicate is between 0.05～0.3%;
Can use in the above anti two or more simultaneously, but total consumption can not exceed 0.05～0.2% between or between 0.05～0.3%;
Calcium stearate is adopted in described opening agent, between its amount ranges 0.05～0.2%;
Described slipping agent adopts amine hydroxybenzene, erucicamide or silicone, and wherein the addition of erucicamide is preferably in 0.05～0.3%; Wherein the content of silicone slipping agent is generally 0.2～1.5%;
Can adopt two or more slipping agent wherein simultaneously, total amount can not exceed desired scope when adopting simultaneously.
Major-minor oxidation inhibitor adopts phosphite stablizer and suffocated amine antioxidant to be used, two kinds of oxidation inhibitor add and consumption between 0.05～0.2%.
Because auxiliary agent particle diameters such as the synthetic silicide of lightweight are little, and bigger specific surface area arranged, and above-mentioned various auxiliary agents are after mixing, the total amount that joins among the PP still is smaller, for various auxiliary agents fully being disperseed and bringing into play its due impact of performance, also the component of various necessity can be prefabricated into the antistatic adhesion-resistant slippery master batch earlier, be the other method that the present invention is prepared the present composition.
Above-described " mixing granulation of preparation antistatic adhesion-resistant slippery BOPP composition " reaches " prefabricated antistatic master granule ", all adopts the agglomeration technique of powder.
More optimize and in particular, preparation antistatic adhesion-resistant slippery BOPP composition and " prefabricated antistatic master granule " all adopt the granulation of double-screw extruding pelletizing unit.
In order to make auxiliary agent energy and full and uniform the working of BOPP resin such as static inhibitor, opening agent, slipping agent, oxidation inhibitor, processing and thermo-stabilizer, the present invention has adopted these auxiliary agents has been mixed the mode that the back directly is metered in the granulation stage of resin; Perhaps adopt these auxiliary agents are prefabricated into master batch, the present invention adopts the agglomeration technique of powder, and continuous production high-content master batch is metered into the granulation section of prefabricated master batch at resin smoothly, produces BOPP resin PP Pipe Compound again.
The type of cooling has certain influence to surface resistivity, this is owing to the decision of PP specific molecular structure, PP is big ball crystalline molecular structure, and the static inhibitor molecule is present in the non-crystalline region of crystalline polymer, and by non-crystalline region to surface transport, antistatic molecule with the melt blending process of polymkeric substance in, there are some static inhibitor molecules can build lattice into PP, can not lose antistatic property to surface transport again after the moulding, so the migration that the crystallinity of resin density difference different and that cause is thus resisted electrostatic agent has remarkably influenced.PP is typical crystalline polymer, and in molding process, the type of cooling that changes goods can change the crystal property of PP.Degree of crystallinity height when cooling off gradually, spherulite size is bigger, and the ratio of non-crystalline region is little; Degree of crystallinity is low during quenching, and crystalline size is less, and the ratio of non-crystalline region is big, helps static inhibitor to surface transport.Therefore the type of cooling has remarkable influence to surface resistivity.In prioritization scheme of the present invention, the goods that processes obtains by quenching, its antistatic property are better than by cooling off the goods that obtain gradually.
During prefabricated master batch, for the particularly inorganic opening agent of various high-load additives in masterbatch need be carried out surface treatment, be that coupling agent is a requisite surface treatment agent of handling the opening agent, can be divided into silicane, titanate ester, aluminium esters of gallic acid, zirconium class, organic chromium class and complex class etc. by its chemical structure coupling agent.Above-mentioned several big class coupling agent is domestic all production at present basically, wherein before two classes and complex class be widely used.What the present invention adopted is silane coupling agent, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, vinyl tripropoxy silane, γ-(methacrylic acyloxy) propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan all be suitable for the present invention in the processing of opening agent.
In order to make the coupling agent uniform distribution, generally be mixed with 0.5～1.0% diluent during use.The kind of dosage of silane coupling agent and silane coupling agent is relevant with the surface-area of filler.Silane coupling agent is mixed with non-aqueous solution and uses, and its solvent can be selected organic solvents such as formaldehyde, ethanol, acetone or benzene for use.Consumption is generally needs about 1% of processing treatment weight.
In order to increase the dispersiveness of each auxiliary agent component in the masterbatch, low-molecular-weight wax or mineral wax are exactly the unavoidable composition that lacks, and the fusing point of low-molecular-weight wax is low, melting range is wide, if low-molecular-weight wax adds too much, the master batch melt fluidity is big, can play outer lubrication by work in-process, weaken shearing action; Moreover, can produce the precipitate of white because add-on too much can make the machine-shaping difficulty.
So requisitely in masterbatch will add dispersion agent low-molecular-weight wax, perhaps mineral wax.The add-on of low-molecular-weight wax or mineral wax is: between 0.2～2%.Add-on is more suitable between 0.2～1% when adopting low-molecular-weight wax; Want big if adopt the mineral wax consumption.
Described low-molecular-weight wax can adopt Poly Propylene Wax and polyethylene wax;
The preparation method of low-molecular-weight wax mainly contains two kinds: cracking process and polymerization.The molecular weight product that cracking process is produced is not easy control, molecular weight distribution broad; Adopt polymerization, the polyethylene wax molecular weight of this method preparation is controlled easily, and narrow distribution.The result shows that polyethylene wax number average relative molecular mass has dispersion effect preferably when 1000～4000 scopes, and the polyethylene wax relative molecular mass is high more, dispersive ability is strong more, and the consumption of polyethylene wax changes to some extent with the difference of polyethylene wax relative molecular mass, processed and applied condition.Molecular weight distribution has certain influence to the performance of polyethylene wax.The low-molecular-weight wax that preferably adopts polymerization to produce among the present invention requires 300 ℃ not decompose or seldom decompose: number average relative molecular weight 3000～4000; Molecular weight distribution is narrower, is preferably in below 5.
Low molecular polyethylene generally is irregular laminar, and when high-speed mixing, easily sticking dirt takes place the inwall at mixing tank, the present invention preferably adopts median size at 4～40 microns, the outward appearance Powdered micronization PE wax that is white in color can improve the blended effect, reduces the sticking dirty phenomenon of wax.
The softening temperature of Poly Propylene Wax, apparently higher than polyethylene wax, have nontoxic, non-corrosiveness, fusing point height, hardness height, good toughness, oilness are good, moisture-proof, oil resistant and have high brightness and characteristics such as smooth finish.That the PP wax that we adopt is that outward appearance is white in color is Powdered, median size is at 4～40 microns.
Mineral wax has montanin wax, paraffin, purification ceresine, mineral tallow etc. natively.The present invention generally only adopts white purified wax work.
The present invention recommends to adopt crystalline wax when adopting mineral wax, helps disperseing and reduces sticking dirty phenomenon in the mixing process.Can select for use and cover cured or paraffin of dawn.Consumption 1～2%.
The general masterbatch that uses is the hyperconcentration antistatic master batch, adapts to curtain coating, blowing, extrudes, wire drawing and plastic shapings processing such as braiding, hollow, have thermostability preferably and with the synergetic property of other auxiliary agents.In this important function for of research,, be unfavorable for the material homodisperse if adopt pellet and the blend of powdery auxiliary agent.The masterbatch of this problem development is exactly in order not have under the situation of powder, must to carry out the research of static inhibitor as base-material with pellet, and so, adopting masterbatch is a mode preferably.But, be not masterbatch use many more, sheet resistance value descends big more, but certain limit is arranged, this and anlistatig performance have relation, this mainly be because static inhibitor constantly from sample inside to surface transport, many more thereby the static inhibitor of specimen surface is assembled, its sheet resistance value is just low more; But the static inhibitor molecular arrangement of specimen surface has a degree of saturation, so its sheet resistance value also has a stationary value.The prepared high-load masterbatch of the present invention, when the content that adds masterbatch was 2%, antistatic property was stable after one month; But add content and be 5% and at 8% o'clock, PP Pipe Compound is comparatively steady from start to finish, the attenuating trend in the design occurs, but in the short period of time, bigger consumption can make fast the static inhibitor molecule to surface transport.This is that degree institute is extremely because the static inhibitor molecular arrangement of specimen surface reaches capacity.So add too much master batch, be a kind of surplus waste of performance.
Because static inhibitor exists that fusing point is low, poor heat stability, mix than problems such as difficulties with resin, difficulty in actual applications.Usually the content of static inhibitor is lower than 10%.For other performances to PP Pipe Compound produce as far as possible little influence, my problem has been developed add-on 10% above masterbatch.Employing has the composite anti-static agent prescription of synergistic effect, then in the PP Pipe Compound course of processing not only the masterbatch consumption can reduce and the stable yield of product.Along with the increase of master batch consumption, the mechanical property of PP Pipe Compound lowers small, stable performance.
The method for preparing antistatic adhesion-resistant slippery masterbatch of the present invention is as follows:
Super mixer is put in the opening agent, and entering the mouth from adding of mixing tank adds diluted coupling agent, mixes after 4 minutes, and again with slipping agent, static inhibitor, oxidation inhibitor, hot-work stablizer etc. also have the PP powder, add in proportion, mix the time more than 1 minute.
The ratio of various auxiliary agents in the masterbatch: 30～90 parts of PP powders, 2～8 parts in static inhibitor, 1～4 part of opening agent, 1～30 part of slipping agent, 1～4 part in oxidation inhibitor, 1～4 part of calcium stearate, 2～6 parts of low-molecular-weight wax.
Through the twin screw extruder granulation, the preparation master batch is provided with 190～210 ℃ of temperature with the material that mixes.
The use master batch prepares antistatic BOPP method for compositions of the present invention and is; in PP; ratio with antistatic adhesion-resistant slippery masterbatch 1.25～20%; with master batch accurately successive adding on the feeder of the side position of double-screw extruding pelletizing unit; make antistatic adhesion-resistant slippery composition of the present invention, prilling temperature is controlled between 190～250 ℃.
Add the preparation method for compositions, composition all can keep original performance of BOPP resin, and the kinetic friction coefficient of BOPP resin reaches 0.18～0.22, and surface resistivity reduces to 10
12～14Ω satisfies normal the production and application requiring of general coating materials production of articles factory.
The present invention has kept original performance of BOPP with the auxiliary agent of low amount, gives polypropylene antistatic, antiblocking, premium properties such as smooth, can be applicable to injection moulding, extrudes, casting film, blowing, thermoforming, film and fiber process.On the packing of film, has purposes widely especially.
Embodiment
Embodiment 1
Antistatic BOPP composite formula is:
PP:100% (selecting F1002B powder, F401 powder, F401H powder, F680L powder, F680M powder, the F680H powder of raising plastic molding and processing plant of sub-petrochemical industry stock company for use)
Static inhibitor: 0.3% (selects AB-33, ASA-51, ASP-2, the ASH-1 of Research Inst. of Chemical Industry, Beijing for use; Chemical Engineering Institute, HangZhou City HZ-1, HKD-151, HKD-196; Or the ATMER 129 of vapour Bagong department, ATMER 163, ATMER AS 290G all can)
Opening agent (synthetic silica): 0.08%
Slipping agent (erucicamide): 0.1%
1010 oxidation inhibitor (chemical name: four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester): 0.08% (select the IRGANOX1010 of Shanghai vapour Bagao bridge chemistry company limited for use, or Ningbo gold being regreted the product of refined precious chemical industry company limited);
168 oxidation inhibitor (chemical name: three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester): 0.08% (selecting the phosphite oxidation inhibitor IRGAFOS168 of Shanghai vapour Bagao bridge chemistry company limited for use)
Processing and thermo-stabilizer (calcium stearate): 0.1%
Performance (data are measured value):
(F401 powder) F401 of embodiment 1
Degree of cleaning, look grain, grain/kg resin≤5≤5
Melt flow rate (MFR), g/10min 1.8 1.9
Density, g/cm
30.90 0.90
Tensile yield strength, Mpa 34.3 32.0
Elongation at break, % 458 374
Isotactic index, % 96.0 96.0
The powder ash content, % (m/m) 0.02 0.02
Flake, 0.8mm, individual/1520cm
221
Flake, 0.4mm, individual/1520cm
255
Static friction coefficient 0.232 0.330
Kinetic friction coefficient 0.210 0.322
Surface resistivity, Ω 8.4 * 10
128.4 * 10
16
Performance data is the measured value after two weeks of placement, does not find bad phenomenon such as oily bloom in the film-forming process.
Embodiment 2
Antistatic adhesion-resistant slippery masterbatch: 1.25%
PP powder or pellet: 98.75% (selecting F1002B, the F401, F401H, F680L, F680M, the F680H that raise plastic molding and processing plant of sub-petrochemical industry stock company for use)
Formula of master batch wherein:
Coupling agent: 1% (employing be silane coupling agent, the A-186 β in dawn chemical plant, Nanjing-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; The perhaps A-151 thiazolinyl tripropoxy silane of Tianjin reagent one factory; Perhaps Nanjing dawn chemical plant, Yaohua Glass-making Plant, Shanghai, Tianjin reagent one factory etc. A-174 γ-(methacrylic acyloxy) propyl trimethoxy silicane; The perhaps A-1100 in chemical plant, Gai County, Liaoyang, γ-An Bingjisanyiyangjiguiwan)
PP powder: 44% (selecting F1002B powder, F401 powder, F401H powder, F680L powder, F680M powder, the F680H powder of raising plastic molding and processing plant of sub-petrochemical industry stock company for use)
Static inhibitor: 8% (static inhibitor is selected AB-33, ASA-51, ASP-2, the ASH-1 of Research Inst. of Chemical Industry, Beijing for use; Or Chemical Engineering Institute, HangZhou City HZ-1, HKD-151, HKD-196; Or the ATMER 129 of vapour Bagong department, ATMER 163, ATMER AS 290G all can)
Opening agent (synthetic silica): 4%
Slipping agent (erucicamide): 30%
1010 oxidation inhibitor: 2% (selecting for use IRGANOX1010, the Ningbo gold of Shanghai vapour Bagao bridge chemistry company limited to regret the product of refined precious chemical industry company limited)
168 oxidation inhibitor: 2% (selecting the phosphite oxidation inhibitor IRGAFOS168 of Shanghai vapour Bagao bridge chemistry company limited for use)
Processing and thermo-stabilizer (calcium stearate): 4%
Poly Propylene Wax: 6% (selecting the product of scientific and technological development institute of Fushun City TongYuan for use)
Performance (data are measured value):
The F401 powder F401 of embodiment 1
Degree of cleaning, look grain, grain/kg resin≤5≤5
Melt flow rate (MFR), g/10min 1.9 1.9
Density, g/cm
30.90 0.90
Tensile yield strength, Mpa 33.8 32.0
Elongation at break, % 488 374
Isotactic index, % 96.0 96.0
The powder ash content, % (m/m) 0.02 0.02
Flake, 0.8mm, individual/1520cm
211
Flake, 0.4mm, individual/1520cm
255
Static friction coefficient 0.246 0.330
Kinetic friction coefficient 0.220 0.322
Surface resistivity, Ω 5.9 * 10
148.4 * 10
16
Performance data is the measured value after two weeks of placement, does not find bad phenomenon such as oily bloom in the film-forming process.
Embodiment 3
Antistatic adhesion-resistant slippery masterbatch: 5%
PP powder or pellet: 95%
Each component consumption in the master batch among the embodiment 2 is changed into:
Coupling agent: 0.1%
PP powder: 90%
Static inhibitor: 2%
Opening agent (synthetic silica)): 1%
Slipping agent (erucicamide): 1%
1010 oxidation inhibitor: 0.5%
168 oxidation inhibitor: 0.5%
Processing and thermo-stabilizer (calcium stearate): 1%
Poly Propylene Wax: 4%
Embodiment 4
Composite formula is identical with embodiment 1, the static inhibitor consumption among the embodiment 1 is changed into: 0.1%.
Embodiment 5
Composite formula is identical with embodiment 1, the static inhibitor consumption among the embodiment 1 is changed into: 0.2%.
Embodiment 6
Composite formula is identical with embodiment 1, the static inhibitor consumption among the embodiment 1 is changed into: 0.4%.
Embodiment 7
Composite formula is identical with embodiment 1, the static inhibitor consumption among the embodiment 1 is changed into: 0.5%.
Embodiment 8
Composite formula is identical with embodiment 1, changes the static inhibitor among the embodiment 1 into composite antistatic agent (negatively charged ion and non-ionic antistatic agent are compound), and anionic antistatic agents accounts for 10% of static inhibitor total amount, and composite static inhibitor consumption is: 0.3%.(anionic antistatic agents can adopt the fatty group sulfonate of Shanghai chemical reagents corporation, and non-ionic antistatic agent can adopt the hydroxyethyl aliphatic amide of Dechang, Hangzhou chemical company)
Embodiment 9
Composite formula is identical with embodiment 1, changes the static inhibitor among the embodiment 1 into composite antistatic agent (negatively charged ion and non-ionic antistatic agent are compound), and anionic antistatic agents accounts for 15% of static inhibitor total amount, and composite static inhibitor consumption is: 0.3%.
The compound process of a small amount of interpolation anionic fatty group sulfonate is simple, but can make nonionic surfactants static inhibitor hydroxyethyl aliphatic amide that the antistatic effect of PP material is improved nearly 2 orders of magnitude, reaches 8.2*10
11Ω makes the surface resistivity of PP material reach balance time and foreshortens to 3～4 days; The compatibility performance of this two component is good, and the physicals of PP material is not affected, and antistatic effect is good.
Embodiment 10
Composite formula is identical with embodiment 1, changes the static inhibitor among the embodiment 1 into composite antistatic agent (negatively charged ion and non-ionic antistatic agent are compound), and anionic antistatic agents accounts for 20% of static inhibitor total amount, and composite static inhibitor consumption is: 0.3%.
Embodiment 11
Composite formula is identical with embodiment 1, changes the static inhibitor among the embodiment 1 into composite antistatic agent, can adopt the Hangzhou chemical industry to grind.Study carefully static inhibitor HKD-151 of institute and HKD-520, its mass ratio is 1: 1, and composite static inhibitor consumption is: 0.5%.
Embodiment 12
Composite formula is identical with embodiment 1, the opening agent consumption among the embodiment 1 is changed into: 0.05%.
Embodiment 13
Composite formula is identical with embodiment 1, the opening agent consumption among the embodiment 1 is changed into: 0.1%.
Embodiment 14
Composite formula is identical with embodiment 1, the opening agent consumption among the embodiment 1 is changed into: 0.12%.
Embodiment 15
Composite formula is identical with embodiment 1, the opening agent consumption among the embodiment 1 is changed into: 0.15%.
Embodiment 16
Composite formula is identical with embodiment 1, the opening agent consumption among the embodiment 1 is changed into: 0.2%.
Embodiment 17
Composite formula is identical with embodiment 1, changes the opening agent among the embodiment 1 into synthetic silicate, and consumption changes into: 0.05% (the available magnificent friendship development in science and technology SAB-8 of company limited of opening agent, the agent of SAB-9 silicate opening).
Embodiment 18
Composite formula is identical with embodiment 1, changes the opening agent among the embodiment 1 into synthetic silicate, and consumption changes into: 0.1%
Performance data and embodiment 1 are basic identical, and having only haze value is 10% obviously reduction (the available magnificent friendship development in science and technology SAB-8 of company limited of opening agent, the agent of SAB-9 silicate opening).
Embodiment 19
Composite formula is identical with embodiment 1, changes the opening agent among the embodiment 1 into synthetic silicate, and consumption changes into: 0.15% (the available magnificent friendship development in science and technology SAB-8 of company limited of opening agent, the agent of SAB-9 silicate opening).
Embodiment 20
Composite formula is identical with embodiment 1, changes the opening agent among the embodiment 1 into synthetic silicate, and consumption changes into: 0.2% (the available magnificent friendship development in science and technology SAB-8 of company limited of opening agent, the agent of SAB-9 silicate opening).
Embodiment 21
Composite formula is identical with embodiment 1, the slipping agent consumption among the embodiment 1 is changed into: 0.05%.
Embodiment 22
Composite formula is identical with embodiment 1, the slipping agent consumption among the embodiment 1 is changed into: 0.08%.
Embodiment 23
Composite formula is identical with embodiment 1, the slipping agent consumption among the embodiment 1 is changed into: 0.15%.
Embodiment 24
Composite formula is identical with embodiment 1, the slipping agent consumption among the embodiment 1 is changed into: 0.2%.
Embodiment 25
Composite formula is identical with embodiment 1, the slipping agent consumption among the embodiment 1 is changed into: 0.3%.
Embodiment 26
Composite formula is identical with embodiment 1, changes the slipping agent among the embodiment 1 into silicone, and consumption changes into: 0.2%.
Embodiment 27
Composite formula is identical with embodiment 1, changes the slipping agent among the embodiment 1 into silicone, and consumption changes into: 0.5%.
Embodiment 28
Composite formula is identical with embodiment 1, changes the slipping agent among the embodiment 1 into silicone, and consumption changes into: 0.8%.
Embodiment 29
Composite formula is identical with embodiment 1, changes the slipping agent among the embodiment 1 into silicone, and consumption changes into: 1.1%.
Embodiment 30
Composite formula is identical with embodiment 1, changes the slipping agent among the embodiment 1 into silicone, and consumption changes into: 1.3%.
Embodiment 31
Composite formula is identical with embodiment 1, changes the slipping agent among the embodiment 1 into silicone, and consumption changes into: 1.5%.
Embodiment 32
Composite formula is identical with embodiment 1, the oxidation inhibitor consumption among the embodiment 1 is changed into be 1010:0.1%, 168:0.1%.
Embodiment 33
Composite formula is identical with embodiment 1, changes the oxidation inhibitor consumption among the embodiment 1 into 1010:0.12%, 168:0.12%.
Embodiment 34
Composite formula is identical with embodiment 1, changes the oxidation inhibitor consumption among the embodiment 1 into 1010:0.15%, 168:0.15%.
Embodiment 35
Composite formula is identical with embodiment 1, changes the oxidation inhibitor consumption among the embodiment 1 into 1010:0.05%, 168:0.10%.
Embodiment 36
Composite formula is identical with embodiment 1, the calcium stearate consumption among the embodiment 1 is changed into: 0.05%.
Embodiment 37
Composite formula is identical with embodiment 1, the calcium stearate consumption among the embodiment 1 is changed into: 0.15%.
Embodiment 38
Composite formula is identical with embodiment 1, the calcium stearate consumption among the embodiment 1 is changed into: 0.2%.
Embodiment 39
Composite formula is identical with embodiment 2, and the master batch consumption among the embodiment 2 is changed into: 3%, and PP powder or pellet: 97%.
Performance is: static friction coefficient: 0.231, kinetic friction coefficient: 0.204, surface resistivity, 8.4 * 10
13Ω;
Performance data is the measured value after two weeks of placement, does not find bad phenomenon such as oily bloom in the film-forming process.
Embodiment 40
Composite formula is identical with embodiment 2, and the master batch consumption among the embodiment 2 is changed into: 5%, and PP powder or pellet: 95%
Performance is: static friction coefficient: 0.228, kinetic friction coefficient: 0.188, surface resistivity, 5.4 * 10
12Ω
Performance data is the measured value after two weeks of placement, does not find bad phenomenon such as oily bloom in the film-forming process.
Embodiment 41
Composite formula is identical with embodiment 3, and the master batch consumption among the embodiment 3 is changed into: 10%, and PP powder or pellet: 90%.
Embodiment 42
Composite formula is identical with embodiment 3, and the master batch consumption among the embodiment 3 is changed into: 15%, and PP powder or pellet: 85%
Embodiment 43
Composite formula is identical with embodiment 3, and the master batch consumption among the embodiment 3 is changed into: 20%, and PP powder or pellet: 80% embodiment.
Claims (10)
1, a kind of antistatic biaxially oriented polypropylene composition is a base-material with the polypropylene, includes opening agent, slipping agent, static inhibitor, oxidation inhibitor, processing and thermo-stabilizer, it is characterized in that,
Described static inhibitor is selected from: fatty mono glyceride or diester, fatty acid polyglycol ester, amides and/or ethyl amine; Its amount ranges is between 0.1～0.4%;
Anti adopts the inorganics or the particulate state crosslinked polysiloxane of silicon-dioxide series, and its particle diameter is less than 8 μ m;
Synthetic silicon-dioxide or silicate are adopted in described opening agent; Wherein, the granularity of synthetic silicon-dioxide be 2 μ m～4 μ m ask that consumption is between 0.05～0.2%; The consumption of described synthetic silicate is between 0.05～0.3%;
Calcium stearate is adopted in described opening agent, between its amount ranges 0.05～0.2%;
Described slipping agent adopts amine hydroxybenzene, erucicamide and/or silicone, and wherein the addition of erucicamide is 0.05～0.3%; Wherein the content of silicone slipping agent is 0.2～1.5%;
Major-minor oxidation inhibitor adopts phosphite stablizer and suffocated amine antioxidant to be used, two kinds of oxidation inhibitor add and consumption between 0.05～0.2%.
2, according to the described antistatic biaxially oriented polypropylene composition of claim 1, it is characterized in that, described base-material, the density of the PP of employing is: 0.90～0.91g/cm
3
3, according to claim 1 or 2 described antistatic biaxially oriented polypropylene compositions, it is characterized in that the amount ranges of described static inhibitor is between 0.15～0.3%;
In the described anti, the granularity of synthetic silicon-dioxide is 1 μ m～3 μ m.
4, according to the described antistatic biaxially oriented polypropylene composition of claim 3, it is characterized in that, described static inhibitor is that wherein the add-on of anionic fatty group sulfonate is 15%～20% of a composite antistatic agent total mass with non-ionic antistatic agent and the compound use of ionic anti-static agent.
5, the preparation method of the described antistatic biaxially oriented polypropylene composition of a kind of claim 1, step is as follows:
In the granulation section of producing Biaxially oriented polypropylene film (BOPP), with static inhibitor, opening agent, slipping agent, oxidation inhibitor, the hot-work stablizer joins mixing in the poor jar of airtight mixing by proportioning, in being metered into PP, melting mixing is a granulated into the antistatic biaxially oriented polypropylene PP Pipe Compound again; Perhaps various components are prefabricated into the antistatic adhesion-resistant slippery master batch earlier;
Described static inhibitor is selected from: fatty mono glyceride or diester, fatty acid polyglycol ester, amides and/or ethyl amine; Its amount ranges is between 0.1～0.4%; Preferably scope is 0.15～0.3%
Anti adopts the inorganics or the particulate state crosslinked polysiloxane of silicon-dioxide series, and its particle diameter is less than 8 μ m; Synthetic silicon-dioxide or silicate are adopted in described opening agent; Wherein, the granularity of synthetic silicon-dioxide is asking of 2 μ m～4 μ m, best 1 μ m～3 μ m, and consumption is between 0.05～0.2%; The consumption of described synthetic silicate is between 0.05～0.3%;
Calcium stearate is adopted in described opening agent, between its amount ranges 0.05～0.2%;
Described slipping agent adopts amine hydroxybenzene, erucicamide and/or silicone, and wherein the addition of erucicamide is 0.05～0.3%; The addition of silicone slipping agent is 0.2～1.5%;
Major-minor oxidation inhibitor adopts phosphite stablizer and suffocated amine antioxidant to be used, two kinds of oxidation inhibitor add and consumption between 0.05～0.2%.
6, according to the preparation method of the described antistatic biaxially oriented polypropylene composition of claim 5, it is characterized in that, described " mixing granulation of preparation antistatic adhesion-resistant slippery BOPP composition " reaches " prefabricated antistatic master granule ", all adopts the agglomeration technique of powder.
According to the preparation method of the described antistatic biaxially oriented polypropylene composition of claim 5, it is characterized in that 7, preparation antistatic adhesion-resistant slippery BOPP composition and " prefabricated antistatic master granule " all adopt the granulation of double-screw extruding pelletizing unit.
8, according to the preparation method of claim 5 or 6 or 7 described antistatic biaxially oriented polypropylene compositions, it is characterized in that,
The method for preparing the antistatic adhesion-resistant slippery masterbatch is as follows:
Super mixer is put in the opening agent, and entering the mouth from adding of mixing tank adds diluted coupling agent, mixes after 4 minutes, and again with slipping agent, static inhibitor, oxidation inhibitor, hot-work stablizer etc. also have the PP powder, add in proportion, mix the time more than 1 minute;
Described coupling agent adopts silane coupling agent, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, vinyl tripropoxy silane, γ-(methacrylic acyloxy) propyl trimethoxy silicane or γ-An Bingjisanyiyangjiguiwan; Consumption is for needing about 1% of processing treatment weight;
During use, this coupling agent is mixed with 0.5～1.0% diluent, and its solvent is selected organic solvents such as formaldehyde, ethanol, acetone or benzene for use;
Simultaneously, masterbatch also is added with low-molecular-weight wax or mineral wax; The add-on of this low-molecular-weight wax or mineral wax is between 0.2～2%.
9, according to the preparation method of the described antistatic biaxially oriented polypropylene composition of claim 8, it is characterized in that Poly Propylene Wax or polyethylene wax that described low-molecular-weight wax adopts polymerization to produce; Require 300 ℃ not decompose or seldom decompose: number average relative molecular weight 3000～4000;
Low molecular polyethylene adopts median size at 4～40 microns, the outward appearance Powdered micronization PE wax that is white in color.
Add-on is between 0.2～1% when adopting low-molecular-weight wax;
Be selected from when adopting mineral wax and cover cured or paraffin of dawn; Consumption 1～2%.
According to the preparation method of the described antistatic biaxially oriented polypropylene composition of claim 9, it is characterized in that 10, the amount ranges of described static inhibitor is 0.15～0.3%;
The granularity of described opening agent synthetic silicon-dioxide is 1 μ m～3 μ m.
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