CN103224676B - Vinylidene chloride copolymer composition, its manufacture method and film thereof or sheet material - Google Patents
Vinylidene chloride copolymer composition, its manufacture method and film thereof or sheet material Download PDFInfo
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Abstract
The present invention relates to vinylidene chloride copolymer composition, its manufacture method and film thereof or sheet material.Vinylidene chloride copolymer composition of the present invention is the copolymer compositions be made up of vinylidene chloride and polymerizable vinyl monomer, it is characterized in that, the weight average particle diameter of this copolymer compositions is the scope of 200 μm ~ 500 μm, further, the full width at half maximum (FWHM) of the size distribution represented with weight average is less than 150 μm.
Description
Technical field
The present invention relates to vinylidene chloride copolymer composition, its manufacture method, its film or sheet material and use the food container of this film or sheet material, described vinylidene chloride copolymer composition extrudes excellent in stability when melt molding.
Background technology
For the film manufactured by vinylidene chloride copolymer composition, sheet material, container, be suitable for packaging material for food, preservative film etc. due to excellences such as its oxygen barrier, moistureproofness, the transparency, chemical proofing, oil-proofness, adaptation, heat-shrinkables.In the manufacture method of the vinylidene chloride analog copolymer composition for food packaging film, have suspension polymerization and emulsion polymerization, but because suspension polymerization do not have the problem such as residual of emulsifying agent so generally use suspension polymerization.Suspension polymerization is following method: containing in the water of dispersion agent, after being formed the blending dispersion oil droplet of vinylidene chloride and polymerizable vinyl monomer, add polymerization starter and be polymerized by mechanical stirring.
When obtaining food packaging film, using the vinylidene chloride copolymer obtained by suspension polymerization, adopting common melt molding method to stretch or being processed into film or the sheet material of single or multiple lift when not stretching.
From patent documentation 1, patent documentation 2 etc., the vinylidene chloride copolymer generally obtained by suspension polymerization is particulate state.In addition, patent documentation 3 discloses a kind of vinylidene chloride copolymer composition obtained by suspension polymerization, and it has specific particle diameter, contained molecule quantity be a certain amount of below, and there is specific bulk density.Patent documentation 3 discloses following content: in order to obtain this vinylidene chloride copolymer composition, can prevent from realizing near the limit of polymkeric substance sedimentation by its stirring velocity being set in when suspension polymerization.
Prior art document
Patent documentation 1: Japanese Patent Publication 55-18242 publication
Patent documentation 2: Japanese Patent Publication 57-9575 publication
Patent documentation 3: International Publication No. 2003/006548 brochure
Summary of the invention
In general, the vinylidene chloride copolymer obtained by suspension polymerization can only obtain the wide vinylidene chloride copolymer of size distribution.When using the melt molding method vinylidene chloride copolymer composition wide to size distribution to stretch, due to the shape of vinylidene chloride copolymer particle and the uneven distribution of size, that the volume production of the multipolymer be filled in die head in machine barrel is changed is dynamic, thus has influence on the output of forcing machine.Therefore the pressure of pressure head produces variation, and result causes the membrane thickness unevenness of the film extruded.When high frequency sealing is carried out to obtain film wrapping body to the film of membrane thickness unevenness, then easily reduce productivity because sealing intensity is uneven.
In addition, in the vinylidene chloride copolymer composition described in patent documentation 3, not about preventing the description generating the large particle of particle diameter, in recent years, for the reason and under becoming the melt molding condition of more and more harsher vinylidene chloride copolymer composition, stability can not be extruded fully such as boosting productivity.
The object of the present invention is to provide a kind of vinylidene chloride copolymer composition, its film or sheet material and use the food packaging container of this film or sheet material, described vinylidene chloride copolymer composition extrudes excellent in stability when melt molding, and the film uniformity of described film or sheet material, high frequency seal compatibility and boiling adaptability are excellent.
The present inventor furthers investigate repeatedly for solving the problem, and found that, has specific weight average particle diameter by the vinylidene chloride copolymer composition of following manufacture method manufacture, and the full width at half maximum (FWHM) of the size distribution represented with weight average be constant below.The feature of described manufacture method is, adds softening agent in the front and back of vinylidene chloride and polymerizable vinyl monomer copolymerization, and the addition of softening agent after polymerization is less than the addition of the softening agent before polymerization.
The present inventor finds further, by melt molding method by described vinylidene chloride copolymer composition processing film forming or sheet material time, the rate of change that easily can obtain thickness be less than 10% and the impurity that length is more than 0.5mm to count be 0.01/m
2following film or sheet material, by these films or sheet material are used for food packaging film, high frequency sealing intensity when manufacturing film wrapping body becomes even, can boost productivity.
Extrude excellent in stability during vinylidene chloride copolymer composition melt molding of the present invention, the film obtained by said composition or sheet material because film uniformity is excellent, high frequency seal compatibility and boiling adaptability excellent.
Accompanying drawing explanation
Fig. 1 is the explanatory view of the measuring method representing full width at half maximum (FWHM).
Embodiment
Then, embodiments of the present invention are described.Following embodiment is in order to example of the present invention is described, and does not mean that the present invention is only limitted to this embodiment.The present invention only otherwise depart from its main idea, can be implemented by various mode.
The weight average particle diameter of vinylidene chloride copolymer of the present invention is the scope of 200 ~ 500 μm, is preferably 200 ~ 400 μm, is more preferably 200 ~ 300 μm.If particle diameter is in this scope, then extrude load constant when vinylidene chloride copolymer composition being stretched by melt molding method, can carry out stable extruding processing.Result can make the uniform film thickness of film or the sheet material obtained.
In addition, the full width at half maximum (FWHM) of the size distribution represented with weight average of vinylidene chloride copolymer of the present invention is less than 150 μm, is preferably less than 140 μm, is more preferably less than 130 μm.So-called full width at half maximum (FWHM) is the index of the width degree representing the measured value being distributed as the chevron shown in Fig. 1, and it refers to, obtains the particle diameter that the frequency of a plurality of 1/2 value with representing frequency maximum value is corresponding, the wherein difference of maximum value and minimum value.When the full width at half maximum (FWHM) of the size distribution represented with weight average is below 150 μm, then when using melt molding method to stretch to vinylidene chloride copolymer composition, the variation being filled into the amount of the multipolymer in machine barrel in die head caused by the shape of vinylidene chloride copolymer particle or the skewness of size can be suppressed, the variation of the output of forcing machine can be suppressed, result can obtain uniform film thickness and the impurity such as thermal degradation when impurity are counted few film or sheet material.
Weight average particle diameter and the full width at half maximum (FWHM) of size distribution represented with weight average can be measured by the particle size distribution analyzer based on Ku Erte calculating instrument.
Vinylidene chloride copolymer composition in the present invention makes vinylidene chloride and can obtain with the polymerizable vinyl monomer copolymerization of this monomer copolymerization.
As can with the polymerizable vinyl monomer of vinylidene chloride copolymerization, as long as being rich in copolymerizable can be then arbitrary vinyl monomer, as industrial useful compound, such as vinylchlorid can be enumerated; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) glycidyl acrylate; The vinyl acetate of the aliphatic carboxylic acid such as vinyl-acetic ester, propionate; The unsaturated aliphatic carboxylic acids such as vinylformic acid, methacrylic acid, methylene-succinic acid, β-crotonic acid, toxilic acid, fumaric acid, maleic anhydride; The half ester of the unsaturated aliphatic such as toxilic acid, methylene-succinic acid carboxylic acid and dibasic acid esters; The aromatic vinyl such as vinylbenzene, alpha-methyl styrene; (methyl) vinyl cyanide, (methyl) acrylamide etc. have the alkene class of copolymerizable double bond; Isoprene, divinyl etc. have the muriate of the dienes such as dienes and chloroprene of 2 copolymerizable double bonds; There is in molecule as (methyl) acrylate of divinylbenzene, dibasic aliphatic alcohol the monomer etc. of 2 copolymerizable double bonds.These can be used alone with the polymerizable vinyl monomer of vinylidene chloride copolymerization, also can mix two or more and use.Among these compounds, particularly preferably vinylchlorid, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) vinyl cyanide, vinylbenzene, be more preferably vinylchlorid.
For obtaining vinylidene chloride copolymer composition of the present invention, any one method such as suspension polymerization, emulsion polymerization, solution polymerization process can be used, preferably use suspension polymerization.When using suspension polymerization to manufacture, in polymerizer, dropping into other the additive such as the mixture of vinylidene chloride and polymerizable vinyl monomer, water, suspension agent, polymerization starter and softening agent, forming initiated polymerization after monomer oil droplet by stirring.As the forming method of monomer oil droplet, following arbitrary suspension method can be used: the direct suspension method of adding monomer in the water dissolving suspension agent; Or add in monomer and dissolved the water of suspension agent, via monomer mutually for after external phase, water is the dispersion state of disperse phase, make the suspension method that monomer is disperse phase, water is the dispersion of external phase.
In order to make polymerization carry out well, preferably the atmosphere such as nitrogen, argon gas will be set as in polymerizer.Polymerization temperature, polymerization time can determine aptly according to the kind, amount etc. of the kind of the kind of vinylidene chloride and polymerizable vinyl monomer, amount, polymerization starter, amount and chain-transfer agent, but preferably general 30 ~ 90 DEG C of polymerizations 10 ~ 100 hours, be more preferably 20 ~ 60 hours, more preferably 25 ~ 50 hours.
As the suspension agent used to utilize suspension polymerization to manufacture vinylidene chloride polymer composition of the present invention, the derivatived celluloses such as methylcellulose gum, ethyl cellulose, hydroxypropylcellulose, hydroxyethylmethyl-cellulose, Vltra tears can be used; The partly-hydrolysed thing etc. of polyvinyl alcohol and polyvinyl acetate.Among these, particularly preferably methylcellulose gum, Vltra tears.For these suspension agents 0.2 % by weight the aqueous solution in the surface tension of 20 DEG C, be preferably more than 5mN/m from the viewpoint of the particle diameter obtained, be preferably below 60mN/m from the progressive viewpoint of polymerization.
Relative to the mixed solution of vinylidene chloride and polymerizable vinyl monomer, the usage quantity of suspension agent is preferably 300 ~ 1000ppm.By being set in such scope, suspension polymerization stability can be obtained, effectively can produce weight average particle diameter and being 200 ~ 500nm and the vinylidene chloride copolymer composition that is minimized less than the amount of the molecule of 150 μm of particle diameter.Suspension agent once all can add and also can gradation add, and does not limit period its interpolation.
As polymerization starter, the peroxycarbonates class initiators such as such as peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxide-butyl carbonate, peroxy dicarbonate two (2-ethyl hexyl) ester can be enumerated; The tertiary own ester of new peroxide tert-butyl caprate, peroxidation neodecanoic acid, peroxidation neodecanoic acid tert-pentyl ester, peroxidation neodecanoic acid α-isopropyl phenyl ester, peroxidation neodecanoic acid 1,1,3, the tertiary own ester of 3-tetramethyl-butyl ester, tert-Butyl peroxypivalate, t-amyl peroxypivalate, peroxidation PIVALIC ACID CRUDE (25), peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-2 ethyl hexanoic acid 1,1, the peresters class initiators such as 3,3-tetramethyl-butyl ester, the new heptanoic acid tert-butyl ester of peroxidation; The peroxidation two acyl class initiator such as dilauroyl peroxide, diisobutyryl peroxide, peroxidation two (3,5,5-trimethyl acetyl), dibenzoyl peroxide; Tertbutyl peroxide, the α-hydroperoxide kind such as isopropyl benzene hydroperoxide, 1，1，3，3-tetramethylbutylhydro-peroxide initiator; The dialkyl peroxide class initiators such as the tertiary butane of peroxidation two, the tertiary hexane of peroxidation two, t-butylcumylperoxide; 2, the azo-initiators such as 2 '-Diisopropyl azodicarboxylate; The water-soluble peroxides such as Potassium Persulphate, ammonium persulphate, Sodium Persulfate; Or in these, be added with the polymerization starter etc. of the reductive agent such as amine, sodium bisulfite.For making polymerization rate homogenization, these polymerization starters can combinationally use the different polymerization starter of 10 hr half-life temperature of more than two kinds.In addition, these polymerization starters can directly use, and use after also can being made into aqueous emulsion, aqeous suspension.Among these, particularly preferably di-isopropyl peroxydicarbonate, peroxidation neodecanoic acid α-isopropyl phenyl ester, tert-Butyl peroxypivalate, peroxide-2-ethyl hexanoic acid tert-butyl, dilauroyl peroxide.
Relative to the mixed solution of vinylidene chloride and polymerizable vinyl monomer, the usage quantity of polymerization starter is preferably 100 ~ 7000ppm, is more preferably 500 ~ 5000ppm, more preferably 1000 ~ 3000ppm.
In addition, because the corrosion speed in polymerization machine and in the device of subsequent handling accelerates, so in order to make the pH value of vinylidene chloride copolymer slurries unduly decline, in polymerization initial stage or polymerization way, minimally alkaline matter can be added for the object of adjusted to ph.
In order to manufacture vinylidene chloride copolymer composition of the present invention, also the chain-transfer agents such as mixing trieline, dodecyl mercaptans, spicy thioalcohol, Thiovanic acid, thioglycollic acid-2-ethyl hexyl ester can be added when being polymerized.
In general, vinylidene chloride copolymer composition, being added the deterioration being easily subject to man-hour being caused by thermal conductance by melt molding method, extrudes poor stability.Therefore extrude stability add softening agent in order to improve in vinylidene chloride copolymer composition.In vinylidene chloride copolymer composition of the present invention, need to add at least one softening agent, will based on following methods when importantly adding.
That is, vinylidene chloride copolymer composition of the present invention is when the suspension polymerization by vinylidene chloride and polymerizable vinyl monomer manufactures, and utilizes following manufacture method manufacture.The feature of described manufacture method is, comprise following operation: in the mixture that polymerization starts forward direction vinylidene chloride and polymerizable vinyl monomer, add at least one softening agent, and then in the vinylidene chloride copolymer composition obtained, add at least one softening agent after completion of polymerization; And the addition of softening agent after polymerization is less than the addition of the softening agent before polymerization.
By using this addition means to add softening agent, the full width at half maximum (FWHM) that can obtain the size distribution represented with weight average is for below 150-and the little vinylidene chloride copolymer composition of the interdependence of the plasticizer loading of particle diameter.Except this method, such as, when adding the softening agent of full dose before polymerization, because softening agent easily causes the coalescent of monomer oil droplet so have lost polymerization stability thus easily generate huge particle, the stability of extruding during melt molding worsens.On the other hand, when adding the softening agent of full dose after polymerisation, then can show the interdependence that the larger thus load per unit of volume of softening agent of the less surface-area relative to particle volume of particle diameter becomes the plasticizer loading of many so-called particle diameters, when melt molding, fluxing point easily departs from, and therefore extrudes stability and worsens.In order to suppress these phenomenons, obtaining having the vinylidene chloride copolymer composition of suitable size distribution and softening agent distribution, needing to add softening agent before polymerization with after polymerization, and the addition of softening agent after polymerization is less than the addition of the softening agent before polymerization.The ratio of the addition of the softening agent added before polymerization and after polymerization depends on the total amount of added softening agent, before preferred polymeric: after polymerization=6: 4 ~ 9: 1.Be more preferably 7: 3 ~ 8: 2.
As softening agent, the phthalic ester such as dioctyl phthalate (DOP), diisononyl phthalate can be enumerated; The citrates such as tributyl acetylcitrate; The fatty group dibasic acids such as Uniflex DBS, dioctyl sebacate, diisobutyl adipate; The triglyceride level such as vanay, tributyrin; Epoxidized vegetable oil after epoxidation has been carried out to soybean oil, linseed oil, Oleum Cocois, Thistle oil, sunflower seed oil, cottonseed wet goods; The epoxidized fat acid monoesters such as epoxidized octyl stearate; The epoxidized fat acid diesters that the glycol ester of unsaturated fatty acids obtains through epoxidation; The cycloaliphatic epoxides such as epoxidation six hydrogen phthalate; The epoxy resin etc. such as bisphenol A diglycidyl ether.Among these, particularly preferably tributyl acetylcitrate, Uniflex DBS, epoxidised soybean oil.These softening agent can be used alone, and also can mix two or more and use, preferably two or more use of mixing.Mix in the situation of two or more softening agent use, softening agent is roughly divided into the epoxy compounds in its molecule with epoxy group(ing) and other softening agent without epoxy group(ing), if use this two kinds of softening agent, plasticization effect and thermostability can be had concurrently, so more preferably.
Relative to vinylidene chloride copolymer composition 100 mass parts, the total amount of the addition of softening agent is preferably 0.1 ~ 10 mass parts, is more preferably 0.2 ~ 6 mass parts.Wherein, the addition of epoxy compounds is preferably 0.05 ~ 5 mass parts, is more preferably 0.1 ~ 3 mass parts, and the addition of other softening agent is preferably 0.05 ~ 10 mass parts, is more preferably 0.1 ~ 6 mass parts.
In vinylidene chloride copolymer composition of the present invention, suitably can add the additives such as antioxidant, thermo-stabilizer, lubricant, tensio-active agent, photostabilizer, the agent of pears face, gelation improving agent, pH adjusting agent, antistatic agent, linking agent, defoamer, Scale inhibitors, pigment, filler.As these additives, such as vitamin E, butylhydroxy toluene (BHT), thio-2 acid alkyl ester, triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3 can be enumerated, 5-di-t-butyl-4-hydroxyphenyl) antioxidant such as propionic ester, four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane; The representative examples of saturated aliphatic monocarboxylic acids such as citric acid and an alkali metal salt, carbonate, sulfites, trisodium phosphate, tripoly phosphate sodium STPP, acetic acid and the organic or inorganic such as the saturated aliphatic dicarboxylic acids such as alkaline metal salt, succsinic acid and alkaline metal salt thereof acid and the thermo-stabilizers such as inorganic salts such as salt, ethylenediamine tetraacetic acid (EDTA) and alkaline metal salt thereof, magnesium oxide, magnesium hydroxide; The lubricants such as the monoamide of the fatty acid esters such as wax, monoglyceride such as oxidized polyethlene wax, paraffin, montanic acid ester type waxes, lipid acid or diamide; The nonionogenic tensides such as sorbitan fatty acid esters, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid esters; The photostabilizers such as 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-Chloro-Benzotriazole; The pears face agent etc. such as silicon-dioxide, hydrated magnesium silicate, calcium carbonate.These additives preferably use as required.
The blending means of these additives is not particularly limited, existing method can be applied, be polymerized after in vinylidene chloride before can being added into polymerization in advance and the mixture of polymerizable vinyl monomer, also can or be added in the vinylidene chloride polymer composition of pulp-like after polymerization in polymerization way, can also be added in the pulverous vinylidene chloride copolymer composition before melt molding.Mix in the situation of these additives in pulverous vinylidene chloride copolymer composition, the mixing of mixing, adopting the agitator such as propeller agitator or helix agitator to carry out can undertaken by such as employing duo mill, the mixing etc. adopting Henschel super mixer to carry out, any one mode of the heating hybrid mode of application more than 60 DEG C or the low-temperature mixed mode below 60 DEG C.
The stirrer of the polymerizer for suspension polymerization is not particularly limited, baffle plate can be used as required.In stirrer, the impeller vane, fan turbine blade, three leaf swept-back (Pfaudler) blades, Burmagin blade etc. that usually use in polyvinyl chloride-base monomer polymerization can be enumerated, but wherein preferably use the three leaf swept-back vanes easily controlling monomer oil droplet footpath.Finger-type, round tube type, D type and ring-like etc. can be enumerated as baffle plate.
For obtaining the vinylidene chloride copolymer particle of the specific weight average particle diameter of the present invention, need the balance of the stirring velocity maintaining capillary decline and the stirrer caused by suspension agent well, make the polymer beads not sedimentation of generation simultaneously or do not stick on polymerizer or stirrer, completing polymerization thus.For this reason, the agitation condition controlling machinery is particularly important, particularly by selected stirring velocity and agitation revolution, while making polymer beads swim, makes it be polymerized.
In general, for making polymer beads swim, stirring velocity is set as the high speed that polymer beads is fully swum, but in this case, polymer beads is subject to the shearing force of agitating vane, the particle diameter of polymkeric substance diminishes.On the other hand, if make polymkeric substance particle diameter become large and stirring velocity is set as low speed, then polymkeric substance starts sedimentation, and the cohesion that polymkeric substance also can occur adheres to, and has the danger all sticked in polymerizer.In the present invention, for preventing the sedimentation of this polymkeric substance and suppressing the formation of molecule, need to carry out suspension polymerization near the limit that sedimentation does not occur polymkeric substance.Such as, when using three leaf swept-back vanes, when the stirring velocity represented with following formula 11 is set as more than 0.7m/sec, then suspension polymerization can stably be carried out, therefore preferably; When being set as below 5.5m/sec, then the particle diameter of obtained polymkeric substance, in suitable scope, is preferred.Concrete condition needs to change according to the size of the scale of stirring.
[formula 11] stirring velocity (m/sec)=n π d/60
(n: the revolution (rpm) of agitating vane, π: pi, d: agitating vane length (m))
Such as agitating vane length is
when, when 60 ~ 200rpm, stirring velocity is 1.3 ~ 4.2m/sec, so preferably, in addition, span of foil is
when, when 20 ~ 50rpm, stirring velocity is 2.0 ~ 5.3m/sec, so preferably.
The weight-average molecular weight of vinylidene chloride copolymer composition of the present invention is preferably 60,000 ~ 200,000, is more preferably 70,000 ~ 150,000, and more preferably 80,000 ~ 130,000.Weight-average molecular weight when this scope, from during melt molding extrude stability, high frequency stopping property, the adaptive viewpoint of boiling be preferred.Also can, by being coordinated with arbitrary ratio by vinylidene chloride copolymer compositions of more than two kinds different for weight-average molecular weight, make the weight-average molecular weight of composition in described scope.Weight-average molecular weight uses the polystyrene conversion weight-average molecular weight based on gel permeation chromatography to measure.
When using vinylidene chloride copolymer composition of the present invention, then the rate of change that can easily obtain thickness by melt molding method be less than 10% and the impurity that length is more than 0.5mm to count be 0.01/m
2following film or sheet material.To the film made with about 300m length measurment average film thickness and standard deviation, obtain the rate of change of thickness according to following formula 1.The rate of change of thickness is more preferably less than 6%.
The rate of change (%)=(standard deviation/average film thickness) × 100 of [formula 1] thickness
In addition, when carrying out melt molding, by using the determination of foreign matter equipment of image sensor mode, the number that the length be mixed in film after beginning melt molding is the thermal degradation when impurity of the vinylidene chloride copolymer of more than 0.5mm size being detected, obtains impurity thus and count.Impurity is counted and is more preferably 0.006/m
2below.
When these films or sheet material are used for food packaging film or sheet material for food packaging, for obtained film or sheet-material package body and carry out high frequency sealing time, because electrode can be made to adhere with film or sheet material under an even pressure always, so sealing intensity can be made even, can reduce when packaging is filled and cooking disinfection time the breaking of film wrapping body, can boost productivity.
High frequency seal compatibility is evaluated as follows: the film of incision or sheet material are arranged at film supply unit, high frequency sealing, automatic filling portion, automatic filling clipper (ADP (trade(brand)name) that such as Asahi Chemical Industry's chemistry (strain) manufactures) after ligation integrally, high frequency sealing is adopted to be packed into sausage raw meat in the cylindric film or sheet material of middle envelope (セ Application タ mono-シ mono-Le) as weighting material, obtain the wrapping body of two ends wire clamping, record broken bag number now, broken bag incidence when calculating filling by following formula 2, evaluate high frequency seal compatibility thus.During filling, broken bag incidence is more better close to 0 high frequency seal compatibility, but from the viewpoint of productivity be preferably less than 0.02%, be more preferably less than 0.01%.
Broken bag incidence (%)=(during filling broken bag frequency/filling radical) × 100 when [formula 2] fills
Boiling adaptability is evaluated as follows: Heating temperature be 120 DEG C, under heat-up time is the condition of 20 minutes, to being carried out heating and pressurizing germicidal treatment (so-called boiling process) by the wrapping body obtained in the evaluation of above-mentioned high frequency seal compatibility, maintain heating tank internal pressure afterwards constant, it is after 25 DEG C that pressurization is cooled to temperature, relief pressure, wrapping body is taken out from heating tank, record is now from the quantity that the hermetic unit of wrapping body breaks, calculate boiling broken bag incidence by following formula 3, evaluate boiling adaptability thus.Boiling broken bag incidence is more better close to 0 boiling adaptability, but from the viewpoint of productivity be preferably less than 0.02%, be more preferably less than 0.01%.
[formula 3] boiling broken bag incidence (%)=(boiling broken bag radical/boiling process radical) × 100
Vinylidene chloride copolymer composition of the present invention can adopt common melt molding method to stretch, or is processed into film or the sheet material of single or multiple lift when not stretching.Wherein, the following 2 kinds of making methods of suitable use: inflation method, namely, extrude from the circular die of screw extrusion press, make tubular extrudate by after the 1st cooling bath below room temperature, passing into the 2nd pre-heating bath, making its bubble forming expansion thus the method making film or sheet material to importing air between 2 groups of pinch rolls; Or T modulus method, namely extrude cooling by T mould, thus make the method for film or sheet material.More preferably inflation method is used.
When supplying vinylidene chloride copolymer composition of the present invention to forcing machine, if use the vinylidene chloride copolymer composition continuous measurement to loading hopper device inside on trend of purchasing machine and the material feeder of weight feed, then effect of the present invention is more remarkable, so preferably.Such as screw feeder, annular material feeder, electromagnetism material feeder, weight-type material feeder, volumetric feeder etc. can be enumerated as this material feeder.Wherein, preferred operating weight formula material feeder carries out the method that mixes.By using the material feeder of weight feed vinylidene chloride copolymer composition, can suppress uneven to forcing machine supply further, extrude add man-hour the variation of screw-rod engine load, the variation of extrusion capacity, can improve and extrude stability.In addition, can modified resin resolvent in the adhesion inhibition of die head spout, the painted Sum decomposition logistics that also can reduce resin goes out.
For uneven to supply during forcing machine supply vinylidene chloride copolymer composition, it is evaluated by the rate of change such as measuring material feeder feed speed.The rate of change of material feeder feed speed is evaluated as follows: by measuring feed rate for several times in the Time constant of the scope of such as 10 ~ 20 minutes, according to its simple average value (single Pure mean value) and standard deviation, calculated by following formula 4, thus evaluate.The rate of change of material feeder feed speed is less, supplies uneven less, is preferably less than 5%.
The rate of change (%)=(standard deviation/simple average value) × 100 of [formula 4] material feeder feed speed
The variation of the screw-rod engine load of forcing machine is evaluated as follows: to the mean value of the screw-rod engine electric current of forcing machine during melt molding with its amplitude of fluctuation is observed, record, calculate screw-rod engine load change rate by following formula 5, thus evaluate.The rate of change of screw-rod engine load is the smaller the better, is preferably less than 8%, is more preferably less than 4%.
[formula 5] screw-rod engine load change rate (%)=(amplitude of fluctuation/average current value of current value) × 100
Vinylidene chloride copolymer composition of the present invention, by supplying to forcing machine via vacuum charging bucket, can improve further and extrude stability, reduces thermal degradation when impurity further.The vacuum tightness of vacuum charging bucket is preferably-6.66 × 10
-2below MPa, is more preferably-7.99 × 10
-2mpa ~-10.1 × 10
-2the scope of MPa.By via being set as that the vacuum charging bucket of this condition supplies said composition to forcing machine, bubble can be suppressed to be mixed in resin melt, stable maintenance can extrude processibility and stretchiness.Through being connected to the forcing machine of vacuum charging bucket bottom, adopting known method to stretch, or form film or sheet material under the condition do not stretched.
Film of the present invention or sheet material carry out orientation by biaxial stretch-formed, there is heat-shrinkable, further, also can be used as aptly can at 120 DEG C (pressurizations 0.245MPa), the thermotolerance film used under such heating and pressurizing sterilization (so-called boiling process) condition for 20 minutes or sheet material.Stretching ratio is longitudinally preferably 2.0 ~ 4.5 times, transverse direction is 3.0 ~ 5.0 times.For the thickness of film or sheet material, monofilm is preferably 5 ~ 30 μm, is more preferably 10 ~ 25 μm.Also can use as two film or sheet material according to purposes.
In addition, vinylidene chloride copolymer composition of the present invention can be processed into multilayer film or sheet material by coetrusion, laminating.
In addition, the post-treatment such as Corona discharge Treatment can be implemented to film of the present invention or sheet material as required.
The film obtained like this or the barrier properties for gases of sheet material, the non-extractable caused by oily food, mechanical property, high frequency seal compatibility, boiling adaptability are excellent, and what can be used as ham, sausage, cheese, prepared food, other food etc. aptly needs the wrapping material of barrier and preservative film etc.Wherein can be used as casing especially aptly.
Embodiment
Then, in further detail the present invention is described by embodiment and comparative example, but the present invention is not by the restriction of these embodiments.
Below provide measuring method and the evaluation method of characteristic in the present invention.
1) weight average particle diameter of vinylidene chloride copolymer composition and the full width at half maximum (FWHM) of size distribution that represents with weight average
Weight average particle diameter and the full width at half maximum (FWHM) of size distribution represented with weight average use particle size distribution analyzer (BeckmanCoulter Co., Ltd. manufactures Multisizer3) to measure.
2) weight-average molecular weight of vinylidene chloride copolymer
Weight-average molecular weight uses gel permeation chromatography (GPC), measures polystyrene conversion weight-average molecular weight according to following condition.
Determinator: gel permeation chromatograph HLC-8020 (manufacture of Tosoh society)
Post: TSKgelSuperHM-H (manufacture of Tosoh society) 7.8mm × 30cm × 2
Elutriant: tetrahydrofuran (THF) (THF)
Flow velocity: 1ml/min
Column temperature: 40 DEG C
Detector: RI
3) rate of change of material feeder feed speed
During melt molding, in spiral material feeder, the feed rate of vinylidene chloride copolymer composition is set as 100kg/hr, 5 times are measured to the feed rate in the Time constant of the scope of 10 ~ 20 minutes, obtain its simple average value and standard deviation.By following formula 6, obtain the rate of change of material feeder feed speed.It should be noted that, use Off ア イ ト ロ Application SK-S (manufacture of Hosokawamicron society) as spiral material feeder herein.
The rate of change (%)=(standard deviation/simple average value) × 100 of [formula 6] material feeder feed speed
4) screw-rod engine load change rate
During melt molding, obtained the screw-rod engine load change rate of forcing machine by following formula 7, as the criterion of extruding stability.
The rate of change (%)=(amplitude of fluctuation/average current value of current value) × 100 of [formula 7] screw-rod engine load
5) rate of change of the thickness of film
To the film made with about 300m length measurment average film thickness and standard deviation, obtained the rate of change of the thickness of film by following formula 8.
The rate of change (%)=(standard deviation/average film thickness) × 100 of the thickness of [formula 8] film
6) impurity is counted
When carrying out melt molding, the determination of foreign matter machine of image sensor mode is used to detect the thermal degradation when impurity of the vinylidene chloride copolymer being mixed into film.After starting melt molding, detect the number that length is the thermal degradation when impurity of more than 0.5mm size, obtain the impurity number of each square metre.
7) high frequency seal compatibility
The duplicature cut in the mode of folding width 40mm is arranged on automatic filling clipper ADP that the Asahi Chemical Industry's chemistry (strain) after by film supply unit, high frequency sealing, automatic filling portion, ligation integrally manufactures, by high frequency sealing, sausage raw meat (pork meat stuffing) is packed in the cylindric film of middle envelope as weighting material, obtains the wrapping body of two ends wire clamping.Observe and record the broken bag number now making 50000 periods, during by following formula 9 to fill, the mode of broken bag incidence is evaluated.
Broken bag incidence (%)=(during filling broken bag frequency/50000 piece) × 100 when [formula 9] fills
8) boiling adaptability
By gauge pressure in heating tank be 0.245MPa, under temperature is the condition of 120 DEG C, 20 minutes, heating and pressurizing germicidal treatment (so-called boiling process) is carried out to by 50000 wrapping bodies obtained in the evaluation of above-mentioned high frequency seal compatibility, maintain heating tank internal pressure afterwards constant, it is after 25 DEG C that pressurization is cooled to temperature, relief pressure, from heating tank, take out wrapping body, it can be used as final packaging body.Investigate the quantity of breaking from the hermetic unit of wrapping body, evaluated in the mode of boiling broken bag incidence by following formula 10.
[formula 10] boiling broken bag incidence (%)=(boiling broken bag radical/50000 piece) × 100
[embodiment 1]
Possessing three leaf swept-back vanes (length footpath 400mm), finger-type baffle plate, temperature take into account in the reactor (internal volume 300L) of nitrogen ingress pipe, add deionized water and suspension agent Vltra tears, prepare suspension 100 mass parts that the Vltra tears concentration of having dissolved is 500ppm.
Then after adding 80 mass parts vinylidene chlorides, 20 mass parts vinylchlorid, 0.15 mass parts initiator di-isopropyl peroxydicarbonate, 3 mass parts Uniflex DBSs (hereinafter referred to as DBS), low whipping speed is be heated to 45 DEG C under 1.4m/sec, nitrogen atmosphere, starts polymerization.After continuing reaction in 10 hours, be warming up to 55 DEG C with 1 hour, stirring velocity be set as 1.2 times (1.68m/sec) of initial stage speed, continue further to carry out polymerization in 15 hours.After reaction terminates, be separated unreacted monomer, the weight average particle diameter of dried vinylidene chloride copolymer composition is 270 μm, and the full width at half maximum (FWHM) of the size distribution represented with weight average is 130 μm.By the vinylidene chloride copolymer composition dissolves that obtains in tetrahydrofuran (THF) (hereinafter referred to as THF), by gel permeation chromatography polystyrene conversion molecular weight, weight-average molecular weight is 110000.
In the vinylidene chloride copolymer composition that 100 mass parts obtain, add 2 mass parts epoxidised soybean oil (hereinafter referred to as ESO), 0.01 mass parts vitamin E, 0.1 mass parts silicon-dioxide, 0.05 mass parts red pigment, obtain vinylidene chloride copolymer composition.
Use spiral material feeder, be set as-9.06 × 10 via Vacuum Pressure
-2it is in the forcing machine of 40mm that the vacuum charging bucket of MPa is put into diameter, extrudes as after ring-type, cools rapidly in the cooling tank of 10 DEG C, then makes it by the warm water bath of 20 DEG C.Further, between the pinch roll that 2 groups of rotational surface velocity are different, be pressed into air make it expand, after length direction 2.8 times, width 3.7 times of stretch orientations, by flat for this tubular film extrusion, obtain the duplicature of thickness 40 μm.Evaluating the rate of change, the screw-rod engine load change rate of material feeder feed speed when extruding masking, the film obtained being measured to the rate of change of average film thickness and thickness.
Then, the duplicature cut in the mode of folding width 40mm is arranged on automatic filling clipper ADP that Asahi Chemical Industry's chemistry (strain) manufactures, evaluates high frequency seal compatibility, then evaluate boiling adaptability.
Result is shown in table 1.
[embodiment 2 ~ 6]
According to suspension agent, initial stage stirring velocity, softening agent addition and addition means that table 1 is recorded, carry out embodiment 2 ~ 6 similarly to Example 1.Result is shown in table 1.
[comparative example 1 ~ 3]
According to suspension agent, initial stage stirring velocity, softening agent addition and addition means that table 1 is recorded, compare example 1 ~ 3 similarly to Example 1.Result is shown in table 1.
[table 1]
Can be proved by embodiment and comparative example, vinylidene chloride copolymer composition of the present invention extrude excellent in stability, the film of film uniformity, high frequency seal compatibility and boiling adaptability excellence can be obtained.
Industrial applicibility
Vinylidene chloride copolymer composition of the present invention extrudes excellent in stability when melt molding, the film uniformity of its film or sheet material, high frequency seal compatibility and boiling adaptability are excellent, therefore, it is possible to be used as ham, sausage, cheese, prepared food, other food etc. aptly need the wrapping material of barrier and preservative film etc.Wherein can be used as casing especially aptly.
Claims (4)
1. a vinylidene chloride copolymer composition, it is the copolymer compositions be made up of vinylidene chloride and polymerizable vinyl monomer, it is characterized in that, the weight average particle diameter of this copolymer compositions is the scope of 200 μm ~ 500 μm, and, the full width at half maximum (FWHM) of the size distribution represented with weight average is less than 150 μm
Described vinylidene chloride copolymer composition is manufactured by following manufacture method:
Softening agent is added in the front and back of reacting at the suspension copolymerization of vinylidene chloride and polymerizable vinyl monomer, and the addition of softening agent after polymerization is less than the addition of the softening agent before polymerization.
2. film or a sheet material, is characterized in that, it is made up of vinylidene chloride copolymer composition according to claim 1, and the rate of change of its thickness is less than 10%, and the impurity that length is more than 0.5mm to count be 0.01/m
2below.
3. a food container, it uses film according to claim 2 or sheet material.
4. food container as claimed in claim 3, it is casing.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529736A (en) * | 2001-07-13 | 2004-09-15 | 旭化成株式会社 | Composition of vinylidene chloride copolymer particles |
| JP2007119583A (en) * | 2005-10-27 | 2007-05-17 | Asahi Kasei Life & Living Corp | Polyvinylidene chloride resin composition and method for producing the same |
| JP2008063418A (en) * | 2006-09-06 | 2008-03-21 | Asahi Kasei Chemicals Corp | Composition for coloring vinylidene chloride resin and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529736A (en) * | 2001-07-13 | 2004-09-15 | 旭化成株式会社 | Composition of vinylidene chloride copolymer particles |
| JP2007119583A (en) * | 2005-10-27 | 2007-05-17 | Asahi Kasei Life & Living Corp | Polyvinylidene chloride resin composition and method for producing the same |
| JP2008063418A (en) * | 2006-09-06 | 2008-03-21 | Asahi Kasei Chemicals Corp | Composition for coloring vinylidene chloride resin and its manufacturing method |
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