CN103224581B - Vinylidene chloride analog copolymer, its composition and film thereof or sheet material - Google Patents
Vinylidene chloride analog copolymer, its composition and film thereof or sheet material Download PDFInfo
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Abstract
The vinylidene chloride generation of vinylidene chloride analog copolymer composition of the present invention when melt molding caused by thermolysis is few; Can obtain film uniformity excellent and thermal degradation when impurity is counted few film or sheet material; And the recirculation adaptability of melt molding processed goods is high; High frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence.Vinylidene chloride analog copolymer of the present invention is the vinylidene chloride analog copolymer be made up of vinylidene chloride and vinylchlorid, wherein, utilize proton magnetic resonance (PMR) optical spectroscopy (
1when H-NMR) carrying out analyzing, be less than 0.5 % by mole from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end relative to the monomeric unit forming vinylidene chloride analog copolymer.
Description
Technical field
The generation of vinylidene chloride when the present invention relates to melt molding caused by thermolysis is few, can obtain film uniformity excellent few film or sheet material and thermal degradation when impurity is counted vinylidene chloride analog copolymer and composition thereof; Its film of high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence or sheet material; And employ the food container of this film or sheet material.
Background technology
For the film, sheet material, the container that are manufactured by vinylidene chloride analog copolymer composition, be suitable in packaging material for food, preservative film etc. due to excellences such as its oxygen barrier, moistureproofness, the transparency, chemical proofing, oil-proofness, tackiness, heat-shrinkables.In the manufacture method of the vinylidene chloride analog copolymer 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 analog 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.But the poor heat stability of vinylidene chloride analog copolymer, thus when its melt molding, easily part is subject to the oxidative degradation caused by thermal degradation when or oxygen, and therefore products formed can be painted, has the danger that significantly infringement goods are worth.In addition, known vinylidene chloride analog copolymer can generate vinylidene chloride due to thermolysis, vinylidene chloride is the material that residual quantity in food packaging film purposes in products formed is subject to legal restrictions, requires to reduce as far as possible its remaining quantity in products formed.
In order to improve the thermostability of vinylidene chloride analog copolymer, carried out a lot of research in the past.Patent Document 1 discloses following method: in vinylidene chloride analog copolymer, imported the structural unit with double bond by copolymerization one chloroacetylene, improving tone and the outward appearance of formed body by controlling recrystallization temperature.In addition, Patent Document 2 discloses following content: the UV value corresponding to 3 ~ 4 conjugated double bond amounts is in the vinylidene chloride analog copolymer film forming thing of certain relation with the NMR value of the isolated double bond amount corresponding to molecular chain inside, tonal variation caused by thermal degradation when is few, can suppress the rheological parameters' change with time processing rear tone.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-283346 publication
Patent documentation 2: Japanese Unexamined Patent Publication 9-286865 publication
Summary of the invention
In order to improve the thermostability of vinylidene chloride analog copolymer, usually widely use the antioxidants such as the thermo-stabilizers such as epoxy compounds, sulphur system antioxidant, hindered phenol system antioxidant.But, even if when adding these thermo-stabilizers and antioxidant, thermal stability result during melt molding can not be said fully, and, add the generation that such additive can not suppress the vinylidene chloride of vinylidene chloride analog copolymer caused by thermolysis, be strongly required the vinylidene chloride analog copolymer not being vulnerable to thermolysis.
In the vinylidene chloride analog copolymer that patent documentation 1 is recorded, when utilizing melt molding method to carry out stretch process, can not get sufficient thermostability, and the particular monomers needing importing one chloroacetylene such, be unsuitable for commercially producing.In the vinylidene chloride analog copolymer film forming thing described in patent documentation 2, although the rheological parameters' change with time of the tint permanence of products formed and tone makes moderate progress, but effect is also insufficient, and if have the twin screw extruder not using complex structure, need altitude mixture control technology carry out melt molding processing, the shortcoming of object film forming thing cannot be obtained.In addition, in patent documentation 1 and patent documentation 2, vinylidene chloride this point is generated all without description due to thermolysis for vinylidene chloride analog copolymer, under melt molding condition harsh in recent years, the generation of vinylidene chloride can not be suppressed.
In addition; in recent years; from the aspect improving environmental protection consciousness and boost productivity; be strongly required the recycling adaptability (so-called recirculation adaptability) of melt molding processed goods, and this point is considered to due to the poor heat stability of vinylidene chloride analog copolymer to reach in the prior art.
The object of the present invention is to provide the vinylidene chloride generation when melt molding caused by thermolysis few, the also high vinylidene chloride analog copolymer composition of the recirculation adaptability of film uniformity excellent few film or sheet material, melt molding processed goods and thermal degradation when impurity is counted can be obtained; And the food container of high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence.
The present inventor conducts in-depth research repeatedly in order to solve above-mentioned problem, found that, for the multipolymer of vinylidene chloride and vinylchlorid, utilize based on proton magnetic resonance (PMR) optical spectroscopy (
1h-NMR) molecular diffusivity measures (DOSY, when DiffusionOrderedNMRSpectroscopY) carrying out analyzing, if have the spread coefficient ratio of specific summit, then when utilizing melt molding method to process film forming or sheet material, the generation of the vinylidene chloride caused by thermolysis is few, excellent heat stability, film uniformity when thus can obtain melt molding is excellent, few film or sheet material and thermal degradation when impurity is counted, the recirculation adaptability of melt molding processed goods is also high, by such film or sheet material are used in food packaging film, so-called electrode saltus step (ス キ Star プ) phenomenon can be suppressed when carrying out high frequency sealing when obtaining film wrapping body, when thus filling, broken bag is few, heating and pressurizing sterilization adaptability (so-called boiling adaptability) is excellent, can boost productivity.
That is, the present invention relates to following content.
(1) a vinylidene chloride analog copolymer, it is the vinylidene chloride analog copolymer be made up of vinylidene chloride and vinylchlorid, wherein, utilize proton magnetic resonance (PMR) optical spectroscopy (
1when H-NMR) carrying out analyzing, be less than 0.5 % by mole from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end relative to the monomeric unit forming vinylidene chloride analog copolymer;
(2) the vinylidene chloride analog copolymer as described in (1), wherein, utilization based on proton magnetic resonance (PMR) optical spectroscopy (
1h-NMR) molecular diffusivity measures (DOSY; When DiffusionOrderedNMRSpectroscopY) carrying out analyzing, chemical shift is the ratio that spread coefficient and the chemical shift of the summit of the signal of 3.95ppm is the spread coefficient of the summit of the signal of 3.25ppm is 1: 1.5 ~ 1: 5;
(3) a vinylidene chloride analog copolymer composition, it contains (1) or vinylidene chloride analog copolymer (a) described in (2) of 100 mass parts, the softening agent (b) of 0.1 mass parts ~ 10 mass parts, the epoxy compounds (c) of 0.05 mass parts ~ 5 mass parts and the antioxidant (d) of 0.01 mass parts ~ 1 mass parts;
(4) film or a sheet material, it carries out melt molding to the vinylidene chloride analog copolymer composition described in (3) and obtains;
(5) food container, it uses the film described in (4) or sheet material;
(6) food container as described in (5), it is casing.
The generation of the vinylidene chloride of vinylidene chloride analog copolymer composition of the present invention when melt molding caused by thermolysis is few, can obtain film uniformity excellence and thermal degradation when impurity is counted few film or sheet material, and the recirculation adaptability of melt molding processed goods is high, high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence.
Accompanying drawing explanation
Fig. 1 be utilize based on proton magnetic resonance (PMR) optical spectroscopy (
1h-NMR) molecular diffusivity measures the example that (DOSY) carries out measuring.
Embodiment
Below embodiments of the present invention are described.Following embodiment is for illustration of example of the present invention, 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.
For vinylidene chloride analog copolymer of the present invention, utilize proton magnetic resonance (PMR) optical spectroscopy (
1when H-NMR) carrying out analyzing, be less than 0.5 % by mole from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end relative to the monomeric unit forming vinylidene chloride analog copolymer.From the signal of the carbon-to-carbon double bond of molecule chain end integrated value can by the high-resolution proton magnetic resonance (PMR) optical spectroscopy of more than 400MHz (
1h-NMR) measure.Prepare the deuterated tetrahydrofuran solution of 5 quality % of sample, measure with the integral number of times of about 1000 times, to obtain with tetramethylsilane be benchmark, take chemical shift as the spectrogram of transverse axis.Wherein, the integrated value that can be the signal of 2.5ppm, 3.3ppm, 4.0ppm by chemical shift is obtained and is formed the vinylidene chloride of vinylidene chloride analog copolymer and the ratio of vinylchlorid.Further, the integrated value that can be 5.75ppm ~ 7.00ppm by the chemical shift of the signal as the carbon-to-carbon double bond from molecule chain end obtains its ratio.Now, should be noted that removing from integrated value in chemical shift is the singlet peak of the double bond from molecular chain inside that 7.10ppm occurs.
When integrated value from the signal of the carbon-to-carbon double bond of molecule chain end is below 0.5 % by mole relative to the monomeric unit of formation vinylidene chloride analog copolymer, melt molding then can be suppressed to add the generation of the vinylidene chloride of vinylidene chloride analog copolymer in man-hour caused by thermolysis, the dehydrochlorination reaction reacted as thermal degradation when is suppressed simultaneously, thus can obtain thermal degradation when impurity and to count few film or sheet material.Further, owing to having excellent thermostability, even if thus when carrying out again melt molding processing to the goods having carried out a melt molding processing, the deterioration of tone is also little, can use aptly.Integrated value from the signal of the carbon-to-carbon double bond of molecule chain end is preferably less than 0.2 % by mole, is more preferably less than 0.14 % by mole.There is no particular restriction for lower value, more low more preferred, but in reality be more than 0.05 % by mole.
Vinylidene chloride analog copolymer of the present invention more preferably utilization based on proton magnetic resonance (PMR) optical spectroscopy (
1h-NMR) molecular diffusivity measures (DOSY; When DiffusionOrderedNMRSpectroscopY) analyzing, chemical shift is the ratio that spread coefficient and the chemical shift of the summit of the signal of 3.95ppm is the spread coefficient of the summit of the signal of 3.25ppm is 1: 1.5 ~ 1: 5.So-called based on
1it is the assay method changing magnetic field gradient strength that the molecular diffusivity of H-NMR measures (DOSY), and it is is the longitudinal axis with spread coefficient, take chemical shift as the one of the two-dimentional NMR of transverse axis, can obtain the spectrogram that measurement example shown in Fig. 1 is such.Vinylidene chloride analog copolymer
1in H-NMR, the signal indication vinylidene chloride-vinylidene chloride chain of 3.95ppm and the signal indication of 3.25ppm vinylidene chloride-vinylchlorid chain.On the other hand, for spread coefficient, in the high molecular situation that vinylidene chloride analog copolymer is such, it is the index representing molecular size range, thus based on
1it is the coefficient of the molecular weight dependence of the amount representing each composition in molecular diffusivity mensuration (DOSY) of H-NMR.For the condition determination of DOSY, prepare the deuterated tetrahydrofuran solution of 0.5 quality % of sample, use more than 400MHz high-resolution proton magnetic resonance (PMR) optical spectroscopy (
1h-NMR), change magnetic field gradient strength, sets suitable magnetic field gradient pulse width (δ) and diffusion time (Δ) measures, and evaluates thus.
The chemical shift of vinylidene chloride analog copolymer is ratio that spread coefficient and the chemical shift of the summit of the signal of 3.95ppm is the spread coefficient of the summit of the signal of 3.25ppm when being 1: 1.5 ~ 1: 5, represent in low molecular weight compositions the monomeric unit had in a large number from vinylchlorid, mobility during the excellent and melting of meltability during owing to applying heat is excellent, thus can obtain film or the sheet material of film uniformity excellence by carrying out melt molding processing, be preferred.Further, owing to having excellent melt molding flexibility of operation, even if thus add and also can use aptly man-hour carrying out again melt molding to the goods having carried out a melt molding processing.In addition, when this ratio is less than 1: 5, the molecular weight of the molecule containing a large amount of vinylchlorid can not become too small, is preferred from the aspect of barrier properties for gases.More preferably chemical shift is the ratio that spread coefficient and the chemical shift of the summit of the signal of 3.95ppm are the spread coefficient of the summit of the signal of 3.25ppm is 1: 1.8 ~ 1: 3.
In addition, based on proton magnetic resonance (PMR) optical spectroscopy (
1when H-NMR) measuring, preferably measure after utilizing reprecipitation method to carry out refinement treatment.By utilizing reprecipitation method to process, the additives such as softening agent contained in vinylidene chloride analog copolymer composition etc. can be removed, accurately can carry out the analysis of vinylidene chloride analog copolymer.Fine purification treatment process based on reprecipitation method carries out as follows: be dissolved in 20ml tetrahydrofuran (THF) (THF) by 1g vinylidene chloride analog copolymer or composition or film or sheet material, after filtering indissolvable component, in filtrate, slowly drip 80ml methyl alcohol under stirring, the vinylidene chloride analog copolymer of precipitation is leached and drying.
Vinylidene chloride analog copolymer in the present invention makes vinylidene chloride and chloroethylene copolymer obtain.
In order to obtain vinylidene chloride analog copolymer of the present invention, any one method such as suspension polymerization, emulsion polymerization, solution polymerization process can be used, preferably use suspension polymerization.When utilizing suspension polymerization to manufacture, in polymerizer, dropping into other additives such as the mixture of vinylidene chloride and vinylchlorid, water, suspension agent, polymerization starter and softening agent, forming initiated polymerization after monomer oil droplet by carrying out stirring.Total mass and the quality optimization of the water used of vinylidene chloride and vinylchlorid are in the ratio of 1: 0.5 ~ 1: 2.This ratio is more preferably 1: 0.8 ~ 1: 1.5.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 be dissolved with 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 reduce the carbon-to-carbon double bond amount of molecule chain end, preferably get rid of the oxygen in polymerizer as far as possible.The cause-effect relationship of the carbon-to-carbon double bond of oxygen and molecule chain end is still not clear, but by inference, may being react with the free radical of molecule chain end with the reactivity of free radical because oxygen has, next generating double bond when departing from molecule chain end.
In order to reduce the oxygen concn in polymerizer, the method for the few water of the oxygen in water concentration that is used in for being polymerized can be enumerated, reduced pressure in polymerizer inside after utilize nitrogen or argon gas etc. to replace to reduce the method etc. of gas phase oxygen.As the dissolved oxygen concentration in the water for being polymerized, being preferably below 3mg/L, being more preferably below 2mg/L.In order to reduce the dissolved oxygen concentration in the water for being polymerized, the method blasting nitrogen or argon gas etc. in advance in the water for being polymerized can be enumerated.In addition, the dissolved oxygen concentration in water can utilize commercially available dissolved oxygen meter to measure.Further, in order to reduce the gas phase oxygen of polymerizer inside, preferably before drop into raw material in polymerizer, carrying out being decompressed to vacuum tightness and reaching and be preferably-6.66 × 10
-2below MPa, be more preferably-7.99 × 10
-2mPa ~-10.1 × 10
-2the scope of MPa, then imports nitrogen or argon gas etc., makes polymerizer inside become the atmosphere such as nitrogen or argon gas.Preferably repeatedly carry out the operation of more than 3 times these decompressions, displacement further.
Polymerization temperature, polymerization time can according to the ingredient proportions of vinylidene chloride and vinylchlorid; Kind, the amount of the kind of polymerization starter, amount and chain-transfer agent; Object percent polymerization etc. determines aptly, but roughly 10 DEG C ~ 80 DEG C (preferably 20 DEG C ~ 60 DEG C) polymerization, 15 hours ~ 100 hours (being more preferably 20 hours ~ 60 hours, more preferably 23 hours ~ 50 hours).The molecular diffusivity utilizing vinylidene chloride analog copolymer to carry out measures in (DOSY), the ratio be spread coefficient and the chemical shift of the summit of the signal of 3.95ppm for making chemical shift being the spread coefficient of the summit of the signal of 3.25ppm is 1: 1.5 ~ 1: 5, initiated polymerization at temperature preferably below 10 hr half-life temperature of used polymerization starter, carry out the polymerization of more than 5 hours at this constant temperature after, be slowly warming up to the temperature of higher than 10 hr half-life temperature more than 10 DEG C with more than 10 hours.In addition, when using two or more polymerization starter, adopt, with molar fraction, design temperature condition is come to the value that 10 hr half-life temperature are averaged.The ratio that to make chemical shift be spread coefficient and the chemical shift of the summit of the signal of 3.95ppm be the spread coefficient of the summit of the signal of 3.25ppm by adopting such temperature condition is that the reason of preferred value is still not clear, may be by inference due to, decomposition rate and the polymerization rate of polymerization starter average out, and the reaction ratio for vinylidene chloride and vinylchlorid brings desirable influence with the molecular weight of the molecule generated.
In addition, think that the chain transfer reaction by the molecule chain end free radical in polymerization process and monomer also can generate the carbon-to-carbon double bond of the molecule chain end of vinylidene chloride analog copolymer, thus, in vinylidene chloride analog copolymer of the present invention, the average polymerization temperature particularly in polymerization is preferably less than 45 DEG C, is more preferably less than 40 DEG C.By being set as such temperature condition, the chain transfer reaction that the monomer in polymerization process produces can be suppressed, the carbon-to-carbon double bond amount of molecule chain end can be reduced.
Target polymerization rate in the present invention is preferably 90 quality % ~ 97 quality %.Be more preferably 91 quality % ~ 95 quality %.Vinylchlorid has the character of the large quantitative response of phase after polymerisation, and the phase generates low molecular weight compositions in a large number after polymerisation, thus when percent polymerization is more than 90 quality %, through DOSY to measure chemical shift be spread coefficient and the chemical shift of the summit of the signal of 3.95ppm be the spread coefficient of the summit of the signal of 3.25ppm be in the scope of 1: 1.5 ~ 1: 5 than easy; If it is not and more than 97 quality %, then the carbon-to-carbon double bond amount of molecule chain end is easily more than 0.5 % by mole, thus preferred.
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 1,1,3, the peresters class initiators such as 3-tetramethyl-butyl ester, the new heptanoic acid tert-butyl ester of peroxidation, peroxidation neodecanoic acid 3-hydroxyl-1,1-dimethyl butyl ester; 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 these polymerization starters, for making polymerization rate homogenizing, the polymerization starter that 10 hr half-life temperature of more than two kinds are different can be combinationally used.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, peroxidation neodecanoic acid 3-hydroxyl-1,1-dimethyl butyl ester.
Relative to the mixed solution of vinylidene chloride and vinylchlorid, the usage quantity of polymerization starter is preferably 100ppm ~ 7000ppm, is more preferably 500ppm ~ 5000ppm, more preferably 800ppm ~ 3000ppm.
As the suspension agent used to utilize suspension polymerization to manufacture vinylidene chloride analog copolymer 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 vinylchlorid, the usage quantity of suspension agent is preferably 300ppm ~ 1000ppm.By being set in such scope, suspension polymerization stability can be obtained, the vinylidene chloride analog copolymer that the amount can effectively producing huge particle or molecule is minimized.Suspension agent once all can add and also can gradation add, and does not limit period its interpolation.
In addition, because the corrosion speed in polymerization machine and in the device of subsequent handling accelerates, thus in order to make the pH value of vinylidene chloride analog 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 analog copolymer 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.
The weight-average molecular weight of vinylidene chloride analog copolymer of the present invention is preferably 60,000 ~ about 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 seal compatibility, heating and pressurizing sterilization adaptability (so-called boiling adaptability) viewpoint be preferred.Also can, by being coordinated with arbitrary ratio by vinylidene chloride analog copolymer compositions of more than two kinds different for weight-average molecular weight, make the weight-average molecular weight of composition in above-mentioned scope.Weight-average molecular weight can use the polystyrene conversion weight-average molecular weight based on gel permeation chromatography to measure.
The weight average particle diameter of vinylidene chloride analog copolymer of the present invention is the scope of 200 μm ~ 500 μm.If particle diameter is in this scope, then the load of extruding when being stretched to vinylidene chloride analog copolymer composition by melt molding method is easy to become constant, can carry out stable extruding processing.Result easily can make the uniform film thickness of film or the sheet material obtained.
For polymerizer used in suspension polymerization, there is no particular restriction, can adopt known polymerizer, is preferably the polymerizer with glass lining.The stirrer of the polymerizer for suspension polymerization is not particularly limited, also can uses baffle plate as required.In stirrer, the impeller vane, fan turbine blade, three leaf swept-back (Pfaudler) blades, Burmagin blade etc. that usually use in the polymerization of polyvinyl chloride-base monomer 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.The baffle plate of these stirrers is preferably with glass lined layer.
In order to be obtained vinylidene chloride analog copolymer particle by suspension polymerization, need the balance of the stirring velocity maintaining capillary decline and the stirrer caused by suspension agent well, make the vinylidene chloride analog copolymer particle 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 vinylidene chloride analog copolymer particle swim, makes it be polymerized.
In general, in order to make 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, in order to prevent the sedimentation of vinylidene chloride analog copolymer particle and suppress the formation of molecule, need to carry out suspension polymerization near the limit that sedimentation does not occur vinylidene chloride analog copolymer particle.Such as, when using three leaf swept-back vanes, when the stirring velocity represented with following formula 1 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 1] 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 60rpm ~ 200rpm, stirring velocity is 1.3m/sec ~ 4.2m/sec, so preferably; In addition, span of foil is
when, when 20rpm ~ 50rpm, stirring velocity is 2.0m/sec ~ 5.3m/sec, so preferably.
Vinylidene chloride analog copolymer of the present invention after polymerization terminates through MONOMER RECOVERY, dehydration, drying process and make pulverous vinylidene chloride analog copolymer.
For vinylidene chloride analog copolymer of the present invention, in vinylidene chloride analog copolymer (a), coordinate softening agent (b), epoxy compounds (c) and antioxidant (d) to make vinylidene chloride analog copolymer composition, it is used by melt molding method processing film forming or sheet material.
As softening agent (b), 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 etc.Among these, particularly preferably tributyl acetylcitrate, Uniflex DBS.These softening agent (b) can be used alone, and two or more may be used in combination.For the addition of softening agent (b), from the viewpoint of the balance of melt molding processibility and oxygen barrier, be preferably 0.1 mass parts ~ 10 mass parts relative to vinylidene chloride analog copolymer (a) 100 mass parts, be more preferably 0.2 mass parts ~ 6 mass parts.
As epoxy compounds (c), can enumerate and the 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 epoxidation obtains is carried out to the glycol ester of unsaturated fatty acids; The cycloaliphatic epoxides such as epoxidation six hydrogen phthalate; The epoxy resin etc. such as bisphenol A diglycidyl ether.Particularly preferably epoxidised soybean oil among these.These epoxy compoundss (c) can be used alone, and two or more may be used in combination.From the viewpoint of thermostability during melt molding and oxygen barrier, the addition of preferred epoxy compounds (c) is 0.05 mass parts ~ 5 mass parts relative to 100 mass parts vinylidene chloride analog copolymer (a), is more preferably 0.1 mass parts ~ 3 mass parts.
As antioxidant (d), vitamin E, butylhydroxy toluene (BHT), 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) the phenol system antioxidant such as propionic ester, four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane; The sulphur system antioxidants etc. such as thio-2 acid alkyl ester.These antioxidants (d) can be used alone, and two or more may be used in combination, preferably by thio-2 acid alkyl ester and phenol system antioxidant used in combination.From the viewpoint of thermostability during melt molding and tint permanence and economy, the addition of preferred anti-oxidant (d) is 0.01 mass parts ~ 1 mass parts relative to 100 mass parts vinylidene chloride analog copolymer (a), is more preferably 0.02 mass parts ~ 0.5 mass parts.
In vinylidene chloride analog copolymer composition of the present invention, can suitably add the additives such as thermo-stabilizer, lubricant, the agent of pears face, tensio-active agent, photostabilizer, gelation improving agent, pH adjusting agent, antistatic agent, linking agent, defoamer, Scale inhibitors, pigment, filler further.As these additives, can enumerate the representative examples of saturated aliphatic monocarboxylic acid such as such as citric acid and an alkali metal salt thereof, 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 pears face agent such as silicon-dioxide, hydrous magnesium silicate, calcium carbonate; The nonionogenic tensides such as sorbitan fatty acid esters, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid esters; The photostabilizers etc. such as 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-Chloro-Benzotriazole.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 vinylchlorid, also can or be added in the vinylidene chloride polymer of pulp-like after polymerization in polymerization way, can also be added in the pulverous vinylidene chloride analog copolymer composition before melt molding.Mix in the situation of these additives in pulverous vinylidene chloride analog copolymer composition, the mixing etc. that the mixing can undertaken by mixing, the agitator such as employing propeller agitator or helix agitator etc. such as adopting duo mill to carry out, employing Henschel super mixer are carried out is carried out, and any one mode of the heating hybrid mode can applied more than 60 DEG C or the low-temperature mixed mode below 60 DEG C.
Vinylidene chloride analog 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 film bubble forming expansion (bubble) 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 using vinylidene chloride analog copolymer composition of the present invention, can the generation of the vinylidene chloride caused by thermal degradation when during melt molding be suppressed very low.The generation of the vinylidene chloride caused by thermal degradation when during melt molding can be evaluated as follows: based on the test method(s) " N; N-dimethylacetamide amine solvent/headspace method (N; N-ジ メ チ Le ア セ ト ア ミ De dissolving/ヘ Star De ス ぺ mono-ス method) " of the vinylidene chloride of regulation in " the 3rd utensil and the container package " of No. 370th, Japanese Showa 34 years (nineteen fifty-nine) Health and human services department bulletin " the specification benchmark of food, additive etc. ", use gas chromatography to measure the vinylidene chloride content before and after melt molding processing, evaluate thus.
Further, when using vinylidene chloride analog copolymer composition of the present invention, the rate of change that can easily obtain thickness by melt molding method is film or the sheet material of the film uniformity excellence of less than 10%.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 2.The rate of change of thickness is more preferably less than 6%.
The rate of change (%)=(standard deviation/average film thickness) × 100 of the thickness of [formula 2] film
Further, in the film obtained by vinylidene chloride analog copolymer composition of the present invention or sheet material, being mixed into of the impurity caused by thermal degradation when is few.Impurity is counted and is obtained as follows: when carrying out melt molding, use 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 analog copolymer of more than 0.5mm size is detected, obtains impurity thus and count.Impurity is counted and is preferably 0.01/m
2below, 0.006/m is more preferably
2below.
In addition, for the film obtained by vinylidene chloride analog copolymer composition of the present invention or sheet material, painted also little caused by the low and thermal degradation when of vinylidene chloride generation caused by thermal degradation when during melt molding, thus the recirculation adaptability of melt molding processed goods is high, environment affinity is also excellent, also can boost productivity.Recirculation adaptability can be evaluated as follows: melt molding processed goods is carried out melt molding processing again as raw material, measures the tint permanence (film b value) of the recirculation melt molding processed goods obtained, evaluates thus to recirculation adaptability.
When supplying vinylidene chloride analog copolymer composition of the present invention to forcing machine, if use putting into the vinylidene chloride analog copolymer composition continuous measurement of loading hopper device inside on 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 analog copolymer composition, can suppress further to forcing machine supply uneven, extrude add man-hour the variation of screw-rod engine load, the variation of extrusion capacity, can modified resin resolvent in the adhesion inhibition of die head spout, also can reduce being mixed into of the painted of resin and the impurity caused by thermal degradation when.
Vinylidene chloride analog 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, be more preferably-7.99 × 10
-2mPa is to-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, have heat-shrinkable, and also can be used as aptly can at 120 DEG C (pressurizations 0.245MPa), the thermotolerance film used under such boiling treatment condition for 20 minutes or sheet material.Stretching ratio is longitudinally preferably 2.0 times ~ 4.5 times, transverse direction is 3.0 times ~ 5.0 times.For the thickness of film or sheet material, monofilm is preferably 5 μm ~ 30 μm, is more preferably 10 μm ~ 25 μm.Also can use as duplicature or sheet material according to purposes.
In addition, vinylidene chloride analog copolymer composition of the present invention can be processed into multilayer film or sheet material by coetrusion, laminating.
In addition, also the post-treatment such as Corona discharge Treatment can be implemented to film of the present invention or sheet material as required.
In film of the present invention or sheet material, because being mixed into of thermal degradation when impurity is few, thus when for food packaging film or sheet material for food packaging, when carrying out high frequency sealing to obtain film or sheet-material package body, electrode leaves film phenomenon due to impurity can be reduced, thus be easy to keep sealing intensity constant, can reduce when packaging is filled and heating and pressurizing germicidal treatment (so-called boiling process) 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 3, 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 3] fills
Boiling adaptability is evaluated as follows: Heating temperature be 120 DEG C, under heat-up time is the condition of 20 minutes, boiling process is carried out to 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, takes out wrapping body from heating tank, and record is now from the quantity that the hermetic unit of wrapping body breaks, calculate boiling broken bag incidence by following formula 4, 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 4] boiling broken bag incidence (%)=(boiling broken bag radical/boiling process radical) × 100
For the film obtained like this or sheet material, the vinylidene chloride content generated by thermolysis is few, film uniformity is excellent, and thermal degradation when impurity is counted few, thus high frequency seal compatibility and heating and pressurizing sterilization adaptability are excellent, thus can be used as ham, sausage, cheese, prepared food, other food etc. aptly and need the wrapping material of barrier and preservative film etc.Wherein can be used as casing especially aptly.Further, in film of the present invention or sheet material, because the recirculation adaptability of melt molding processed goods is also very high, thus environment affinity is excellent, can also boost productivity.
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) dissolved oxygen concentration in deionized water uses automatic DO determinator (ORE society of Co., Ltd. C manufactures CD-3201) to measure.
2) weight average particle diameter of vinylidene chloride analog copolymer
Weight average particle diameter uses particle size distribution analyzer (BeckmanCoulter Co., Ltd. manufactures Multisizer3) to measure.
3) weight-average molecular weight of vinylidene chloride analog 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 Co., Ltd.)
Post: TSKgelSuperHM-H (manufacture of Tosoh Co., Ltd.) 7.8mm × 30cm × 2
Elutriant: tetrahydrofuran (THF) (THF)
Flow velocity: 1ml/min
Column temperature: 40 DEG C
Detector: RI
4) based on proton magnetic resonance (PMR) optical spectroscopy (
1h-NMR) molecular diffusivity measures
Prepare the deuterated tetrahydrofuran solution of 0.5 quality % of sample, use high resolving power proton magnetic resonance (PMR) device (NEC society manufactures ECA400), under the condition of magnetic field gradient strength 0.5T/m ~ 3.0T/m, magnetic field gradient pulse width (δ) 0.5ms, diffusion time (Δ) 50ms, bpp-led-dosy-pfg is used as pulse protocol, measure at 30 DEG C, obtain 24 spectrum.Operational method as Laplace inverse transformation uses CONTIN, makes the setting range of spread coefficient be 0.1um
2/ s ~ 1000um
2/ s carries out DOSY process, the two-dimentional NMR spectrogram that to obtain take spread coefficient as the longitudinal axis, chemical shift is transverse axis.The chemical shift wherein obtaining expression vinylidene chloride-vinylidene chloride chain is the spread coefficient of the summit of the signal of 3.95ppm and represents that the chemical shift of vinylidene chloride-vinylchlorid chain is the spread coefficient of the summit of the signal of 3.25ppm.
5) measuring method of terminal double link amount
Utilize reprecipitation method to carry out refinement treatment (vinylidene chloride analog copolymer 1g to be dissolved in tetrahydrofuran (THF) (THF) 20ml, after filtering indissolvable component, in filtrate, slowly methyl alcohol 80ml is dripped under stirring, the vinylidene chloride analog copolymer of precipitation is leached and drying), obtain vinylidene chloride analog copolymer, prepare the deuterated tetrahydrofuran solution of its 5 quality %, utilize high resolving power proton magnetic resonance (PMR) device (BrukerBioSpin Co., Ltd. manufacture AVANCE600) repeatedly with pulse wait time 1 second, the condition that integral number of times is 1024 times measures, obtain taking tetramethylsilane as benchmark, take chemical shift as the spectrogram of transverse axis.Wherein, be the integrated value of the signal of 2.5ppm, 3.3ppm, 4.0ppm according to the chemical shift from the vinylidene chloride and vinylchlorid that form vinylidene chloride analog copolymer and be the integrated value of the signal of 5.75ppm ~ 7.00ppm from the chemical shift of the carbon-to-carbon double bond of molecule chain end, obtain the ratio (% by mole) of terminal double link amount.
6) the vinylidene chloride content in vinylidene chloride analog copolymer
Based on the test method(s) " N; N-dimethylacetamide amine solvent/headspace method " of the vinylidene chloride of regulation in " the 3rd utensil and the container package " of No. 370th, Japanese Showa 34 years (nineteen fifty-nine) Health and human services department bulletin " the specification benchmark of food, additive etc. ", the vinylidene chloride content in vinylidene chloride analog copolymer is measured.Carry out before and after being determined at melt molding processing, the change of the vinylidene chloride content caused by melt molding processing is evaluated.
7) rate of change of the thickness of film
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 5.
[formula 5]
The rate of change (%)=(standard deviation/average film thickness) × 100 of the thickness of film
8) impurity in film is counted
When carrying out melt molding, the determination of foreign matter machine (Co., Ltd. Futec 3R4003) of image sensor mode is used to detect the thermal degradation when impurity of the vinylidene chloride analog copolymer be mixed in film.After beginning melt molding, detect the number that length is the thermal degradation when impurity of more than 0.5mm size, obtain every 1m
2in impurity number.
9) recirculation adaptability (the aberration b value of recirculation melt molding processing of films)
Recirculation adaptability is evaluated as follows: melt molding processing of films is carried out melt molding processing again as raw material, measures, evaluate thus the tint permanence (aberration b value) of obtained recirculation melt molding processing of films.For the aberration b value of film, according to " the optical characteristics test methods of plastics " (JISK7105), 10 recirculation melt molding processing of films are overlapping, gather the measurement sample of 400 ± 10 μm of ranges of thicknesses, utilize colour examining colour-difference-metre (Japanese electric look industry (strain) society manufactures Z-300A) to measure the aberration b value of the reflected light from the reflection of this color standard white face.
10) 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 and now make 50, the broken bag number of 000 period, during by following formula 6 to fill, the mode of broken bag incidence is evaluated.
Broken bag incidence (%)=(broken bag frequency/50 during filling, 000) × 100 when [formula 6] fills
11) boiling adaptability
By gauge pressure in heating tank be 0.245MPa, under temperature is the condition of 120 DEG C, 20 minutes, to by obtain in the evaluation of above-mentioned high frequency seal compatibility 50,000 wrapping body carries out hot digestion process, maintain heating tank internal pressure afterwards constant, it is after 25 DEG C that pressurization is cooled to temperature, relief pressure, takes out wrapping body from heating tank, 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 7.
[formula 7] boiling broken bag incidence (%)=(boiling broken bag radical/50,000) × 100
[embodiment 1]
The reactor with glass lining (internal volume 300L) possessing three leaf swept-back vanes (length footpath 400mm), finger-type baffle plate, temperature take into account nitrogen ingress pipe is decompressed to-9.00 × 10
-2mPa also imports nitrogen simultaneously, makes polymerizer inside for nitrogen atmosphere.After the operation of this decompression, nitrogen replacement carries out 3 times repeatedly, polymerization starter di-isopropyl peroxydicarbonate 0.15 mass parts, vinylchlorid (VC) 18 mass parts, vinylidene chloride (VDC) 82 mass parts, 3 is dropped in reactor, 3-Tyox B (DLTDP) 0.03 mass parts, Uniflex DBS (hereinafter referred to as DBS) 3 mass parts, carry out stirring for 20 minutes to mixed solution with the stirring velocity of 1.4m/sec.Following interpolation water temperature is that the deionized water of 20 DEG C (has carried out the nitrogen bubble of 2 hours to reduce dissolved oxygen concentration to this deionized water, after this operation, dissolved oxygen concentration is 0.8mg/L) 100 mass parts, suspension agent Vltra tears concentration be the aqueous solution 2.5 mass parts of 2 quality %, stir after within 20 minutes, confirming to form particle, be heated to polymerization initial stage temperature 35 DEG C under nitrogen atmosphere, initiated polymerization.Stirring velocity, after 15 hours, is set to 1.2 times (1.68m/sec) of initial stage speed by sustained reaction, is warming up to polymerization latter temperature 62 DEG C with 15 hours, proceeds polymerization in 2 hours further.After reaction terminates, slowly pressure in open reactor, then reduces pressure with vacuum pump, next with 1 hour, interior temperature is warmed up to 75 DEG C, proceeds further to stir for 3 hours, is separated unreacted monomer.Dewater subsequently, 70 DEG C of dryings 24 hours, obtain pulverous vinylidene chloride analog copolymer composition.To spread coefficient, the terminal double link amount of the polymerisation conversion of obtained vinylidene chloride analog copolymer composition, weight average particle diameter, weight-average molecular weight, to be the spread coefficient of the summit of the signal of 3.95ppm and chemical shift based on the chemical shift of DOSY the be summit of the signal of 3.25ppm.
In the vinylidene chloride analog 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, adopt the Henschel super mixer of low-temperature mixed mode to mix.Vinylidene chloride content in vinylidene chloride analog copolymer composition before the processing of obtained melt molding is measured.
Use spiral material feeder, be set as-9.00 × 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.Impurity in the rate of change of the thickness of the vinylidene chloride content of obtained film, average film thickness and film, film is counted and measures.Further, obtained film is carried out again melt molding processing as raw material, the tint permanence (aberration b value) of obtained recirculation melt molding processing of films is measured, evaluate recirculation adaptability.
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, boiling adaptability.
The results are shown in table 1.
[embodiment 2]
For the condition of polymerization temperature, if polymerization initial stage temperature is 35 DEG C, after this temperature proceeds reaction in 15 hours, be warming up to polymerization latter temperature 62 DEG C with 1 hour, proceed polymerization in 16 hours further, operate similarly to Example 1 in addition.The results are shown in table 1.
[embodiment 3]
Except the deionized water that use dissolved oxygen concentration is 7.5mg/L, operate similarly to Example 1.The results are shown in table 1.
[embodiment 4]
Except the vacuum operating before not feeding intake, operate similarly to Example 1.The results are shown in table 1.
[embodiment 5]
For the condition of polymerization temperature, if polymerization initial stage temperature is 35 DEG C, after this temperature proceeds reaction in 10 hours, be warming up to polymerization latter temperature 62 DEG C with 15 hours, proceed polymerization in 2 hours further, operate similarly to Example 1 in addition.The results are shown in table 1.
[comparative example 1]
Vacuum operating before not feeding intake, and, for the condition of polymerization temperature, if polymerization initial stage temperature is 35 DEG C, after this temperature proceeds reaction in 15 hours, be warming up to polymerization latter temperature 62 DEG C with 1 hour, proceed polymerization in 12 hours further, operate similarly to Example 1 in addition.The results are shown in table 1.
[comparative example 2]
Vacuum operating before feeding similarly to Example 1, and, use the deionized water that dissolved oxygen concentration is 7.5mg/L, in addition, operate in the same manner as comparative example 1.The results are shown in table 1.
[comparative example 3]
Use the deionized water that dissolved oxygen concentration is 7.5mg/L, and, for the condition of polymerization temperature, if polymerization initial stage temperature is 35 DEG C, after this temperature proceeds reaction in 10 hours, be warming up to polymerization latter temperature 62 DEG C with 15 hours, proceed polymerization in 2 hours further, in addition, operate in the same manner as comparative example 1.The results are shown in table 1.
[comparative example 4]
Use the deionized water that dissolved oxygen concentration is 7.5mg/L, and, for the condition of polymerization temperature, if polymerization initial stage temperature is 35 DEG C, after this temperature proceeds reaction in 15 hours, be warming up to polymerization latter temperature 62 DEG C with 1 hour, proceed polymerization in 16 hours further, in addition, operate in the same manner as comparative example 1.The results are shown in table 1.
Can be confirmed by embodiment and comparative example, vinylidene chloride generation when vinylidene chloride analog copolymer of the present invention can obtain melt molding caused by thermolysis is few, film uniformity is excellent and thermal degradation when impurity is counted few film or sheet material, and the recirculation adaptability of melt molding processed goods is high, high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence.
Industrial applicibility
Vinylidene chloride generation when vinylidene chloride analog copolymer of the present invention can obtain melt molding caused by thermolysis is few, film uniformity is excellent and thermal degradation when impurity is counted few film or sheet material, and the recirculation adaptability of melt molding processed goods is also high, high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) are excellent, and thus 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.
Claims (5)
1. a vinylidene chloride analog copolymer, it is the vinylidene chloride analog copolymer be made up of vinylidene chloride and vinylchlorid, wherein, utilize proton magnetic resonance (PMR) optical spectroscopy (
1when H-NMR) carrying out analyzing, be less than 0.5 % by mole from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end relative to the monomeric unit forming vinylidene chloride analog copolymer, and, utilization based on proton magnetic resonance (PMR) optical spectroscopy (
1h-NMR), when molecular diffusivity measures and carries out analyzing, chemical shift is the ratio that spread coefficient and the chemical shift of the summit of the signal of 3.95ppm is the spread coefficient of the summit of the signal of 3.25ppm is 1:1.5 ~ 1:5.
2. a vinylidene chloride analog copolymer composition, it contains vinylidene chloride analog copolymer (a) according to claim 1 of 100 mass parts, the softening agent (b) of 0.1 mass parts ~ 10 mass parts, the epoxy compounds (c) of 0.05 mass parts ~ 5 mass parts and the antioxidant (d) of 0.01 mass parts ~ 1 mass parts.
3. film or a sheet material, it carries out melt molding to vinylidene chloride analog copolymer composition according to claim 2 and obtains.
4. a food container, it uses film according to claim 3 or sheet material.
5. food container as claimed in claim 4, it is casing.
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Effective date of registration: 20160427 Address after: Tokyo, Japan, Japan Patentee after: Asahi Kasei Kogyo K. K. Address before: Tokyo, Japan, Japan Patentee before: Asahi Kasei Chemical K. K. |