CN103224581A - Vinylidene chloride copolymer, its composition, and its membrane or sheet material - Google Patents
Vinylidene chloride copolymer, its composition, and its membrane or sheet material Download PDFInfo
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- CN103224581A CN103224581A CN2012100210640A CN201210021064A CN103224581A CN 103224581 A CN103224581 A CN 103224581A CN 2012100210640 A CN2012100210640 A CN 2012100210640A CN 201210021064 A CN201210021064 A CN 201210021064A CN 103224581 A CN103224581 A CN 103224581A
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Abstract
The invention relates to a vinylidene chloride copolymer and its composition, the output of the vinylidene chloride due to thermal decomposition during a melt molding process is little; the membrane or the sheet material with the excellent membrane thickness uniformity and little thermal degradation impurity points can be obtained; and the high frequency seal adaptability and heating pressurization sterilization adaptability (so-called boiling adaptability) of the provided membrane or the sheet material are excellent. The vinylidene chloride copolymer is the vinylidene chloride copolymer formed by vinylidene chloride and a polymerism vinyl monomer, wherein, under the condition that a proton magnetic resonance optical spectroscopy (1H-NMR) is used for analysis, integral value of a signal of carbon-carbon double bond of the terminal of a molecular chain is less than 0.5 mole% by comparing with that of a monomer unit using for forming the vinylidene chloride copolymer.
Description
Technical field
Generation by the vinylidene chloride due to the thermolysis when the present invention relates to melt molding is few, can access film uniformity excellence and thermal degradation when impurity count the vinylidene chloride analog copolymer and the composition thereof of few film or sheet material; Its film or sheet material that high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) are excellent; And used the food container of this film or sheet material.
Background technology
For film, sheet material, the container made by vinylidene chloride analog copolymer composition, owing to excellences such as its resistance oxygen, moistureproofness, the transparency, chemical proofing, oil-proofness, tackiness, heat-shrinkable are suitable in packaging material for food, the preservative film etc.Manufacture method at the vinylidene chloride analog copolymer that is used for the used for packing foods film has suspension polymerization and emulsion polymerization, so but because suspension polymerization does not have the problem such as residual of emulsifying agent generally to use suspension polymerization.Suspension polymerization is following method: in containing the water of dispersion agent, behind the blending dispersion oil droplet by mechanical stirring formation vinylidene chloride and polymerizability vinyl monomer, add polymerization starter and carry out polymerization.
In the situation that obtains the used for packing foods film, use the vinylidene chloride analog copolymer that obtains by suspension polymerization, adopts common melt molding method stretching or under tensile situation not, be processed into the film or the sheet material of single or multiple lift.But, the poor heat stability of vinylidene chloride analog copolymer, thus when its melt molding easily part be subjected to oxidative degradation due to thermal degradation when or the oxygen, so moulding product can be painted, and the danger of remarkable infringement goods value is arranged.In addition, known vinylidene chloride analog copolymer can be owing to thermolysis generates vinylidene chloride, vinylidene chloride is the material that the residual quantity in the moulding product is subjected to legal restrictions in used for packing foods film purposes, requires to reduce as far as possible its remaining quantity in the moulding product.
In order to improve the thermostability of vinylidene chloride analog copolymer, carried out a lot of research in the past.Following method is disclosed in patent documentation 1: import the structural unit with two keys by copolymerization one chloroacetylene in the vinylidene chloride analog copolymer, improve the tone and the outward appearance of formed body by the control recrystallization temperature.In addition, following content is disclosed in patent documentation 2: be in the vinylidene chloride analog copolymer film forming thing of certain relation corresponding to the UV value of 3～4 conjugated double bond amounts and NMR value corresponding to the isolated double bond amount of molecular chain inside, tonal variation due to the thermal degradation when is few, can suppress to process the back tone through the time change.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-283346 communique
Patent documentation 2: Japanese kokai publication hei 9-286865 communique
Summary of the invention
In order to improve the thermostability of vinylidene chloride analog copolymer, being extensive use of thermo-stabilizer, sulphur such as epoxy compounds usually is that antioxidant, hindered phenol are antioxidants such as antioxidant.But, even under the situation of adding these thermo-stabilizers and antioxidant, thermal stability result during melt molding can not be said fully, and, add such additive and can not suppress the generation of vinylidene chloride analog copolymer by the vinylidene chloride due to the thermolysis, strong request is not vulnerable to pyrolysated vinylidene chloride analog copolymer.
In the vinylidene chloride analog copolymer of patent documentation 1 record, utilizing the melt molding method to carry out can not get sufficient thermostability under the situation of stretch process, and needing to import the such particular monomers of a chloroacetylene, be unsuitable for commercially producing.In patent documentation 2 described vinylidene chloride analog copolymer film forming things, although the tint permanence of moulding product and tone through the time change and to make moderate progress, but effect and insufficient, and have if not the utilization structure complexity, need the twin screw extruder of altitude mixture control technology to carry out the shortcoming that melt molding processing then can't obtain purpose film forming thing.In addition, in patent documentation 1 and patent documentation 2, all do not have record owing to thermolysis generates the vinylidene chloride this point, under harsh in recent years melt molding condition, can not suppress the generation of vinylidene chloride for the vinylidene chloride analog copolymer.
In addition; in recent years; from the aspect that improves environmental protection consciousness and boost productivity; strong request melt molding processed goods utilize adaptability (so-called recirculation adaptability) again, and this point is considered to reach owing to the poor heat stability of vinylidene chloride analog copolymer in the prior art.
The object of the present invention is to provide few by the vinylidene chloride generation due to the thermolysis when melt molding, can access count the also high vinylidene chloride analog copolymer composition of recirculation adaptability of few film or sheet material, melt molding processed goods of film uniformity excellence and thermal degradation when impurity; And high frequency seal compatibility and the excellent food container of heating and pressurizing sterilization adaptability (so-called boiling adaptability).
The inventor furthers investigate repeatedly in order to solve above-mentioned problem, found that, for the multipolymer of vinylidene chloride and vinylchlorid, utilize based on the proton magnetic resonance (PMR) optical spectroscopy (
1H-NMR) molecular diffusivity is measured (DOSY; Diffusion Ordered NMR SpectroscopY) under the situation about analyzing, if have the spread coefficient ratio of specific summit, then when utilizing melt molding method processing film forming or sheet material, because the generation of the vinylidene chloride due to the thermolysis is few, excellent heat stability, thereby the film uniformity excellence can access melt molding the time, and thermal degradation when impurity count few film or sheet material, the recirculation adaptability of melt molding processed goods is also high, by such film or sheet material are used for the used for packing foods film, when obtaining the film wrapping body, carry out to suppress so-called electrode saltus step (ス キ Star プ) phenomenon under the situation of high frequency sealing, thereby broken bag is few when filling, heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence can be boosted productivity.
That is, the present invention relates to following content.
(1) a kind of vinylidene chloride analog copolymer, it is the vinylidene chloride analog copolymer that is made of vinylidene chloride and vinylchlorid, wherein, utilize the proton magnetic resonance (PMR) optical spectroscopy (
1Under the situation about H-NMR) analyzing, it is 0.5 mole below the % with respect to the monomeric unit that constitutes the vinylidene chloride analog copolymer from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end;
(2) as (1) described vinylidene chloride analog copolymer, wherein, utilize based on the proton magnetic resonance (PMR) optical spectroscopy (
1H-NMR) molecular diffusivity is measured (DOSY; Diffusion Ordered NMR SpectroscopY) under the situation about analyzing, chemical shift is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is 1: 1.5～1: 5;
(3) a kind of vinylidene chloride analog copolymer composition, it contains (1) or (2) the described vinylidene chloride analog copolymer (a) 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) a kind of film or sheet material, it carries out melt molding to (3) described vinylidene chloride analog copolymer composition and obtains;
(5) a kind of food container, it has used film or the sheet material described in (4);
(6) food container described in (5), it is a casing.
Vinylidene chloride analog copolymer composition of the present invention generation by the vinylidene chloride due to the thermolysis when melt molding is few, can access film uniformity excellence and thermal degradation when impurity count few film or sheet material, and the recirculation adaptability height of melt molding processed goods, high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence.
Description of drawings
Fig. 1 be utilize based on the proton magnetic resonance (PMR) optical spectroscopy (
1H-NMR) molecular diffusivity is measured the example that (DOSY) measures.
Embodiment
Below embodiments of the present invention are described.Following embodiment is to be used to illustrate example of the present invention, and does not mean that the present invention only limits to this embodiment.The present invention only otherwise break away from its main idea can implement by various modes.
For vinylidene chloride analog copolymer of the present invention, utilize the proton magnetic resonance (PMR) optical spectroscopy (
1Under the situation about H-NMR) analyzing, it is 0.5 mole below the % with respect to the monomeric unit that constitutes the vinylidene chloride analog copolymer from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end.From the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end can by the high-resolution proton magnetic resonance (PMR) optical spectroscopy more than the 400MHz (
1H-NMR) measure.5 quality % deuteriums of preparation sample are measured with the integral number of times about 1000 times for tetrahydrofuran solution, and to obtain with the tetramethylsilane be benchmark, be the spectrogram of transverse axis with the chemical shift.Wherein, can be that the integrated value of the signal of 2.5ppm, 3.3ppm, 4.0ppm is obtained the vinylidene chloride that constitutes the vinylidene chloride analog copolymer and the ratio of vinylchlorid by chemical shift.Further, can obtain its ratio by the integrated value that as chemical shift is 5.75ppm～7.00ppm from the signal of the carbon-to-carbon double bond of molecule chain end.At this moment, should be noted that removing in chemical shift is the singlet peak from two keys of molecular chain inside that 7.10ppm occurs from integrated value.
Is that 0.5 mole of % is when following from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end with respect to the monomeric unit that constitutes the vinylidene chloride analog copolymer, then can suppress melt molding and add man-hour vinylidene chloride analog copolymer by the generation of the vinylidene chloride due to the thermolysis, simultaneously the dehydrochlorination reaction as thermal degradation when reaction is suppressed, thereby can access thermal degradation when impurity count few film or sheet material.And, owing to have excellent thermostability, even thereby the goods that carried out a melt molding processing are being carried out once more under the situation of melt molding processing, the deterioration of tone is also little, can use aptly.Be preferably 0.2 mole below the %, more preferably 0.14 mole below the % from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end.There is no particular restriction for lower value, low more preferred more, but be 0.05 mole more than the % in the reality.
Vinylidene chloride analog copolymer of the present invention more preferably utilize based on the proton magnetic resonance (PMR) optical spectroscopy (
1H-NMR) molecular diffusivity is measured (DOSY; Diffusion Ordered NMR SpectroscopY) when analyzing, chemical shift is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is 1: 1.5～1: 5.So-called based on
1It is the assay method that changes magnetic field gradient strength that the molecular diffusivity of H-NMR is measured (DOSY), and it is is the longitudinal axis with the spread coefficient, be two-dimentional NMR a kind of of transverse axis with the chemical shift, can obtain the such spectrogram of example of measuring shown in Figure 1.The vinylidene chloride analog copolymer
1Among the H-NMR, signal indication vinylidene chloride-vinylchlorid chain of the signal indication of 3.95ppm vinylidene chloride-vinylidene chloride chain and 3.25ppm.On the other hand, for spread coefficient, under the such high molecular situation of vinylidene chloride analog copolymer, it is the index of expression molecular weight size, thus based on
1The molecular diffusivity of H-NMR is measured in (DOSY) coefficient of molecular weight dependence of the amount that is each composition of expression.For the condition determination of DOSY, 0.5 quality % deuterium of preparation sample is for tetrahydrofuran solution, use the above high-resolution proton magnetic resonance (PMR) optical spectroscopy of 400MHz (
1H-NMR), change magnetic field gradient strength, set suitable magnetic field gradient pulse width (δ) and diffusion time (Δ) and measure, estimate thus.
The chemical shift of vinylidene chloride analog copolymer is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is under 1: 1.5～1: 5 the situation, have monomeric unit in the expression low molecular weight compositions in a large number from vinylchlorid, because mobile excellent when applying fusion excellence when hot and fusion, thereby can process film or the sheet material that obtains the film uniformity excellence by carrying out melt molding, be preferred.And, owing to have excellent melt molding flexibility of operation, even thereby add and also can use aptly man-hour the goods that carried out a melt molding processing being carried out once more melt molding.In addition, this ratio is that the molecular weight that contains the molecule of a large amount of vinylchlorid can not become too small under 1: 5 following situation, is preferred from the aspect of barrier properties for gases.More preferably chemical shift is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is 1: 1.8～1: 3.
In addition, based on the proton magnetic resonance (PMR) optical spectroscopy (
1When H-NMR) measuring, preferably utilizing reprecipitation method to carry out measuring after the refinement treatment.By utilizing reprecipitation method to handle, can remove the additives such as softening agent that contained in vinylidene chloride analog copolymer composition etc., can accurately carry out the analysis of vinylidene chloride analog copolymer.Carry out based on the fine purification treatment process of reprecipitation method is following: 1g vinylidene chloride analog copolymer or composition or film or sheet material are dissolved in the 20ml tetrahydrofuran (THF) (THF), behind the filtering indissolvable component, stir and in filtrate, slowly drip 80ml methyl alcohol down, the vinylidene chloride analog copolymer of separating out is leached also dry.
Vinylidene chloride analog copolymer among the present invention obtains vinylidene chloride and chloroethylene copolymer.
In order to obtain vinylidene chloride analog copolymer of the present invention, can use any methods such as suspension polymerization, emulsion polymerization, solution polymerization process, preferably use suspension polymerization.Under the situation of utilizing suspension polymerization to make, in polymerizer, drop into other additives such as mixture, water, suspension agent, polymerization starter and softening agent of vinylidene chloride and vinylchlorid, by stirring initiated polymerization behind the formation monomer oil droplet.The total mass of vinylidene chloride and vinylchlorid and the quality optimization of employed water be in 1: 0.5～1: 2 ratio.This ratio more preferably 1: 0.8～1: 1.5.As the forming method of monomer oil droplet, suspension method arbitrarily below can using: in the water that has dissolved suspension agent, add monomeric direct suspension method; Or in monomer, add the water that is dissolved with suspension agent, be that making monomer was that disperse phase, water are the suspension method of the dispersion of external phase after external phase, water were the dispersion state of disperse phase mutually via monomer.
In order to reduce the carbon-to-carbon double bond amount of molecule chain end, preferably get rid of the oxygen in the polymerizer as far as possible.The cause-effect relationship of the carbon-to-carbon double bond of oxygen and molecule chain end is still indeterminate, but by inference, may be because oxygen has with the reactivity of free radical and reacts with the free radical of molecule chain end, next generates two keys at molecule chain end when breaking away from.
In order to reduce the oxygen concn in the polymerizer, can enumerate method of utilizing nitrogen or argon gas etc. to replace after use is reduced pressure in the method that is used for the few water of polymeric oxygen in water concentration, to polymerizer inside to reduce gas phase oxygen etc.As the dissolved oxygen concentration that is used for polymeric water, be preferably below the 3mg/L, more preferably below the 2mg/L.In order to reduce the dissolved oxygen concentration that is used for polymeric water, can enumerate in advance to being used for the method that polymeric water blasts nitrogen or argon gas etc.In addition, the dissolved oxygen concentration in the water can utilize commercially available dissolved oxygen meter to measure.And,, preferably before in polymerizer, dropping into raw material, be decompressed to vacuum tightness and reach and be preferably-6.66 * 10 in order to reduce the gas phase oxygen of polymerizer inside
-2MPa is following, more preferably-7.99 * 10
-2MPa～-10.1 * 10
-2The scope of MPa imports nitrogen or argon gas etc. then, makes polymerizer inside become atmosphere such as nitrogen or argon gas.Further preferably carry out these decompressions more than 3 times, metathetical operation repeatedly.
Polymerization temperature, polymerization time can be according to the ingredient proportions of vinylidene chloride and vinylchlorid; The kind of the kind of polymerization starter, amount and chain-transfer agent, amount; Purpose percent polymerizations etc. determine aptly, but roughly in 10 ℃～80 ℃ (preferred 20 ℃～60 ℃) polymerizations 15 hours～100 hours (more preferably 20 hours～60 hours, more preferably 23 hours～50 hours).The molecular diffusivity that utilizes the vinylidene chloride analog copolymer to carry out is measured in (DOSY), for making chemical shift is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is 1: 1.5～1: 5, preferred initiated polymerization under 10 hours temperature below the half life temperature of employed polymerization starter, after this temperature continues to carry out polymerization more than 5 hours, with slowly being warming up to more than 10 hours than 10 hours high temperature more than 10 ℃ of half life temperature.In addition, use under the situation of two or more polymerization starters, adopt with molar fraction the value that 10 hours half life temperatures average is come the design temperature condition.By adopting such temperature condition to make chemical shift is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is that the reason of preferred value is still indeterminate, may be by inference because, the decomposition rate and the polymerization rate of polymerization starter average out, and have brought desirable influence for the reaction ratio of vinylidene chloride and vinylchlorid and the molecular weight of the molecule that is generated.
In addition, think the carbon-to-carbon double bond that also can generate the molecule chain end of vinylidene chloride analog copolymer by molecule chain end free radical in the polymerization process and monomeric chain transfer reaction, thereby, in the vinylidene chloride analog copolymer of the present invention, particularly the average polymerization temperature in the polymerization be preferably below 45 ℃, more preferably below 40 ℃.By being set at such temperature condition, can suppress the chain transfer reaction that monomer produced in the polymerization process, can reduce the carbon-to-carbon double bond amount of molecule chain end.
Target polymerization rate among the present invention is preferably 90 quality %～97 quality %.91 quality %～95 quality % more preferably.Vinylchlorid has the character at big quantitative response of polymerization later stage, and at a large amount of low molecular weight compositions that generate of polymerization later stage, thereby percent polymerization is under the above situation of 90 quality %, and measuring chemical shift through DOSY is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is in 1: 1.5～1: 5 the scope easily; And if surpass 97 quality %, then the carbon-to-carbon double bond amount of molecule chain end is 0.5 mole more than the % easily, thereby not preferred.
As polymerization starter, can enumerate for example peroxycarbonates class initiators such as peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, peroxide-butyl carbonate, peroxy dicarbonate two (the 2-ethyl is own) ester; New peroxide tert-butyl caprate, the own ester of peroxidation neodecanoic acid uncle, peroxidation neodecanoic acid tert-pentyl ester, peroxidation neodecanoic acid α-isopropyl benzene ester, peroxidation neodecanoic acid 1,1,3,3-tetramethyl-butyl ester, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, peroxide PIVALIC ACID CRUDE (25) tert-pentyl ester, the own ester of peroxidation PIVALIC ACID CRUDE (25) uncle, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-2 ethyl hexanoic acid 1,1,3,3-tetramethyl-butyl ester, the new enanthic acid tert-butyl ester of peroxidation, peroxidation neodecanoic acid 3-hydroxyl-1, peresters class initiators such as 1-dimethyl butyl ester; Peroxidation two acyl class initiators such as dilauroyl peroxide, diisobutyryl peroxide, peroxidation two (3,5, the 5-trimethyl acetyl), dibenzoyl peroxide; Hydroperoxide kind initiators such as tertbutyl peroxide, α-isopropyl benzene hydroperoxide, 1; Dialkyl peroxide class initiators such as peroxidation two uncle's butane, peroxidation two uncle's hexanes, tert-butyl peroxide isopropyl benzene; 2, azo-initiators such as 2 '-Diisopropyl azodicarboxylate; Water-soluble peroxides such as Potassium Persulphate, ammonium persulphate, Sodium Persulfate; Or be added with polymerization starter of reductive agents such as amine, sodium bisulfite etc. in these.For these polymerization starters,, can be used in combination 10 hours different polymerization starters of half life temperature more than 2 kinds for making the polymerization rate homogenizing.In addition, these polymerization starters can directly use, and use after also can being made into aqueous emulsion, aqeous suspension.Among these, preferred especially di-isopropyl peroxydicarbonate, peroxidation neodecanoic acid α-isopropyl benzene ester, peroxidation neodecanoic acid 3-hydroxyl-1,1-dimethyl butyl ester.
With respect to the mixed solution of vinylidene chloride and vinylchlorid, the usage quantity of polymerization starter is preferably 100ppm～7000ppm, more preferably 500ppm～5000ppm, more preferably 800ppm～3000ppm.
Suspension agent as using in order to utilize suspension polymerization to make vinylidene chloride analog copolymer composition of the present invention can use derivatived celluloses such as methylcellulose gum, ethyl cellulose, hydroxypropylcellulose, hydroxyethylmethyl-cellulose, Vltra tears; The partly-hydrolysed thing of polyvinyl alcohol and polyvinyl acetate etc.Among these, special preferable methyl Mierocrystalline cellulose, Vltra tears., be preferably more than the 5mN/m in 20 ℃ surface tension for the aqueous solution of 0.2 weight % of these suspension agents, be preferably below the 60mN/m from the progressive viewpoint of polymerization from the viewpoint of the particle diameter that obtains.
With respect 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, can access suspension polymerization stability, the vinylidene chloride analog copolymer that the amount of huge particle or molecule can produced effectively is minimized.Suspension agent can once all add also and can gradation add, to its interpolation period without limits.
In addition, because in the polymerization machine and the corrosion speed in the device of subsequent handling accelerate, thereby for the pH value that makes vinylidene chloride analog copolymer slurries excessive descent not, can be for the purpose inferior limit ground interpolation alkaline matter of adjusting pH value in polymerization initial stage or polymerization way.
In order to make vinylidene chloride analog copolymer of the present invention, also can when polymerization, add chain-transfer agents such as mixing trieline, dodecyl mercaptans, spicy thioalcohol, Thiovanic acid, thioglycollic acid-2-ethyl hexyl ester.
The weight-average molecular weight of vinylidene chloride analog copolymer of the present invention is preferably about 60,000～200,000, and more preferably 70,000～150,000, more preferably 80,000～130,000.Weight-average molecular weight is when this scope, and the viewpoint of extruding stability, high frequency seal compatibility, heating and pressurizing sterilization adaptability (so-called boiling adaptability) during from melt molding is preferred.Also can be by the vinylidene chloride analog copolymer composition more than 2 kinds that weight-average molecular weight is different with ratio cooperation arbitrarily, the weight-average molecular weight that makes composition is in above-mentioned scope.Weight-average molecular weight can be used based on the polystyrene conversion weight-average molecular weight of gel permeation chromatography and measure.
The weight average particle diameter of vinylidene chloride analog copolymer of the present invention is the scope of 200 μ m～500 μ m.If particle diameter is in this scope, the load of extruding when then by the melt molding method vinylidene chloride analog copolymer composition being stretched is easy to become constant, can carry out the stable processing of extruding.The result can easily make the film that obtains or the uniform film thickness of sheet material.
There is no particular restriction for polymerizer used in the suspension polymerization, can adopt known polymerizer, is preferably the polymerizer that has the glass lining.Stirrer to the polymerizer that is used for suspension polymerization is not particularly limited, and also can use baffle plate as required.In stirrer, can enumerate the common impeller vane that in the monomeric polymerization of polyvinyl chloride-base, uses, fan turbine blade, three leaf swept-back (Pfaudler) blades, Burmagin blade etc., but the wherein preferred control monomer oil droplet three leaf swept-back vanes directly easily that use.Can enumerate finger type, round tube type, D type and ring-like etc. as baffle plate.The baffle plate of these stirrers preferably has the glass lining.
In order to obtain vinylidene chloride analog copolymer particle by suspension polymerization, need keep the balance of the stirring velocity of the capillary decline that causes by suspension agent and stirrer well, make the vinylidene chloride analog copolymer not sedimentation of particle of generation simultaneously or do not stick on polymerizer or the stirrer, finish polymerization thus.For this reason, the agitation condition of control machinery is a particularly important, by selecting stirring velocity and stirring revolution, makes its polymerization when vinylidene chloride analog copolymer particle is swum specifically.
In general, swim in order to make polymer beads, stirring velocity is set at the high speed that polymer beads is fully swum, but in this case, polymer beads is subjected to the shearing force of agitating vane, the particle diameter of polymkeric substance diminishes.On the other hand, if make the polymkeric substance particle diameter become big and stirring velocity be set at low speed, then polymkeric substance begins sedimentation, the cohesion that polymkeric substance also can take place adheres to, and has the danger that all sticks in the polymerizer.Among the present invention,, need near the settled limit does not take place vinylidene chloride analog copolymer particle, not carry out suspension polymerization in order to prevent the particulate sedimentation of vinylidene chloride analog copolymer and to suppress the formation of molecule.For example, use under the situation of three leaf swept-back vanes, will be set at 0.7m/sec with the stirring velocity of following formula 1 expression when above, then suspension polymerization can stably be carried out, and is therefore preferred; Be set at 5.5m/sec when following, then the particle diameter of resulting polymkeric substance is preferred in suitable scope.Concrete condition need change according to the size of the scale of stirring.
[formula 1] stirring velocity (m/sec)=n π d/60
(n: the revolution of agitating vane (rpm), π: pi, d: agitating vane exhibition long (m))
For example agitating vane exhibition length is
Situation under, stirring velocity is 1.3m/sec～4.2m/sec when 60rpm～200rpm, so preferred; In addition, span of foil is
Situation under, stirring velocity is 2.0m/sec～5.3m/sec when 20rpm～50rpm, so preferred.
Vinylidene chloride analog copolymer of the present invention is made pulverous vinylidene chloride analog copolymer through MONOMER RECOVERY, dehydration, drying process after polymerization finishes.
For vinylidene chloride analog copolymer of the present invention, in vinylidene chloride analog copolymer (a), cooperate 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), can enumerate phthalic esters such as dioctyl phthalate (DOP), diisononyl phthalate; Citrates such as tributyl acetylcitrate; Fatty group dibasic acids such as Uniflex DBS, dioctyl sebacate, diisobutyl adipate; Triglyceride level such as vanay, tributyrin etc.Among these, preferred especially tributyl acetylcitrate, Uniflex DBS.These softening agent (b) can use separately, also can two or more mixing use.For the addition of softening agent (b), consider from the equilibrated viewpoint of melt molding processibility and resistance oxygen, be preferably 0.1 mass parts～10 mass parts with respect to vinylidene chloride analog copolymer (a) 100 mass parts, more preferably 0.2 mass parts～6 mass parts.
As epoxy compounds (c), can enumerate soybean oil, linseed oil, Oleum Cocois, Thistle oil, sunflower seed oil, cottonseed wet goods have been carried out the epoxidized vegetable oil behind the epoxidation; Epoxidized fatty acid monoesters such as epoxidation octyl stearate; Glycol ester to unsaturated fatty acids carries out the resulting epoxidized fatty acid diester of epoxidation; Cycloaliphatic epoxides such as epoxidation six hydrogen phthalates; Resins, epoxy such as bisphenol A diglycidyl ether etc.Preferred especially epoxidised soybean oil among these.These epoxy compoundss (c) can use separately, also can two or more mixing use.The viewpoint of thermostability during from melt molding and resistance oxygen considers, the addition of preferred epoxy compounds (c) is 0.05 mass parts～5 mass parts, 0.1 mass parts～3 mass parts more preferably with respect to 100 mass parts vinylidene chloride analog copolymers (a).
As antioxidant (d), can enumerate vitamin E, butylhydroxy toluene (BHT), triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) phenol such as propionic ester, four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane is antioxidant; Sulphur such as thio-2 acid alkyl ester are antioxidant etc.These antioxidants (d) can use separately, also can two or more mixing use, and preferably be that antioxidant mixes use with thio-2 acid alkyl ester and phenol.The viewpoint of thermostability during from melt molding and tint permanence and economy considers, the addition of preferred anti-oxidant (d) is 0.01 mass parts～1 mass parts, 0.02 mass parts～0.5 mass parts more preferably with respect to 100 mass parts vinylidene chloride analog copolymers (a).
In vinylidene chloride analog copolymer composition of the present invention, can further suitably add additives such as thermo-stabilizer, lubricant, the agent of pears face, tensio-active agent, photostabilizer, gelation improving agent, pH regulator agent, antistatic agent, linking agent, defoamer, Scale inhibitors, pigment, filler.As these additives, for example can enumerate thermo-stabilizers such as inorganic salts such as representative examples of saturated aliphatic monocarboxylic acids such as citric acid and an alkali metal salt thereof, carbonate, sulfites, trisodium phosphate, tripoly phosphate sodium STPP, acetate and organic or inorganic acid such as saturated aliphatic dicarboxylic acids such as alkaline metal salt, succsinic acid and alkaline metal salt thereof thereof and salt, ethylenediamine tetraacetic acid (EDTA) and alkaline metal salt thereof, magnesium oxide, magnesium hydroxide; Lubricants such as the monoamide of fatty acid esters such as wax, monoglyceride such as oxidized polyethlene wax, paraffin, montanic acid ester type waxes, lipid acid or diamide; Pears face agent such as silicon-dioxide, hydrous magnesium silicate, lime carbonate; Nonionogenic tensides such as sorbitan fatty acid esters, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid esters; Photostabilizers such as 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzene and triazole etc.These additives preferably use as required.
Blending means to these additives is not particularly limited, can use existing method, carry out polymerization after can being added in the mixture of vinylidene chloride before the polymerization and vinylchlorid in advance, also can or be added into after the polymerization in the vinylidene chloride polymer of pulp-like in the polymerization way, can also be added in the preceding pulverous vinylidene chloride analog copolymer composition of melt molding.In pulverous vinylidene chloride analog copolymer composition, mix in the situation of these additives, can by for example adopt that duo mill carries out mixing, adopt mixing that agitators such as propeller agitator or helix agitator carry out, the mixing of adopting the Henschel super mixer to carry out waits and carries out, and can use the heating hybrid mode that surpasses 60 ℃ or in any mode of the low-temperature mixed mode below 60 ℃.
Vinylidene chloride analog copolymer composition of the present invention can adopt common melt molding method to stretch, or is processed into the film or the sheet material of single or multiple lift under tensile situation not.Wherein, the following 2 kinds of making methods of suitable use: inflation method, promptly, extrude from the circular die of screw extrusion press, after making tubular extrudate pass through the 1st following cooling bath of room temperature, feed the 2nd pre-heating bath, between 2 groups of pinch rolls, import air and make it form expansible film bubble (bubble) thereby the method for making film or sheet material; Or the T modulus method, promptly extrude cooling, thereby make the method for film or sheet material by the T mould.More preferably use inflation method.
When using vinylidene chloride analog copolymer composition of the present invention, the generation of the vinylidene chloride due to the thermal degradation when in the time of can be with melt molding suppresses very lowly.The generation of the vinylidene chloride due to the thermal degradation when during melt molding can followingly be estimated: the test method(s) " N; N-N,N-DIMETHYLACETAMIDE dissolving/headspace method (N; N-ジ メ チ Le ア セ ト ア ミ De dissolving/ヘ Star De ス ぺ one ス method) " of vinylidene chloride of regulation in " the 3rd utensil and the container package " of and 34 years (nineteen fifty-nine) Health and human services department bulletin No. 370 " the specification benchmark of food, additive etc. " clear based on Japan, the using gas chromatography is measured melt molding first being processed and vinylidene chloride content afterwards, estimates thus.
And when using vinylidene chloride analog copolymer composition of the present invention, the rate of change that can easily obtain thickness by the melt molding method is the film or the sheet material of the film uniformity excellence below 10%.The film made with about 300m length measurment average film thickness and standard deviation, is obtained the rate of change of thickness according to following formula 2.The rate of change of thickness is more preferably below 6%.
The rate of change (%)=(standard deviation/average film thickness) * 100 of the thickness of [formula 2] film
Further, in the film or sheet material that is obtained by vinylidene chloride analog copolymer composition of the present invention, sneaking into of the impurity due to the thermal degradation when is few.Impurity following the obtaining of counting: when carrying out melt molding, use the determination of foreign matter equipment of image sensor mode, it is that the number of the thermal degradation when impurity of the vinylidene chloride analog copolymer of size more than the 0.5mm detects that beginning is blended into length in the film behind the melt molding, obtains impurity thus and counts.Impurity is counted and is preferably 0.01/m
2Below, 0.006/m more preferably
2Below.
In addition, for the film or the sheet material that obtain by vinylidene chloride analog copolymer composition of the present invention, because the vinylidene chloride generation due to the thermal degradation when during melt molding is low and thermal degradation when due to painted also little, thereby the recirculation adaptability height of melt molding processed goods, the environment affinity is also excellent, also can boost productivity.Recirculation adaptability can followingly be estimated: the melt molding processed goods is carried out melt molding processing once more as raw material, measure the tint permanence (film b value) of resulting recirculation melt molding processed goods, thus recirculation adaptability is estimated.
When forcing machine is supplied with vinylidene chloride analog copolymer composition of the present invention, if use to the vinylidene chloride analog copolymer composition continuous measurement of putting into loading hopper device inside on the machine and the material feeder of weight feed, effect then of the present invention is more remarkable, so preferred.Can enumerate for example screw feeder, annular material feeder, electromagnetism material feeder, weight-type material feeder, volumetric feeder etc. as this material feeder.Wherein, preferred operating weight formula material feeder carries out the blended method.By using the material feeder of weight feed vinylidene chloride analog copolymer composition, can further suppress inhomogeneous, extrude the change of the screw-rod engine load that adds man-hour, the change of extrusion capacity to the forcing machine supply, can the modified resin resolvent suppress effect, also can reduce sneaking into of impurity due to the painted and thermal degradation when of resin etc. in the adhesion of die head spout.
Vinylidene chloride analog copolymer composition of the present invention can further improve and extrude stability by supplying with to forcing machine via the vacuum charging bucket, further reduces thermal degradation when impurity.The vacuum tightness of vacuum charging bucket is preferably-6.66 * 10
-2MPa is following, more preferably-7.99 * 10
-2MPa is to-10.1 * 10
-2The scope of MPa.By supplying with said composition to forcing machine via the vacuum charging bucket that is set at this condition, can suppress bubble and in resin melt, sneak into, can stable maintenance extrude processibility and stretchiness.Through being connected in the forcing machine of vacuum charging bucket bottom, adopting known method to stretch, or do not forming film or sheet material under the tensile condition.
Film of the present invention or sheet material are orientated by biaxial stretch-formed, have heat-shrinkable, and, also can be aptly as can be at 120 ℃ (pressurization 0.245MPa), the thermotolerance film or the sheet material that used under such boiling treatment condition in 20 minutes.Stretching ratio preferably vertically is 2.0 times～4.5 times, laterally is 3.0 times～5.0 times.For the thickness of film or sheet material, monofilm is preferably 5 μ m～30 μ m, more preferably 10 μ m～25 μ m.Also can be used as duplicature or sheet material use 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 can implement post-treatment such as Corona discharge Treatment to film of the present invention or sheet material as required.
In film of the present invention or the sheet material, because sneaking into of thermal degradation when impurity is few, thereby under the situation that is used for used for packing foods film or used for packing foods sheet material, when carrying out the high frequency sealing in order to obtain film or sheet-material package body, can reduce electrode leaves film owing to impurity phenomenon, thereby be easy to keep sealing intensity constant, the breaking of film wrapping body in the time of can reducing packing and fill and during heating and pressurizing germicidal treatment (so-called boiling processing) can be boosted productivity.
The high frequency seal compatibility is estimated as follows: the film or the sheet material that cut are arranged at the automatic filling clipper behind film supply unit, high frequency sealing, automatic filling part, the ligation integrally (for example ADP (trade(brand)name) of Asahi Chemical Industry's chemistry (strain) manufacturing), adopt the high frequency sealing that sausage is packed in the cylindric film or sheet material of middle envelope (セ Application タ one シ one Le) as weighting material with raw meat, obtain the wrapping body that two ends clamp with wire, record broken bag number at this moment, the broken bag incidence is estimated the high frequency seal compatibility thus when calculating filling by following formula 3.To approach 0 high frequency seal compatibility more good more for the broken bag incidence during filling, but consider to be preferably below 0.02% from the aspect of productivity, more preferably below 0.01%.
Broken bag incidence (%)=(broken bag frequency/filling radical during filling) * 100 when [formula 3] fills
Boiling adaptability is estimated as follows: in Heating temperature is that 120 ℃, heat-up time are under 20 minutes the condition, handle carry out boiling by the wrapping body that obtains in the evaluation of above-mentioned high frequency seal compatibility, it is constant to keep the heating tank internal pressure afterwards, pressurization is cooled to after temperature is 25 ℃, relief pressure takes out wrapping body from heating tank, write down the hermetic unit disruptive quantity of this moment from wrapping body, calculate boiling broken bag incidence by following formula 4, estimate boiling adaptability thus.It is good more that boiling broken bag incidence approaches 0 boiling adaptability more, but consider to be preferably below 0.02% from the aspect of productivity, more preferably below 0.01%.
[formula 4] boiling broken bag incidence (%)=(radical is handled in boiling broken bag radical/boiling) * 100
For film that obtains like this or sheet material, the vinylidene chloride content that generates by thermolysis is few, the film uniformity excellence, and thermal degradation when impurity is counted few, thereby high frequency seal compatibility and heating and pressurizing sterilization adaptability excellence, thereby can be used as ham, sausage, cheese, prepared food, other food etc. aptly needs the wrapping material of barrier, reach preservative film etc.Wherein can be used as casing especially aptly.Further, in film of the present invention or the sheet material, because the recirculation adaptability of melt molding processed goods is also very high, thereby environment affinity excellence, can also boost productivity.
Embodiment
Then, by embodiment and comparative example the present invention is described in further detail, but the present invention is not subjected to the restriction of these embodiment.
Below provide the measuring method and the evaluation method of characteristic among the present invention.
1) dissolved oxygen concentration in the deionized water uses automatic DO determinator (ORE society of Co., Ltd. C makes CD-3201) to measure.
2) weight average particle diameter of vinylidene chloride analog copolymer
Weight average particle diameter uses particle size distribution analyzer (Beckman Coulter Co., Ltd. makes Multisizer 3) to measure.
3) weight-average molecular weight of vinylidene chloride analog copolymer
Weight-average molecular weight is used gel permeation chromatography (GPC), measures the polystyrene conversion weight-average molecular weight according to following condition.
Determinator: gel permeation chromatograph HLC-8020 (manufacturing of Tosoh Co., Ltd.)
Post: TSKgel Super HM-H (manufacturing of Tosoh Co., Ltd.) 7.8mm * 30cm * 2
Elutriant: tetrahydrofuran (THF) (THF)
Flow velocity: 1ml/min
Column temperature: 40 ℃
Detector: RI
4) based on the proton magnetic resonance (PMR) optical spectroscopy (
1H-NMR) molecular diffusivity is measured
0.5 quality % deuterium of preparation sample is for tetrahydrofuran solution, use high resolving power proton magnetic resonance (PMR) device (NEC society makes 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, use bpp-led-dosy-pfg as pulse protocol, measure at 30 ℃, obtain 24 spectrum.Operational method as the Laplace inverse transformation uses CONTIN, and the setting range that makes spread coefficient is 0.1um
2/ s～1000um
2/ s carries out DOSY to be handled, and obtaining with the spread coefficient is that the longitudinal axis, chemical shift are the two-dimentional NMR spectrogram of transverse axis.The chemical shift of wherein obtaining expression vinylidene chloride-vinylidene chloride chain is that the spread coefficient of summit of signal of 3.95ppm and the chemical shift of expression vinylidene chloride-vinylchlorid chain are the spread coefficient of summit of the signal of 3.25ppm.
5) measuring method of terminal double link amount
Utilizing reprecipitation method to carry out refinement treatment (is dissolved in vinylidene chloride analog copolymer 1g among tetrahydrofuran (THF) (THF) 20ml, behind the filtering indissolvable component, stir and in filtrate, slowly drip methyl alcohol 80ml down, the vinylidene chloride analog copolymer of separating out is leached and drying), obtain the vinylidene chloride analog copolymer, prepare its 5 quality % deuterium for tetrahydrofuran solution, utilize high resolving power proton magnetic resonance (PMR) device (Bruker BioSpin Co., Ltd. makes AVANCE600) repeatedly with 1 second pulse waiting time, the condition that integral number of times is 1024 times is measured, and obtaining with the tetramethylsilane is benchmark, with the chemical shift is the spectrogram of transverse axis.Wherein, according to chemical shift be from vinylidene chloride that constitutes the vinylidene chloride analog copolymer and vinylchlorid 2.5ppm, 3.3ppm, 4.0ppm signal integrated value 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 (mole %) of terminal double link amount.
6) the vinylidene chloride content in the vinylidene chloride analog copolymer
The test method(s) " N; N-N,N-DIMETHYLACETAMIDE dissolving/headspace method " of vinylidene chloride of regulation is measured the vinylidene chloride content in the vinylidene chloride analog copolymer in " the 3rd utensil and the container package " of and 34 years (nineteen fifty-nine) Health and human services department bulletin No. 370 " the specification benchmark of food, additive etc. " clear based on Japan.Be determined at the melt molding first being processed and carry out afterwards, the variation of the vinylidene chloride content due to the melt molding processing is estimated.
7) rate of change of the thickness of film
The film made with about 300m length measurment average film thickness and standard deviation, is obtained the rate of change of thickness according to following formula 5.
[formula 5]
The rate of change of the thickness of film (%)=(standard deviation/average film thickness) * 100
8) impurity in the film is counted
When carrying out melt molding, use the determination of foreign matter machine (Futec of Co., Ltd. makes 3R4003) of image sensor mode that the thermal degradation when impurity that is blended into the vinylidene chloride analog copolymer in the film is detected.Behind the beginning melt molding, detecting length is the number of the thermal degradation when impurity of the above size of 0.5mm, obtains every 1m
2In the impurity number.
9) recirculation adaptability (the aberration b value of recirculation melt molding processing of films)
The following evaluation of recirculation adaptability: the melt molding processing of films is carried out melt molding processing once more as raw material, the tint permanence (aberration b value) of resulting recirculation melt molding processing of films is measured, estimate thus.Aberration b value for film, according to " the optical characteristics test methods of plastics " (JIS K 7105), 10 recirculation melt molding processing of films are overlapping, gather 400 ± 10 mu m range Determination of thickness samples, utilize colour examining colour-difference-metre (Japanese electric look industry (strain) society makes Z-300A) to measure from the catoptrical aberration b value of this color standard white face reflection.
10) high frequency seal compatibility
To be arranged at the duplicature that the mode of folding width 40mm is cut on the automatic filling clipper ADP that the Asahi Chemical Industry's chemistry (strain) behind film supply unit, high frequency sealing, automatic filling part, the ligation integrally is made, by the high frequency sealing sausage is packed in the cylindric film of middle envelope as weighting material with raw meat (pork meat stuffing), obtains the wrapping body that two ends clamp with wire.Observe record also and make broken bag number during 50,000 this moment, estimate by the mode of following formula 6 broken bag incidence when filling.
Broken bag incidence (%) when [formula 6] fills=(during filling broken bag frequency/50,000 piece) * 100
11) boiling adaptability
By gauge pressure in heating tank is that 0.245MPa, temperature are under 120 ℃, 20 minutes the condition, to by obtain in the evaluation of above-mentioned high frequency seal compatibility 50,000 wrapping body carries out hot digestion to be handled, it is constant to keep the heating tank internal pressure afterwards, pressurization is cooled to after temperature is 25 ℃, relief pressure takes out wrapping body from heating tank, with it as the final packaging body.Investigation is estimated in the mode of boiling broken bag incidence by following formula 7 from the hermetic unit disruptive quantity of wrapping body.
[formula 7] boiling broken bag incidence (%)=(boiling broken bag radical/50,000) * 100
[embodiment 1]
To possess three leaf swept-back vanes (exhibition major diameter 400mm), refer to that type baffle plate, temperature take into account the reactor that has the glass lining of nitrogen ingress pipe (internal volume 300L) and be decompressed to-9.00 * 10
-2MPa also imports nitrogen simultaneously, and making polymerizer inner is nitrogen atmosphere.After the operation of this decompression, nitrogen replacement is carried out 3 times repeatedly, in reactor, drop into polymerization starter di-isopropyl peroxydicarbonate 0.15 mass parts, vinylchlorid (VC) 18 mass parts, vinylidene chloride (VDC) 82 mass parts, 3,3-Tyox B (DLTDP) 0.03 mass parts, Uniflex DBS (hereinafter referred to as DBS) 3 mass parts carry out stirring in 20 minutes to mixed solution with the stirring velocity of 1.4m/sec.Next (nitrogen bubble that this deionized water has been carried out 2 hours reduces dissolved oxygen concentration to add water temperature and be 20 ℃ deionized water, after this operation, dissolved oxygen concentration is 0.8mg/L) concentration of 100 mass parts, suspension agent Vltra tears is the aqueous solution 2.5 mass parts of 2 quality %, stir confirm to form particle in 20 minutes after, under nitrogen atmosphere, be heated to 35 ℃ of polymerization initial stage temperature, initiated polymerization.After the sustained reaction 15 hours, stirring velocity is made as 1.2 times (1.68m/sec) of initial stage speed, is warming up to 62 ℃ of polymerization latter temperatures with 15 hours, further proceed polymerization in 2 hours.After reacting end, press in the slowly open reactor, reduce pressure with vacuum pump then, next interior temperature is warmed up to 75 ℃, further proceed stirring in 3 hours, the separation unreacted monomer with 1 hour.Dewater subsequently,, obtain pulverous vinylidene chloride analog copolymer composition 70 ℃ of dryings 24 hours.To the polymerisation conversion of resulting vinylidene chloride analog copolymer composition, weight average particle diameter, weight-average molecular weight, based on the chemical shift of DOSY spread coefficient, the terminal double link amount of the summit of the spread coefficient of summit of signal of 3.95ppm and the signal that chemical shift is 3.25ppm.
In the resulting vinylidene chloride analog copolymer of 100 mass parts composition, add 2 mass parts epoxidised soybean oil (to call ESO in the following text), 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 the vinylidene chloride analog copolymer composition before the resulting melt molding processing is measured.
Use spiral material feeder, press via vacuum to be set at-9.00 * 10
-2The vacuum charging bucket of MPa is put into it in forcing machine that diameter is 40mm, extrudes to after the ring-type, and cooling rapidly makes it pass through 20 ℃ warm water bath then in 10 ℃ cooling tank.Further, between the different pinch roll of 2 groups of surface of revolution speed, be pressed into air and make its expansion, behind 2.8 times of length directions, 3.7 times of stretch orientations of width,, obtain the duplicature of thickness 40 μ m the flat extrusion of this tubular film.The rate of change of the thickness of vinylidene chloride content, average film thickness and the film of resulting film, impurity in the film counted measure.And, resulting film is carried out once more melt molding processing as raw material, the tint permanence (aberration b value) of resulting recirculation melt molding processing of films is measured, estimate recirculation adaptability.
Then, will be arranged at the duplicature that the mode of folding width 40mm is cut on the automatic filling clipper ADP of Asahi Chemical Industry's chemistry (strain) manufacturing, estimate high frequency seal compatibility, boiling adaptability.
The results are shown in table 1.
[embodiment 2]
For the condition of polymerization temperature, establishing polymerization initial stage temperature is 35 ℃, after this temperature is proceeded reaction in 15 hours, is warming up to 62 ℃ of polymerization latter temperatures with 1 hour, further proceeds polymerization in 16 hours, operates similarly to Example 1 in addition.The results are shown in table 1.
[embodiment 3]
Except using the deionized water of dissolved oxygen concentration, operate similarly to Example 1 as 7.5mg/L.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, establishing polymerization initial stage temperature is 35 ℃, after this temperature is proceeded reaction in 10 hours, is warming up to 62 ℃ of polymerization latter temperatures with 15 hours, further proceeds polymerization in 2 hours, operates similarly to Example 1 in addition.The results are shown in table 1.
[comparative example 1]
Vacuum operating before not feeding intake, and, condition for polymerization temperature, if polymerization initial stage temperature is 35 ℃, after this temperature is proceeded reaction in 15 hours, be warming up to 62 ℃ of polymerization latter temperatures with 1 hour, further proceed polymerization in 12 hours, 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 of dissolved oxygen concentration as 7.5mg/L, in addition, similarly operate with comparative example 1.The results are shown in table 1.
[comparative example 3]
Use the deionized water of dissolved oxygen concentration as 7.5mg/L, and, condition for polymerization temperature, if polymerization initial stage temperature is 35 ℃, after this temperature is proceeded reaction in 10 hours, be warming up to 62 ℃ of polymerization latter temperatures with 15 hours, further proceed polymerization in 2 hours, in addition, similarly operate with comparative example 1.The results are shown in table 1.
[comparative example 4]
Use the deionized water of dissolved oxygen concentration as 7.5mg/L, and, condition for polymerization temperature, if polymerization initial stage temperature is 35 ℃, after this temperature is proceeded reaction in 15 hours, be warming up to 62 ℃ of polymerization latter temperatures with 1 hour, further proceed polymerization in 16 hours, in addition, similarly operate with comparative example 1.The results are shown in table 1.
Can confirm by embodiment and comparative example, few when vinylidene chloride analog copolymer of the present invention can access melt molding, film uniformity is excellent and thermal degradation when impurity is counted few film or sheet material by the vinylidene chloride generation due to the thermolysis, and the recirculation adaptability height of melt molding processed goods, high frequency seal compatibility and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence.
Industrial applicibility
Few when vinylidene chloride analog copolymer of the present invention can access melt molding, film uniformity is excellent and thermal degradation when impurity is counted few film or sheet material by the vinylidene chloride generation due to the thermolysis, 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) excellence, thereby 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.
Claims (6)
1. vinylidene chloride analog copolymer, it is the vinylidene chloride analog copolymer that is made of vinylidene chloride and vinylchlorid, wherein, utilize the proton magnetic resonance (PMR) optical spectroscopy (
1Under the situation about H-NMR) analyzing, it is 0.5 mole below the % with respect to the monomeric unit that constitutes the vinylidene chloride analog copolymer from the integrated value of the signal of the carbon-to-carbon double bond of molecule chain end.
2. vinylidene chloride analog copolymer as claimed in claim 1, wherein, utilize based on the proton magnetic resonance (PMR) optical spectroscopy (
1H-NMR) molecular diffusivity is measured under the situation about analyzing, and chemical shift is that spread coefficient and the chemical shift of summit of the signal of 3.95ppm is that the ratio of spread coefficient of summit of the signal of 3.25ppm is 1: 1.5～1: 5.
3. vinylidene chloride analog copolymer composition, it contains claim 1 or 2 described vinylidene chloride analog copolymers (a), 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 of 100 mass parts.
4. film or sheet material, it carries out melt molding to the described vinylidene chloride analog copolymer of claim 3 composition and obtains.
5. food container, it has used described film of claim 4 or sheet material.
6. food container as claimed in claim 5, it is a casing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105980259A (en) * | 2014-02-18 | 2016-09-28 | 株式会社吴羽 | Preservative film |
| CN106117974A (en) * | 2016-06-27 | 2016-11-16 | 苏州市鼎立包装有限公司 | A kind of high barrier toiletry bag package material and preparation method thereof |
| CN112745605A (en) * | 2019-10-31 | 2021-05-04 | 旭化成株式会社 | Fresh-keeping film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242484A (en) * | 1978-04-08 | 1980-12-30 | Nippon Zeon Co., Ltd. | Vinylidene chloride copolymer as a material for production of packaging articles |
| CN1215064A (en) * | 1997-10-16 | 1999-04-28 | 旭化成工业株式会社 | Vinylidene chloride like resin film shaped article and preparation process thereof |
| CN1529736A (en) * | 2001-07-13 | 2004-09-15 | 旭化成株式会社 | Composition of vinylidene chloride copolymer particles |
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2012
- 2012-01-30 CN CN201210021064.0A patent/CN103224581B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242484A (en) * | 1978-04-08 | 1980-12-30 | Nippon Zeon Co., Ltd. | Vinylidene chloride copolymer as a material for production of packaging articles |
| CN1215064A (en) * | 1997-10-16 | 1999-04-28 | 旭化成工业株式会社 | Vinylidene chloride like resin film shaped article and preparation process thereof |
| CN1529736A (en) * | 2001-07-13 | 2004-09-15 | 旭化成株式会社 | Composition of vinylidene chloride copolymer particles |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105980259A (en) * | 2014-02-18 | 2016-09-28 | 株式会社吴羽 | Preservative film |
| CN106117974A (en) * | 2016-06-27 | 2016-11-16 | 苏州市鼎立包装有限公司 | A kind of high barrier toiletry bag package material and preparation method thereof |
| CN112745605A (en) * | 2019-10-31 | 2021-05-04 | 旭化成株式会社 | Fresh-keeping film |
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