CN103224582A - Vinylidene chloride copolymer, and its membrane or sheet material - Google Patents
Vinylidene chloride copolymer, and its membrane or sheet material Download PDFInfo
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- CN103224582A CN103224582A CN2012100210689A CN201210021068A CN103224582A CN 103224582 A CN103224582 A CN 103224582A CN 2012100210689 A CN2012100210689 A CN 2012100210689A CN 201210021068 A CN201210021068 A CN 201210021068A CN 103224582 A CN103224582 A CN 103224582A
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Abstract
The invention relates to a vinylidene chloride copolymer composition, the stretch processing adaptability during a melt molding process is excellent, thereby membrane thickness uniformity of the obtained membrane or the sheet material is excellent, 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, through the differential scanning calorimetry thermal detection (DSC), and the heat release summit time of the vinylidene chloride copolymer detected in an isothermal crystallization detection at 70 DEG C is less than 10 minutes.
Description
Technical field
The vinylidene chloride analog copolymer and the composition thereof of the stretch process adaptability excellence when the present invention relates to melt molding, the film that can obtain the film uniformity excellence or sheet material; Fill adaptability and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellent its film or sheet material at a high speed; And the food container of this film of use 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 for packaging material for food, preservative film etc.Manufacture method at the vinylidene chloride analog copolymer composition 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.
Common film or sheet material for membrane thickness unevenness, when carrying out the high frequency sealing in order to obtain wrapping body, because electrode is being adhered with film or sheet material under the pressure always uniformly, thereby sealing intensity is inhomogeneous, productivity often reduces.In addition, in recent years, Autofillingpackagingmachine significantly improves its capacity packing by the high speed fillingization.But, have requirement aspect the bad incidence that packing followed reducing, and use current packaging to be difficult to satisfy this requirement with film.
As the thickness uniform method that makes film or sheet material in order to address this problem, in patent documentation 1, proposed in forcing machine, stably to supply with the vinylidene chloride analog copolymer method for compositions of constant basis, a kind of vinylidene chloride analog copolymer composition that is obtained by suspension polymerization is disclosed, it has specific particle diameter, the molecule amount that is contained is below the constant basis, and has specific bulk density.In addition, in patent documentation 2, disclose by in material resin, add particulate talcum as crystallization nucleating agent improve from molten state carry out recrystallize recrystallize speed, reduce the method for the bad incidence when filling at a high speed.Further, in patent documentation 3, disclose by using and improved the adaptive method of filling at a high speed as the laminated film more than 3 layers of principal constituent with vinylidene chloride resin.
The prior art document
Patent documentation
Patent documentation 1: the international brochure that discloses No. 2003/006548
Patent documentation 2: Japanese kokai publication sho 55-129439 communique
Patent documentation 3: Japanese kokai publication hei 7-68720 communique
Summary of the invention
In general, the vinylidene chloride analog copolymer that is obtained by suspension polymerization can only obtain the wide vinylidene chloride analog copolymer of size distribution.Use the melt molding method that the wide vinylidene chloride analog copolymer composition of size distribution is carried out under the tensile situation, because it is moving that the uneven distribution of vinylidene chloride analog copolymer coating of particles and size makes that the volume production that is filled into the multipolymer in the machine barrel in the die head changes, thereby have influence on the output of forcing machine.Therefore the pressure of pressure head produces change, and the result causes the membrane thickness unevenness of the film extruded.In patent documentation 1 described vinylidene chloride analog copolymer composition,, under harsh in recent years melt molding condition, can not obtain sufficient film uniformity about preventing to generate the record of the big particulate method of particle diameter.In addition, in patent documentation 2 described vinylidene chloride analog copolymers, used the particulate talcum, but can not avoid talcum to assemble for mixed 2 times, had the transparent variation of film, produce problem such as spark when micropore, high frequency sealing occurring.In patent documentation 3 described vinylidene chloride analog copolymers, need to adopt the extruding technology of the precision of utilizing multilayer forcing machine etc., the productivity when extruding is not talkative very abundant.
In recent years, for the purpose of boosting productivity, even strong request also can obtain large-duty method under the melt molding condition of harsh day by day vinylidene chloride analog copolymer composition, filling condition.
The vinylidene chloride analog copolymer of the stretch process adaptability excellence when the object of the present invention is to provide melt molding, the film that can obtain the film uniformity excellence or sheet material; Fill the excellent food container of adaptability and heating and pressurizing sterilization adaptability (so-called boiling adaptability) at a high speed.
The inventor furthers investigate repeatedly for solving above-mentioned problem, found that, heat release summit (the development Hot amount ピ one Network ト ッ プ) time or the thermal discharge that record in isothermal crystal mensuration through differential scanning calorimetry (DSC) by the multipolymer that makes vinylidene chloride and polymerizability vinyl monomer satisfy certain conditions, can provide the vinylidene chloride analog copolymer of stretch process adaptability excellence, the film that can obtain the film uniformity excellence or sheet material; And the film or the sheet material of filling adaptability, heating and pressurizing sterilization adaptability excellence at a high speed, finished the present invention based on above-mentioned discovery.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 polymerizability vinyl monomer, wherein, through differential scanning calorimetry (DSC), the heat release summit time of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration is below 10 minutes.
[2] the vinylidene chloride analog copolymer described in [1], wherein, the thermal discharge that the vinylidene chloride analog copolymer records in 70 ℃ isothermal crystal mensuration through differential scanning calorimetry (DSC) is more than the 20J/g.
[3] the vinylidene chloride analog copolymer described in [1] or [2], wherein, its weight-average molecular weight that contains 0.1 quality %～5 quality % is 100,000～1,000,000 polyvinylidene dichloride.
[4] a kind of film or sheet material, it carries out melt molding to the vinylidene chloride analog copolymer composition that contains each the described vinylidene chloride analog copolymer in [1]～[3] 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.
The stretch process adaptability excellence of vinylidene chloride analog copolymer composition of the present invention when melt molding, the film uniformity excellence of resulting film or sheet material is filled adaptability and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence at a high speed.
Description of drawings
Fig. 1 is the heat release summit time in the expression isothermal crystal mensuration and the explanatory view of thermal discharge.
Embodiment
Then, embodiments of the present invention are described.Following embodiment is for example of the present invention is described, 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, as shown in Figure 1, through differential scanning calorimetry (DSC), the heat release summit time of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration is below 10 minutes.Isothermal crystal mensuration can followingly be carried out: use differential scanning calorimeter (the system DSC-50 of Shimadzu Seisakusho Ltd.), (redeposition is undertaken by following method: the sample 1g that will contain the vinylidene chloride analog copolymer is dissolved among tetrahydrofuran (THF) (THF) 20ml will to carry out redeposition to the sample that contains the vinylidene chloride analog copolymer, behind the filtering indissolvable component, stir and in filtrate, slowly drip methyl alcohol 80ml down, the vinylidene chloride analog copolymer of separating out filtered out and dry) and vinylidene chloride analog copolymer 10mg～15mg of obtaining is warmed up to 190 ℃ with 50 ℃/minute heat-up rate by 30 ℃, after 190 ℃ of maintenances complete fusion in 1 minute, cool to 70 ℃ with 40 ℃/minute cooling rates, in the time of will reaching 70 ℃ as measuring the time opening, with the aluminum oxide is standard, carries out the differential scanning calorimetry when keeping 60 minutes for 70 ℃.
The heat release summit time as if the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration through differential scanning calorimetry (DSC) is below 10 minutes, the recrystallize speed of then representing to carry out from molten state recrystallize is fast, thereby the dimensional stability under the situation of carrying out the inflation moulding is good, film bubble (bubble) dimensionally stable, thereby can access the film or the sheet material of film uniformity excellence.And, because film of the present invention or the dimensional change of sheet material after film forming are little, thereby be not prone to crimping distortion such as (volume I Parties り), compare with existing film or sheet material and can shorten digestion time.Further, will be by melt molding under resulting film or the sheet material situation about using as food container, carry out the high frequency sealing when obtaining wrapping body, be subjected to the effect of high frequency irradiation this moment, the recrystallize speed of fused film is fast, even thereby the also rare broken bag of running speed of raising Autofillingpackagingmachine, film uniformity is also excellent simultaneously, thereby can suppress the poor sealing due to so-called electrode saltus step (the ス キ ッ プ) phenomenon, and heating and pressurizing sterilization adaptability (so-called boiling adaptability) is also excellent.Further the heat release summit time of the vinylidene chloride analog copolymer that preferably records in 70 ℃ isothermal crystal mensuration through differential scanning calorimetry (DSC) is 0 minute～5 minutes.
In addition, in the vinylidene chloride analog copolymer of the present invention, more preferably the thermal discharge of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration through differential scanning calorimetry (DSC) is more than the 20J/g.25J/g～50J/g more preferably.The thermal discharge of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration through differential scanning calorimetry (DSC) can be tried to achieve by the area of chart shown in Figure 1.If the thermal discharge of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration through DSC is big, then be illustrated in when carrying out recrystallize and can form more stable crystalline texture by molten state, think that the aggregation force of vinylidene chloride analog copolymer increases behind the recrystallize, tensile strength increases.That is, the film or the sheet material that are obtained by melt molding processing are more tough, and under situation about using as food container, show the effect of the intensity increase of high frequency sealing when obtaining the film wrapping body.
Further, when the weight-average molecular weight that vinylidene chloride analog copolymer of the present invention contains 0.1 quality %～5 quality % is 100,000～1,000,000 polyvinylidene dichloride, then polyvinylidene dichloride can generate the nuclei of crystallization through differential scanning calorimetry (DSC) apace when carrying out isothermal crystal mensuration for 70 ℃, thereby it is accelerate recrystallize speed, thereby more preferred.The weight-average molecular weight of polyvinylidene dichloride more preferably 150,000～600,000.And the content of polyvinylidene dichloride is 0.3 quality %～3 quality % more preferably.
Vinylidene chloride analog copolymer among the present invention is to make vinylidene chloride and can obtain with the polymerizability vinyl monomer copolymerization of this monomer copolymerization.
As can with the polymerizability vinyl monomer of vinylidene chloride copolymerization, then can be vinyl monomer arbitrarily as long as be rich in copolymerization, as industrial useful monomer, can enumerate for example vinylchlorid; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) glycidyl acrylate; The vinyl acetate of aliphatic carboxylic acid such as vinyl-acetic ester, propionate; Unsaturated aliphatic carboxylic acids such as vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, toxilic acid, fumaric acid, maleic anhydride; The half ester and the dibasic acid esters of unsaturated aliphatic such as toxilic acid, methylene-succinic acid carboxylic acid; Aromatic vinyl such as vinylbenzene, alpha-methyl styrene; (methyl) vinyl cyanide, (methyl) acrylamide etc. have the alkene class of the two keys of copolymerization; Isoprene, divinyl etc. have the muriate of dienes such as the dienes of the two keys of 2 copolymerization and chloroprene; As (methyl) acrylate of divinylbenzene, dibasic aliphatic alcohol, has the monomer etc. of the two keys of 2 copolymerization at intramolecularly.These can use separately with the polymerizability vinyl monomer of vinylidene chloride copolymerization, also can mix more than 2 kinds and use.Among these compounds, preferred especially vinylchlorid, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) vinyl cyanide, vinylbenzene, more preferably vinylchlorid.
The ratio that feeds intake of vinylidene chloride depends on the polymerizability vinyl monomer kind with the vinylidene chloride copolymerization in the vinylidene chloride analog copolymer of the present invention, be under the situation of vinylchlorid for example at the polymerizability vinyl monomer, the ratio that feeds intake of preferred vinylidene chloride is 70 quality %～90 quality %, and the ratio that feeds intake of vinylchlorid is 10 quality %～30 quality %.
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.To utilize under the situation that suspension polymerization makes, the total quality of preferred vinylidene chloride and polymerizability vinyl monomer and the quality 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.Preferably in polymerizer, drop into polymerization starter and vinylidene chloride, carry out mixing more than 1 hour.By carry out such operation when polymerization begins, can generate 0.1 quality %～5 quality % weight-average molecular weight is 100,000～1,000,000 polyvinylidene dichloride.Drop into the polymerizability vinyl monomer, after further mixing, drop into water, suspension agent thereafter, confirm the formation of monomer oil droplet after, temperature in the rising reactor, initiated polymerization.Coexisting when polymerization begins has under the situation of other additives such as softening agent, before polymerization starter drops into or after dropping into, perhaps after the input of water it is put in the polymerizer.It is believed that, by carry out polyvinylidene dichloride that such operation generates through differential scanning calorimetry (DSC) when carrying out isothermal crystal mensuration for 70 ℃ owing to promptly generate the nuclei of crystallization, thereby can accelerate recrystallize speed.In addition, carry out well, preferably will be set at atmosphere such as nitrogen, argon gas in the polymerizer in order to make polymerization.
Polymerization temperature, polymerization time can be according to decisions aptly such as the kind of kind, amount and the chain-transfer agent of the kind of vinylidene chloride and polymerizability vinyl monomer, amount, polymerization starter, amounts, roughly 10 ℃～100 ℃, preferred 30 ℃～80 ℃ polymerizations 10 hours～100 hours, more preferably 15 hours～60 hours, more preferably 20 hours～50 hours.And then the polymerization temperature when further preferably making polymerization final is 60～80 ℃.By making the final temperature of polymerization is 60～80 ℃, can generate the low molecular weight compositions that improves transport properties of molecules, can improve crystalline growth speed, thereby can easily to make the heat release summit time of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration through differential scanning calorimetry (DSC) be below 10 minutes.Polymerization temperature begins to finish to be steady temperature to polymerization from polymerization, and also can change in the polymerization way.
Target polymerization rate among the present invention is preferably 90 quality %～97 quality %.92 quality %～96 quality % more preferably.Owing to generate the low molecular weight compositions of a large amount of raising transport properties of moleculess in the polymerization later stage, thereby can easily to make the heat release summit time of the vinylidene chloride analog copolymer that records through differential scanning calorimetry (DSC) under percent polymerization is situation more than the 90 quality % in 70 ℃ isothermal crystal mensuration be below 10 minutes.
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, peresters class initiators such as 3-tetramethyl-butyl ester, the new enanthic acid tert-butyl ester of peroxidation; 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, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, dilauroyl peroxide.
With respect to the mixed solution of vinylidene chloride and polymerizability vinyl monomer, 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 02 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 polymerizability vinyl monomer, 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.
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.
For vinylidene chloride analog copolymer of the present invention, in vinylidene chloride analog copolymer (a), cooperate softening agent (b), epoxy compounds (c), antioxidant (d) and pears face agent (e) to make vinylidene chloride analog copolymer composition as required, 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 the vinylidene chloride analog copolymer (a) of 100 mass parts, more preferably 02 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).
As pears face agent (e), can enumerate silicon-dioxide, hydrous magnesium silicate, lime carbonate etc.These pears face agent (e) can be used separately, also can two or more mixing use.High frequency seal compatibility when foodstuff package is made considers with the viewpoint of the transparency, and the addition of preferred pears face agent (e) 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, 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; 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 polymerizability vinyl monomer 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.
Vinylidene chloride analog copolymer composition of the present invention is when making film or sheet material by inflation method, carry out the fast and excellent in dimensional stability of recrystallize speed of recrystallize by molten state, thereby the shape of blown film bubble is stable easily, can suppress the periodically variable pulsation of film bubble shape.During the dimensionally stable of blown film bubble, the draw ratio of film bubble peripheral direction is difficult for change, and the change of thickness is inhibited, and can access the film of film uniformity excellence.The shape stability of blown film bubble can be estimated by the wide rate of change of film.The film made with wide mean value and the standard deviation of about 300m length measurment film, is obtained the wide rate of change of film according to following formula 2.The wide rate of change of film is preferably below 5%, more preferably below 3%.
The rate of change (%)=(mean value that standard deviation/film is wide) * 100 that [formula 2] film is wide
When using vinylidene chloride analog copolymer composition of the present invention, can easily obtain the film or the sheet material of film uniformity excellence by the melt molding method.Film uniformity is estimated by the rate of change of thickness, and made film or sheet material with about 300m length measurment average film thickness and standard deviation, are obtained the rate of change of thickness according to following formula 3.The rate of change of thickness is preferably below 10%, more preferably below 6%.
The rate of change (%)=(standard deviation/average film thickness) * 100 of [formula 3] thickness
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 improve film uniformity.In addition, can suppress effect in the adhesion of die head spout by the modified resin resolvent, also can reduce the painted of resin and resolvent outflow etc.
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
-2Below the MPa, 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 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, can implement post-treatment such as Corona discharge Treatment to film of the present invention or sheet material as required.
Under the situation as used for packing foods film or the use of used for packing foods sheet material with film of the present invention or sheet material, carry out the high frequency sealing when obtaining wrapping body, be subjected to the effect of high frequency irradiation this moment, the recrystallize speed of fused film is fast, even thereby the also rare broken bag of running speed of raising Autofillingpackagingmachine, film uniformity is also excellent simultaneously, thereby can suppress the poor sealing due to the so-called electrode saltus step phenomenon, can boost productivity.
Filling adaptability at a high speed estimates as follows: the film or the sheet material that cut are arranged at the film supply unit, the high frequency sealing, automatic filling part, Autofillingpackagingmachine behind the ligation integrally (for example ADP (trade(brand)name) of Asahi Chemical Industry's chemistry (strain) manufacturing), making film feeding speed is 2 times of common operating condition, 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, calculate broken bag incidence when filling at a high speed by following formula 4, estimate thus and fill adaptability at a high speed.The broken bag incidence approaches 0 high speed more to fill adaptability good more when filling at a high speed, but considers 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 4] fills at a high speed
Boiling adaptability is estimated as follows: in Heating temperature is that 120 ℃, heat-up time are under 20 minutes the condition, carry out the boiling processing to fill the wrapping body that obtains in the Adaptability Evaluation by above-mentioned high speed, 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 5, 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 5] boiling broken bag incidence (%)=(radical is handled in boiling broken bag radical/boiling) * 100
The film uniformity excellence of film that obtains like this or sheet material, can shorten digestion time, at a high speed fill adaptability and boiling adaptability excellence, thereby can be used as ham, sausage, cheese, prepared food, other food etc. aptly and need the wrapping material of barrier, reach preservative film etc.Wherein can be used as casing especially aptly.
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) 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.
2) 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 society)
Post: TSKgel SuperHM-H (manufacturing of Tosoh society) 7.8mm * 30cm * 2
Elutriant: tetrahydrofuran (THF) (THF)
Flow velocity: 1ml/min
Column temperature: 40 ℃
Detector: RI
3) content of the percent polymerization of vinylidene chloride analog copolymer and polyvinylidene dichloride
Quality and polymerization by vinylidene chloride that is added and polymerizability vinyl monomer stop after the quality of dehydration, dry resulting vinylidene chloride analog copolymer is calculated.In addition,, the part of solution is taken out in by polymerizer before adding being about to add the polymerizability vinyl monomer, do the quality of the solid polyvinylidene dichloride that calculates in the solution to be contained by making solution for the content of polyvinylidene dichloride; After polymerization stops, dewater, drying, obtain the quality of vinylidene chloride analog copolymer, go out the content of polyvinylidene dichloride by above-mentioned Mass Calculation.
4) the vinylidene chloride analog copolymer is through the isothermal crystal mensuration of differential scanning calorimetry (DSC) in 70 ℃
Use differential scanning calorimeter (the system DSC-50 of Shimadzu Seisakusho Ltd.), (redeposition is undertaken by following method: the sample 1g that will contain the vinylidene chloride analog copolymer is dissolved among tetrahydrofuran (THF) (THF) 20ml will to carry out redeposition to the sample that contains the vinylidene chloride analog copolymer, behind the filtering indissolvable component, stir and in filtrate, slowly drip methyl alcohol 80ml down, the vinylidene chloride analog copolymer of separating out filtered out and dry) and vinylidene chloride analog copolymer 10mg～15mg of obtaining is warmed up to 190 ℃ with 50 ℃/minute heat-up rate by 30 ℃, after 190 ℃ of maintenances complete fusion in 1 minute, cool to 70 ℃ with 40 ℃/minute cooling rates, in the time of will reaching 70 ℃ as measuring the time opening, with the aluminum oxide is standard, carry out the differential scanning calorimetry when keeping 60 minutes for 70 ℃, obtain differential scanning calorimetric figure.According to Fig. 1, calculate the heat release summit time of vinylidene chloride analog copolymer and the thermal discharge of vinylidene chloride analog copolymer by this differential scanning calorimetric figure.
5) stability of blown film bubble
The stability of blown film bubble utilizes the wide rate of change of film to estimate.The film made with wide mean value and the standard deviation of about 300m length measurment film, is obtained the wide rate of change of film according to following formula 6.
The rate of change (%)=(mean value that standard deviation/film is wide) * 100 that [formula 6] film is wide
6) 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 7.
The rate of change (%)=(standard deviation/average film thickness) * 100 of the thickness of [formula 7] film
7) fill adaptability at a high speed
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, carry out the high frequency sealing with 60m/ minute film feeding speed, 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 and write down the broken bag number of making this moment during 50,000, the mode of broken bag incidence is estimated when filling with high speed by following formula 8.
Broken bag incidence (%) when [formula 8] fills at a high speed=(during filling broken bag frequency/50,000 piece) * 100
8) boiling adaptability
By gauge pressure in heating tank is that 0.245MPa, temperature are under 120 ℃, 20 minutes the condition, to fill by above-mentioned high speed obtain in the Adaptability Evaluation 50,000 wrapping body carries out boiling 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 9 from the hermetic unit disruptive quantity of wrapping body.
[formula 9] boiling broken bag incidence (%)=(boiling broken bag radical/50,000) * 100
[embodiment 1]
Possessing three leaf swept-back vanes (exhibition major diameter 400mm), referring to that type baffle plate, temperature take into account in the reactor that has the glass lining of nitrogen ingress pipe (internal volume 300L), under nitrogen atmosphere, drop into polymerization starter di-isopropyl peroxydicarbonate 0.15 mass parts (0.17kg), vinylidene chloride (VDC) 82 mass parts (90.2kg), it is 20 ℃ that mixed solution is adjusted to temperature, with the stirring velocity of 1.4m/sec mixed solution is carried out stirring in 3 hours simultaneously, generate polyvinylidene dichloride.Next before being about to drop into vinylchlorid, take out mixed solution 50g, the weight-average molecular weight of polyvinylidene dichloride growing amount and polyvinylidene dichloride is measured.
Drop into vinylchlorid (VC) 18 mass parts (19.8kg), 3 then, 3-Tyox B (DLTDP) 0.03 mass parts (0.03kg) carries out stirring in 20 minutes to mixed solution with the stirring velocity of 1.4m/sec.The concentration of next adding deionized water 100 mass parts (110kg), suspension agent Vltra tears is the aqueous solution 2.5 mass parts (2.75kg) of 2 quality %, stir confirm to form particle in 20 minutes after, be heated to 35 ℃ of polymerization initial stage temperature, initiated polymerization.After the sustained reaction 20 hours, stirring velocity is made as 12 times (1.68m/sec) of initial stage speed, is warming up to 65 ℃ of the final temperature of polymerization with 1 hour, further proceed polymerization in 10 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.The heat release summit time and the thermal discharge of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration to the polymerisation conversion of resulting vinylidene chloride analog copolymer composition, weight average particle diameter, weight-average molecular weight, through differential scanning calorimetry (DSC) are measured.
In the resulting vinylidene chloride analog copolymer of 100 mass parts composition, add 3 mass parts Uniflex DBSs (hereinafter referred to as DBS), 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, 0.05 mass parts red pigment, adopt the Henschel super mixer of low-temperature mixed mode to mix.
Use spiral material feeder, press via vacuum to be set at-9.10 * 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, 3.6 times of stretch orientations of width,, obtain the duplicature of thickness 40 μ m the flat extrusion of this tubular film.Resulting film is carried out the mensuration of the thickness rate of change of the wide rate of change of film, average film thickness and film.
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, and estimate and fill adaptability, boiling adaptability at a high speed.
The results are shown in table 1.
[embodiment 2～4]
According to mass fraction, the rise time of polyvinylidene dichloride, the final temperature of polymerization of the mass fraction of the vinylidene chloride that feeds intake of table 1 record, the vinylchlorid that feeds intake, carry out embodiment 2～4 similarly to Example 1.The results are shown in table 1.
[embodiment 5]
According to the mass fraction of the mass fraction of the vinylidene chloride that feeds intake of table 1 record, the vinylchlorid that feeds intake, the rise time initiated polymerization of polyvinylidene dichloride, polymerization time under the final temperature of 65 ℃ polymerizations is shortened to 6 hours, carry out embodiment 5 in addition similarly to Example 1.The results are shown in table 1.
[comparative example 1]
Mass fraction, the rise time of polyvinylidene dichloride, the final temperature of polymerization according to the mass fraction of the vinylidene chloride that feeds intake of table 1 record, the vinylchlorid that feeds intake compare example 1 similarly to Example 1.The results are shown in table 1.
[comparative example 2]
According to the mass fraction of the mass fraction of the vinylidene chloride that feeds intake of table 1 record, the vinylchlorid that feeds intake, the rise time initiated polymerization of polyvinylidene dichloride, polymerization time under the final temperature of 58 ℃ polymerization of table 1 record is shortened to 6 hours, compare example 2 in addition similarly to Example 1.The results are shown in table 1.
Can confirm according to embodiment and comparative example, the stretch process adaptability excellence of vinylidene chloride analog copolymer of the present invention when melt molding, the film uniformity excellence of resulting film or sheet material is filled adaptability and heating and pressurizing sterilization adaptability (so-called boiling adaptability) excellence at a high speed.
Industrial applicibility
The stretch process adaptability excellence of vinylidene chloride analog copolymer of the present invention when melt molding, the film uniformity excellence of resulting film or sheet material, at a high speed fill adaptability 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, reach 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 polymerizability vinyl monomer, wherein, through differential scanning calorimetry (DSC), the heat release summit time of the vinylidene chloride analog copolymer that records in 70 ℃ isothermal crystal mensuration is below 10 minutes.
2. vinylidene chloride analog copolymer as claimed in claim 1, wherein, the thermal discharge that the vinylidene chloride analog copolymer records in 70 ℃ isothermal crystal mensuration through differential scanning calorimetry (DSC) is more than the 20J/g.
3. vinylidene chloride analog copolymer as claimed in claim 1 or 2, wherein, the weight-average molecular weight that described vinylidene chloride analog copolymer contains 0.1 quality %～5 quality % is 100,000～1,000,000 polyvinylidene dichloride.
4. film or sheet material, its vinylidene chloride analog copolymer composition to each described vinylidene chloride analog copolymer of containing claim 1～3 carries out melt molding 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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103589067A (en) * | 2013-11-15 | 2014-02-19 | 天津工业大学 | Nano composite plastic with scale inhibition effect and preparation method thereof |
| CN105838000A (en) * | 2016-05-19 | 2016-08-10 | 浙江巨化股份有限公司电化厂 | Preparation method of PVDC resin for inner printed film |
| CN106008781A (en) * | 2016-05-19 | 2016-10-12 | 浙江巨化股份有限公司电化厂 | PVDC (polyvinyl dichloride) resin for reverse printing film |
| CN112745605A (en) * | 2019-10-31 | 2021-05-04 | 旭化成株式会社 | Fresh-keeping film |
| CN114058141A (en) * | 2020-08-07 | 2022-02-18 | 旭化成株式会社 | Vinylidene chloride resin preservative film |
| CN117109457A (en) * | 2023-10-25 | 2023-11-24 | 山东潍森新材料科技股份有限公司 | Detection device for uniformity of wall thickness of cellulose casing |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103589067A (en) * | 2013-11-15 | 2014-02-19 | 天津工业大学 | Nano composite plastic with scale inhibition effect and preparation method thereof |
| CN103589067B (en) * | 2013-11-15 | 2016-11-02 | 天津工业大学 | A kind of composite plastic with scale effect and preparation method thereof |
| CN105838000A (en) * | 2016-05-19 | 2016-08-10 | 浙江巨化股份有限公司电化厂 | Preparation method of PVDC resin for inner printed film |
| CN106008781A (en) * | 2016-05-19 | 2016-10-12 | 浙江巨化股份有限公司电化厂 | PVDC (polyvinyl dichloride) resin for reverse printing film |
| CN105838000B (en) * | 2016-05-19 | 2018-06-22 | 浙江巨化股份有限公司电化厂 | A kind of preparation method of inner die PVDC resins |
| CN112745605A (en) * | 2019-10-31 | 2021-05-04 | 旭化成株式会社 | Fresh-keeping film |
| CN114058141A (en) * | 2020-08-07 | 2022-02-18 | 旭化成株式会社 | Vinylidene chloride resin preservative film |
| CN114058141B (en) * | 2020-08-07 | 2022-12-23 | 旭化成株式会社 | Vinylidene chloride resin preservative film |
| CN117109457A (en) * | 2023-10-25 | 2023-11-24 | 山东潍森新材料科技股份有限公司 | Detection device for uniformity of wall thickness of cellulose casing |
| CN117109457B (en) * | 2023-10-25 | 2023-12-26 | 山东潍森新材料科技股份有限公司 | Detection device for uniformity of wall thickness of cellulose casing |
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Effective date of registration: 20160422 Address after: Tokyo, Japan, Japan Patentee after: Asahi Kasei Kogyo K. K. Address before: Tokyo, Japan, Japan Patentee before: Asahi Kasei Chemical K. K. |