CN102993649A - Biaxial stretching polyester film - Google Patents
Biaxial stretching polyester film Download PDFInfo
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- CN102993649A CN102993649A CN2012103304917A CN201210330491A CN102993649A CN 102993649 A CN102993649 A CN 102993649A CN 2012103304917 A CN2012103304917 A CN 2012103304917A CN 201210330491 A CN201210330491 A CN 201210330491A CN 102993649 A CN102993649 A CN 102993649A
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Abstract
The invention provides a biaxial stretching polyester film, which suppresses attached low-polymer substances that cannot be solved by conventional methods and has the tearing linearity. The biaxial stretching polyester film is formed by polybutylene terephthalate containing a polytetramethylene glycol unit and polyethylene glycol terephthalate and has the tearing linearity. The biaxial stretching polyester film is characterized in that on every film surface of 10000m2, the number of attached substances, with a dimension greater than 0.5 mm, derived from low polymers is smaller than 10, and the number of attached substances, with a dimension greater than 0.2 mm but smaller than 0.5 mm, derived from low polymers is smaller than 50.
Description
Technical field
The present invention relates to the biaxial stretching polyester film.Biaxial stretching polyester film of the present invention, at least the length direction of film tear the rectilinearity excellence, and have excellent intensity, thermotolerance, dimensional stability, take dessert, pickle the food such as thing, salty sauce, soup, jam, frozen food, chilled food, pressure pad food as representative, useful as the wrapping material of pharmaceuticals, daily necessities, makeup etc.
Background technology
In the packing of food, pharmaceuticals, groceries, adopt the packing bag that has utilized various plastic films more, be widely used with the plastic film of two-way stretch and can seal without the oriented plastic lamination more than 2 layers or 3 layers and must packing bag.The weather resistance of biaxial stretching polyester film, moisture resistance, mechanical strength, thermotolerance, oil-proofness excellence are so use the biaxial stretching polyester film of the manufacturings such as periosteum method, simultaneously two-way stretch of horizontal method, one by one two-way stretch method of horizontal to be widely used for food product pack field etc.
But, used the packing bag of biaxial stretching polyester film to have the poor problem of Kaifeng property of tearing.For Kaifeng property is improved, the method that notch is set is arranged, but when tearing from notch, the phenomenon that can not tear point-blank usually occurs, sometimes occur not only that content disperses and causes waste, and the dessert such as cooky cracked or content when Kaifeng pollutes the problem of clothes when being liquid.
As the easily openable material of rectilinearity excellence when the tearing film, have the unilateral stretching polyolefin film carried out lamination as the middle layer and material.As this material, biaxial stretching polyester film/unilateral stretching polyolefin film/without 3 press molds layer by layer of drawing polyolefin film is for example arranged, but the middle layer must specially be set, existing problems aspect cost, purposes is limited.
Therefore, as the biaxial stretching polyester film itself being given the linear method of tearing, proposed biaxial stretching polyester film that following mixture is used as main raw material, described mixture is the thermoplastic polyester (a) that mainly is made of terephthalic acid or naphthalic acid of sour composition and presents the mixture (patent documentation 1) of the thermoplastic polyester (b) of Phase Separating Morphology with this polyester.In addition, in patent documentation 1, put down in writing use PET[polyethylene terephthalate] as (a), use by polytetramethylene glycol unit and PBT[polybutylene terephthalate] the polyether polyester segmented copolymer that forms (following, be called modified PBT) conduct (b).
But, use described mixture to compare during with the polyester film of producing the PET monomer as the biaxial stretching polyester film of raw material, oligopolymer is many to the adhesion amount of film, the problem that exists the quality that makes film to descend.
If oligopolymer is attached on the film, occur when then printing that printing ink comes off (イ Application キ order け), point comes off (De ッ ト order け), or the oligopolymer that comes off is attached to become on the gravure roll of printing usefulness and causes that version hides the reason of (version か ぶ り) from film.Wherein, so-called printing ink come off refer to owing to the oligopolymer as foreign matter be attached to film surface occur concavo-convex, thereby around oligopolymer the phenomenon of non-cohesive printing ink etc.In addition, after the printing, be printing ink when adhering to rear oligopolymer and coming off from the film surface, this part does not have printing ink to adhere to yet, and forms printing ink and comes off.Point come off to be described, and makes printing ink be attached to the printing process on film surface with point-like although have, and oligopolymer can hinder and so that printing ink does not adhere to point-like, this situation is called a little came off this moment.Situation about coming off with printing ink similarly can be because the lower generations such as situation that oligopolymer comes off after concavo-convex and non-cohesive printing ink or printing ink occur adhering to.So-called version hides, and is attached to the phenomenon etc. that unnecessary printing ink that the oligopolymer of gravure roll catches is attached to the unnecessary place on film surface when referring to print.
In the past, carried out preventing in a large number the research of the foreign matters such as oligopolymer.For example, can enumerate the method (patent documentation 2) that the surperficial blow air to stretched film blows away oligopolymer, method (patent documentation 3) that bond roll crimping film is removed etc.
But, in above-mentioned in the past scheme, though can suppress to be derived from adhering to foreign matter and can't saying fully of oligopolymer.This is because in production process, exists to attempt the oligopolymer that these previous methods can not solve and adhere to foreign matter.
In addition, also adopted the film volume that utilizes the inspection of foreign substance machine testing to contain to adhere to foreign matter and be not made into the method for product, but compared with the PET film, the oligopolymer amount is many, and is not preferred from the viewpoint of productivity.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-169962 communique
Patent documentation 2: TOHKEMY 2009-72651 communique
Patent documentation 3: TOHKEMY 2010-179276 communique
Summary of the invention
Problem of the present invention provides a kind of biaxial stretching polyester film that suppresses to adopt the indeterminable foreign matter that is derived from oligopolymer of previous methods, improved quality.
The inventor etc. have carried out conscientiously research, and the result has found out the oligopolymer generation melting that is derived from the contained PBT composition of modified PBT, and it fuses with stretched film, perhaps are attached to the oligopolymer that is derived from the PET composition and fuse with stretched film.Therefore, although apparent upper with the PET oligopolymer do not distinguish, can be clearly for the air of previous methods blows pouring, bond roll, can't eliminate.This be because since the oligopolymer of modified PBT and the oligopolymer of PET to compare thermotolerance low, so in the stretch zones in tentering formula drawing machine than the melting of PET oligopolymer elder generation.That is, be the distinctive problem of mixture of modified PBT and PET.
Therefore, thereby the oligopolymer gas concentration the when discoveries such as the inventor stretch by the control tenter machine in the manufacturing of biaxial stretching polyester film has solved above-mentioned problem, and then reaches the present invention.
That is, purport of the present invention is as described below.
(1) a kind of biaxial stretching polyester film, be formed by the polybutylene terephthalate that contains the polytetramethylene glycol unit and polyethylene terephthalate, have and tear linear film, it is characterized in that every 10000m
2Film surface, size for the above foreign matter that is derived from oligopolymer of 0.5mm to adhere to number be below 10, size for more than the 0.2mm and less than the foreign matter that is derived from oligopolymer of 0.5mm to adhere to number be below 50.
(2) a kind of stacked film is that the biaxial stretching polyester film at least 1 layer of use (1) forms.
(3) a kind of easily openable packaging bag is to use the stacked film of (2) and form according to the mode bag of tearing direction that demonstration is torn linear direction and become bag.
(4) a kind of manufacture method of biaxial stretching polyester film is characterized in that, when making the biaxial stretching polyester film of (1), the oligopolymer gas concentration when stretching drawing sheet not in the stretch zones is as 0.2mg/m
3Following mode is controlled, and described not drawing sheet is that the mixture by the polybutylene terephthalate that contains the polytetramethylene glycol unit and polyethylene terephthalate obtains.
According to the present invention, the adhesion amount that can obtain oligopolymer reduces, be difficult for when supplying with printing occuring printing ink come off and put come off, have and tear linear high-quality polyester film.
Embodiment
Below, describe the present invention in detail.
Of the present invention have tear linear biaxial stretching polyester film, it is characterized in that every 10000m
2Film surface, size for the above foreign matter that is derived from oligopolymer of 0.5mm to adhere to number be below 10, size for more than the 0.2mm and less than the foreign matter that is derived from oligopolymer of 0.5mm to adhere to number be below 50.For the method for counting of the foreign matter that is derived from oligopolymer, in the back narration.
The foreign matter that is derived from oligopolymer is that printing adds fatal shortcoming in man-hour, so wish the least possible.That is, every 10000m
2Film surface, size is preferably below 5 for the number that adheres to of the above foreign matter that is derived from oligopolymer of 0.5mm is necessary for below 10, more preferably below 2, foreign matter that most preferably should size does not exist.
In addition, be to adhere to number, every 10000m more than the 2mm and less than the foreign matter that is derived from oligopolymer of 5mm for size
2Film surface, be necessary for below 50, be preferably below 30, most preferably be below 15.
Should illustrate, if be derived from the foreign matter of oligopolymer be diameter less than the size of 0.2mm, then add in printing and can not occur that printing ink comes off, point such as comes off at the problem man-hour.
In the present invention, importantly the stage before the thermal treatment zone in the drawing machines such as tentering formula drawing machine, reduce as far as possible the chance that stretched film contacts with the oligopolymer that is derived from modified PBT of generation in the drawing machine.Therefore, stretch zones that need to be in drawing machine will be reduced to below the certain value as the oligopolymer gas concentration of the lower molecular weight thing of polyester.Particularly, must make the oligopolymer gas concentration is 0.2mg/m
3Below, be preferably 0.1mg/m
3Below, most preferably be 0.05mg/m
3Below.
If the oligopolymer gas concentration in the stretch zones in the drawing machine is greater than 0.2mg/m
3, then becoming the environment that easy generation is derived from the oligopolymer of modified PBT, the printing ink that size also becomes greatly thereby the generation printing adds man-hour easily comes off, point comes off.
The lower limit of oligopolymer gas concentration is not particularly limited, and there is no need to be reduced to 0.03mg/m
3Below.Even this is because that the oligopolymer gas concentration is reduced to is lower, also few on the impact of the reduction of the oligopolymer that is derived from modified PBT, in addition, technical very difficult mensuration is lower than this concentration.
In the present invention, by measuring the oligopolymer gas concentration in the stretch zones in the highest drawing machine of oligopolymer gas concentration and be controlled in the specialized range in whole operations of biaxial stretching polyester film manufacturing, the result can control the oligopolymer amount that is attached on the film.
In the present invention, method for reducing the oligopolymer gas concentration in the stretch zones in the drawing machine is not particularly limited, as an example, situation to the mode of production of following biaxial stretching film describes, namely extrude in the operation at molten polymer and obtain unstretching film by the T mould, in roll-type longitudinal stretching operation, with its longitudinal stretching, then in tenter machine cross directional stretch operation, carry out cross directional stretch.In the production process of above-mentioned biaxial stretching film, for 3 operations that molten polymer is extruded operation, roll-type longitudinal stretching operation and tentering formula cross directional stretch operation, preferably take for the device that reduces the oligopolymer γ-ray emission.Should illustrate, in the present invention, as bidirectional extending method, can be in the one by one two-way stretch method of utilizing roller and tenter machine to carry out, simultaneously two-way stretch of the tenter machine method any.
Extrude in the operation the preferred resin of having implemented the favourable solid state polymerization of the inhibition of oligopolymer γ-ray emission that uses at molten polymer.In addition, because the high-temperature fusion polymkeric substance of extruding from the T mould produces oligopolymer easily, so preferably near the T mould, vapor pipe is set.
In roll-type longitudinal stretching operation since with the unstretching film temperature adjustment to more than the Tg, pollute easily roller so the oligopolymer in the film oozes out.Therefore, preferred arrange make bond roll and draw roll applying etc. and in production the device of cleaning roller.In addition, the oligopolymer of distillation is deposited in the top of longitudinal stretching operation easily, is effective so at the top vapor pipe is set.
In tenter machine cross directional stretch operation, even the arbitrary place in tenter machine produces oligopolymer, also can be attached on the tenter clip and be transported to the tenter machine entrance, if the air-flow perhaps in the tenter machine is the updrift side of film then oligopolymer flows into the tenter machine entrance, thereby there is the danger of the film surface attachment oligopolymer enter tenter machine cross directional stretch operation, the minimizing oligopolymer that has living space that therefore need to be in tenter machine.In tenter machine, because from film, distil easily at the thermal treatment zone oligopolymer, so expect carrying out air feed and exhaust energetically and making method that the oligopolymer gas concentration descends, make platinum catalyst make the method for oligopolymer oxygenolysis by the circulating air system in thermal treatment zone.In addition, in order to prevent the pollution of tenter clip, effective ways are that surface temperature control with tenter clip is more than 90 ℃.
(tearing the rectilinearity biaxial stretching film)
The PET that uses in the film of the present invention be utilize known method for making, be after the direct esterification of the transesterification reaction method of dimethyl terephthalate (DMT) and ethylene glycol or terephthalic acid and ethylene glycol obtains oligopolymer, carry out melt polymerization or further carry out solid state polymerization obtaining, can other composition of copolymerization in the scope of not damaging effect of the present invention.
As other copolymer composition, can enumerate m-phthalic acid, phthalic acid, 2, the 6-naphthalic acid, 5-sodium sulfo isophthalate, succsinic acid, hexanodioic acid, sebacic acid, dodecanedioic acid, dimeracid, maleic anhydride, toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid, the dicarboxylic acid such as cyclohexane dicarboxylic acid, 4-HBA, 6-caprolactone, the hydroxycarboxylic acids such as lactic acid, 1, ammediol, 1,6-hexylene glycol, the dibasic alcohol such as cyclohexanedimethanol, trimellitic acid, trimesic acid, pyromellitic acid, TriMethylolPropane(TMP), glycerine, the polyfunctional compounds such as tetramethylolmethane.
The molecular weight of the polytetramethylene glycol that uses among the present invention (below, be called PTMG) unit is 600～4000 scopes preferably, are more preferably 1000～3000, and further preferably 1000～2000.Less than 600 o'clock, rectilinearity was torn in very difficult performance at molecular weight, and greater than 4000 o'clock, the performances such as physical strength, dimensional stability, mist degree descend sometimes.
In film of the present invention, from tearing the balance of rectilinearity and physical strength etc., take the integral body of modified PBT as 100 quality %, the content that consists of the PTMG unit of modified PBT is preferably 5～20 quality %, more preferably 10～20 quality %, more preferably 10～15 quality %.
In film of the present invention, the blending ratio of PET and modified PBT is preferably PET/ modified PBT=70/30～95/5(mass ratio from the balance of tearing rectilinearity and physical strength), 80/20～90/10(mass ratio more preferably), 85/15～90/10(mass ratio more preferably).
The modified PBT that uses among the present invention can add PTMG and carry out polycondensation and obtain in the polymerization process of PBT, as easier method, also can obtain by in forcing machine PBT and PTMG being carried out melting mixing.
Should illustrate, in material resin of the present invention, as long as in the scope of not damaging effect of the present invention, can mix other polymkeric substance such as PEN, poly terephthalic acid cyclohexanedimethanoester ester (polycyclohexylenedimethylene terephthalate).
When making film of the present invention, at first, for example the mixture of modified PBT and PET is put in the forcing machine, behind the heating and melting, be extruded into sheet from the nib of T mould, make not drawing sheet.Adopting static to apply casting method (quiet Electricity seal adds キ ャ ス ト method) etc. makes the sheet extruded from the nib of T mould with drum cooler driving fit ground coiling and cools off, then 90～140 ℃ of temperature, stretch with 3.0～5.0 times multiplying power separately in direction in length and breadth, further heat-treat 210～245 ℃ of temperature, make biaxial stretching film.
During less than 90 ℃, sometimes can not obtain the stretched film of homogeneous at draft temperature, greater than 140 ℃ the time, promote the crystallization of PET, sometimes transparent variation.During less than 3.0 times, the stretching film strength that obtains is low at stretching ratio, produces easily pin hole when making bag, and during greater than 5.0 times, difficult sometimes stretches at stretching ratio.In addition, if thermal treatment temp is lower than 210 ℃, it is large that the percent thermal shrinkage of the stretched film that then obtains becomes, behind the bag sometimes bag deform, in addition, if the fusing of film greater than 245 ℃, then occurs in thermal treatment temp sometimes.
The biaxial stretching polyester film of the present invention that as above obtains is torn rectilinearity in length direction (MD) performance at least.This biaxial stretching polyester film also can use as stacked film with other film-stack.In addition, can use this stacked film and tear the mode bag of tearing direction that linear direction becomes bag according to demonstration, thereby make easily openable packaging bag.
In addition, also can implement the surface treatment that Corona discharge Treatment, surface hardening processing, plating, painted processing or various coating are processed to biaxial stretching polyester film of the present invention.
[embodiment]
The evaluation method of embodiment and comparative example is as described below.
(being derived from the measuring method of the foreign matter of oligopolymer)
Make stretched film pass through the optical foreign matter inspection units, check that the film width is that 1m, film length direction are the scope of 10000m.Be that foreign matter more than the 0.1mm is all as sample with the size that detects.The area mean diameter that the size of foreign matter is calculated for this optical foreign matter inspection units.In the foreign matter that obtains, white and judge it is the oligopolymer that is derived from PBT for the material of powdery is counted it as the foreign matter that is derived from oligopolymer.
(oligopolymer concentration measurement method gas)
The oligopolymer gas concentration measuring of the stretch zones in the tenter machine carries out as shown below.
(1) perforate on the wall of the stretch zones in tenter machine penetrates stainless steel tube therein.One end of this stainless steel tube is arranged near the air feed port of hot air circulating system, and the other end purge of gas bottle (Muenck formula) outer with being arranged on tenter machine is connected.Fill the ethylene glycol for dissolving oligopolymer composition in the purge of gas bottle.
(2) utilize the off-gas pump with under meter to make air pass through purge of gas bottle certain hour.
(3) take off the purge of gas bottle, spent glycol purged with purge gas bottle and stainless steel tube are inner.
(4) ethylene glycol that washes out and the ethylene glycol in the gas clean bottles are offered the UV spectrophotometer and carry out absorbance measurement.
(5) use the calibration curve that makes in advance, the absorbancy of measuring is converted into the oligopolymer gas concentration.
(tearing linear evaluation method)
Cut-out length direction (MD) is that 205mm, width (TD) are the strip diaphragm of 40mm from biaxial stretching film, and the central part of a side minor face of 10 these diaphragms of making is with the sample of the switch-in part of long 5mm.Then, tear with hand along MD from switch-in part, with the tear propogation end arrive with the sample radical of the relative minor face in the limit of switch-in part as the linear evaluation of estimate of tearing of MD, evaluation of estimate is qualified more than 8.
Should illustrate, to left part, central part and the right part of the film that batches after stretching thermal treatment implementation evaluation respectively.Show the result in table 1.
(evaluation method of printing adaptability)
Implement 10000m at biaxial stretching film with white ink (Fine Star processed R641 AT is white in Toyo Ink company)
2Behind the field printing, by the optical foreign matter inspection units, carry out the inspection that printing ink comes off.The number that printing ink is come off is shown in table 1.
Embodiment 1
Add dimethyl terephthalate (DMT) 194 mass parts, 1,4-butyleneglycol 108 mass parts and tetrabutyl titanate 80ppm(are converted into titanium metal with respect to the numerical value of the quality of polymkeric substance), from 150 ℃ heat to 210 ℃ one side and carry out 2.5 hour transesterification reaction on one side.Transesterification reaction resultant 90 mass parts that obtain are transferred in the polymerization tank, after adding tetrabutyl titanate 40ppm, add PTMG 10 mass parts of molecular weight 1100, begin decompression, finally under the decompression of 1hPa, from 210 ℃ heat up final under 245 ℃ temperature melt polymerization 2 hours, obtain the modified PBT of relative viscosity 1.60.
Adopt forcing machine that PET and modified PBT are mixed with mass ratio 85/15 simple thin slice and must the material melting after, extrude from the T mould, apply method with static and make its driving fit carry out quenching at the drum cooler with surface temperature temperature adjustment to 20 ℃, obtain the unstretching film of thick 190 μ m.At this moment, between T mould and drum cooler, gas barrier is set, extracts the gas that produces out.
Then, with the preheat roll group of temperature adjustment to 90 ℃ with the unstretching film preheating after, changing the ground longitudinal stretching in the draw roll chien shih circumferential speed of temperature adjustment to 90 ℃ is 3.5 times, obtains the longitudinal stretching film.At this moment, preheat roll, draw roll utilize thoroughly wiping cleaning of alcohol, and the oligopolymer that is attached on the roller is removed fully.In order to remove the oligopolymer of separating out in the mill on roller, bond roll and preheat roll, draw roll are fitted.In addition, in order to prevent the whereabouts of the oligopolymer that cooling forms in the air, in the sky of longitudinal tensile fixture vapor pipe is set.
Then, the longitudinal stretching film being imported in the tentering formula drawing machine, is 4.5 times at 120 ℃ of cross directional stretchs of draft temperature, and then, the relaxation rate that makes transverse direction is 3%, implements thermal treatment at 235 ℃, obtains the stretched film of thick 12 μ m.At this moment, increase the amount to gas and exhaust of thermal treatment zone, the tenter clip surface utilizes thoroughly wiping cleaning of alcohol, and the oligopolymer that is attached on the tenter clip is removed fully.In addition, the surface temperature control of tenter clip more than 90 ℃, is prevented separating out of oligopolymer.The evaluation result of the biaxial stretching polyester film that obtains is shown in table 1.
Embodiment 2
In the circulating air system of tentering formula drawing machine, platinum catalyst is set.Except this point, obtain similarly to Example 2 the double orientation polyester film.The evaluation result of the biaxial stretching polyester film that obtains is shown in table 1.
Comparative example 1
Compare with embodiment 1, do not implement the applying of exhaust, cancellation preheat roll and draw roll and bond roll between T mould and the drum cooler, do not move the vapor pipe in the sky of longitudinal tensile fixture, do not control especially the surface temperature of tenter clip, do not increase the supply and exhaust amount of the thermal treatment zone of tentering formula drawing machine.Except this point, obtain similarly to Example 1 the double orientation polyester film.
The evaluation result of the biaxial stretching polyester film that obtains is shown in table 1.
Comparative example 2
Compare with comparative example 1, the unstretching film that enters before the tentering formula drawing machine is scattered the oligopolymer that obtains in advance, deliberately pollute with oligopolymer thus.Except this point, similarly obtain the double orientation polyester film with comparative example 1.
The evaluation of the biaxial stretching polyester film that obtains, the result since foreign matter to detect number many, so be that 1m, film length direction are that the scope of 5000m is estimated to the film width, be converted into every 10000m
2The foreign matter number, show the result in table 1.
Comparative example 3
On the basis that similarly operates with comparative example 1, further in the tenter machine outlet film surface is blown and drench airflow and blow away foreign matter, thereby obtain the double orientation polyester film.
The evaluation result of the biaxial stretching polyester film that obtains is shown in table 1.
Reference example
Raw material as the biaxial stretching polyester film only uses PET.Except this point, similarly obtain the double orientation polyester film with comparative example 3.
The evaluation result of the two-way stretch polyethylene terephthalate film that obtains is shown in table 1.
In each embodiment of table 1, satisfy the scope of stipulating among the present invention by the number that adheres to that makes the foreign matter that is derived from oligopolymer, can make have good printing adaptability, clean and have and tear linear biaxial stretching polyester film.
Relative therewith, the adhesion amount of oligopolymer is many in the comparative example 1～2, also occur after the printing printing ink come off, the point come off.
In addition, although it is suppressed to be derived from the amount of foreign matter of oligopolymer in the comparative example 3, not exclusively.
In the reference example, because do not contain the PBT oligopolymer, so with method was very effective in the past, the oligopolymer adhesion amount is few.
Claims (4)
1. biaxial stretching polyester film, be formed by the polybutylene terephthalate that contains the polytetramethylene glycol unit and polyethylene terephthalate, have and tear linear film, it is characterized in that every 10000m
2Film surface, size for the above foreign matter that is derived from oligopolymer of 0.5mm to adhere to number be below 10, size for more than the 0.2mm and less than the foreign matter that is derived from oligopolymer of 0.5mm to adhere to number be below 50.
2. a stacked film requires 1 described biaxial stretching polyester film to form at least 1 layer of right to use.
3. easily openable packaging bag is that right to use requires 2 described stacked films and forms according to the mode bag of tearing direction that demonstration is torn linear direction and become bag.
4. the manufacture method of a biaxial stretching polyester film is characterized in that, when making biaxial stretching polyester film claimed in claim 1, the oligopolymer gas concentration when stretching drawing sheet not in the stretch zones is as 0.2mg/m
3Following mode is controlled, and described not drawing sheet is that the mixture by the polybutylene terephthalate that contains the polytetramethylene glycol unit and polyethylene terephthalate obtains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011197195A JP2013056509A (en) | 2011-09-09 | 2011-09-09 | Linearly-tearable biaxially-oriented polyester film that reduces oligomer foreign matter to be deposited thereon |
| JP2011-197195 | 2011-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102993649A true CN102993649A (en) | 2013-03-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103304917A Pending CN102993649A (en) | 2011-09-09 | 2012-09-07 | Biaxial stretching polyester film |
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| JP (1) | JP2013056509A (en) |
| CN (1) | CN102993649A (en) |
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| CN105324434A (en) * | 2013-07-01 | 2016-02-10 | 株式会社钟化 | High thermal conductivity thermoplastic resin composition with excellent injection moldability |
| CN106142785A (en) * | 2016-06-29 | 2016-11-23 | 安徽国风塑业股份有限公司 | A kind of dry plate composite bidirectional stretching mylar and preparation method thereof |
| CN108699207A (en) * | 2016-02-22 | 2018-10-23 | 巴斯夫欧洲公司 | The method for preparing diblock copolymer |
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| JP5399807B2 (en) * | 2009-08-07 | 2014-01-29 | ユニチカ株式会社 | Biaxially stretched plastic film manufacturing method and film manufacturing apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105324434A (en) * | 2013-07-01 | 2016-02-10 | 株式会社钟化 | High thermal conductivity thermoplastic resin composition with excellent injection moldability |
| US10030138B2 (en) | 2013-07-01 | 2018-07-24 | Kaneka Corporation | High thermal conductivity thermoplastic resin composition with excellent injection moldability |
| CN108699207A (en) * | 2016-02-22 | 2018-10-23 | 巴斯夫欧洲公司 | The method for preparing diblock copolymer |
| CN108699207B (en) * | 2016-02-22 | 2021-10-01 | 巴斯夫欧洲公司 | Process for preparing diblock copolymers |
| CN106142785A (en) * | 2016-06-29 | 2016-11-23 | 安徽国风塑业股份有限公司 | A kind of dry plate composite bidirectional stretching mylar and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP2013056509A (en) | 2013-03-28 |
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