CN1193058C - Saturated polyester with good heat resistance and imporosity used for plastic container and its preparing method - Google Patents
Saturated polyester with good heat resistance and imporosity used for plastic container and its preparing method Download PDFInfo
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- CN1193058C CN1193058C CNB021505519A CN02150551A CN1193058C CN 1193058 C CN1193058 C CN 1193058C CN B021505519 A CNB021505519 A CN B021505519A CN 02150551 A CN02150551 A CN 02150551A CN 1193058 C CN1193058 C CN 1193058C
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Abstract
The present invention discloses saturated polyester widely used for various molding containers, such as plastic bottles, plastic cups, etc. and a method for preparing the saturated polyester used for plastic containers. Compared with conventional saturated polyester, the saturated polyester of the present invention has good heat resistance and high tightness. The saturated polyester used for plastic containers is prepared by that nanometer silicon dioxide particles are added during transesterification or esterification period, and polycondensation is carried out by using a DMT method or TPA method. As the nanometer silicon dioxide particles exist in polymer chains, the saturated polyester has favorable heat resistance, high tightness and good physical performance, the saturated polyester of the present invention can be used for packing containers of fruit beverages, beer, green tea products, rice beverages, etc.
Description
Technical field
The present invention relates to be widely used as the saturated polyester of the material of various mold containers such as Plastic Bottle, plastic cup etc., relate more specifically to by in polymer chain, existing nano-size silica particles to have excellent heat resistance and high airproof saturated polyester and preparing the method for this saturated polyester.
Background technology
Saturated polyester is the linear thermoplastic's polymkeric substance that comprises ester bond in main chain as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).Because saturated polyester has dimensional stability, weathering resistance and surface smoothness advantage, and has high transparent and glossy appearance, it has been widely used as the material of various moulded products such as synthon, film, container, shell etc.
Yet the shortcoming that saturated polyester exists is, because it presents low glass transition temp (Tg), bad thermotolerance and to the perviousness of some gas, so it can not be used as the packaging vessel of fruit beverage, beer, green tea product, rice-drink etc.
For solving these shortcomings, the mixed polymer of PEN (PEN) resin and polyethylene terephthalate and PEN has been proposed.These products use at present.Yet therefore the price of PEN (PEN) resin is disadvantageous than polyethylene terephthalate height economically.In addition, reclaim the PEN difficulty.In addition, open the Japanese Patent spy and disclose a kind of improvement thermotolerance, the transparency and airproof method among the No.1997-290457.According to the method, by during PET bottle molding, carrying out the crystalline orientation of biaxial stretch-formed reinforced polyester.Yet some problems of this method are that the crystalline orientation degree can not be increased to more than 40%, and it can not use in being higher than under 92 ℃ PET bottle that beverage packed into the time.In addition, when loading at low temperatures, productivity reduces.
Summary of the invention
Therefore, the present invention has considered the problems referred to above, therefore an object of the present invention is to provide a kind of saturated polyester that is used for plastic containers, this polyester has excellent heat resistance and high gas tightness by nano-size silica particles being dispersed in thus the crystalline orientation degree is increased in the polyester more than 40%.
What another object of the present invention provided that a kind of preparation is used for plastic containers has excellent heat resistance and a high airproof saturated polyester.
According to the present invention, a kind of saturated polyester that comprises nano-size silica particles is provided, this nano-size silica particles has median size 3 to 100nm, and its amount is 20ppm to 10wt%, by the weight of saturated polyester.
Saturated polyester of the present invention then prepares the parent material polycondensation by add nano-size silica particles during transesterification or esterification.
Embodiment
Usually, saturated polyester is by aromatic dicarboxylic acid or become ester derivative and ethylene glycol is produced as initial substance.If necessary, can add other initial substance.The example that is used for aromatic dicarboxylic acid of the present invention comprises m-phthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acids, phthalic acid, hexanodioic acid, sebacic acid and its mixture.As the example that is used for glycol of the present invention, can be with minor amounts of propylene glycol, butyleneglycol, 1,4-cyclohexanedimethanol, neopentyl glycol etc. add in the ethylene glycol.
If necessary, saturated polyester also can comprise additive such as thermo-stabilizer, antiblocking agent, oxidation inhibitor, static inhibitor, UV absorption agent etc.
According to the present invention, during the preparation saturated polyester, add nano-size silica particles.At this moment, nano-size silica particles during reaction must keep constant dimensions.
Being used for nano-size silica particles of the present invention obtains as follows: at first with silication sodium (Na
4Si) form water glass with the water reaction.Subsequently water glass is passed through cation exchange resin column.Remove the sodium oxide with cationic exchange resin adsorption, obtain the fine silica particle thus.So the fine silica particle that obtains has average particle size particle size 0.5nm to 1.0nm.At last, for obtaining to have the nano-size silica particles of desired size, crystalline growth fine silica particle.
So the nano-size silica particles that obtains is presented at dispersiveness good in the water.Yet, because (because of the lower boiling of the water) agglomeration fast when dehydration of this nano-size silica particles, so they will be stored in high boiling liquid such as ethylene glycol or the butyleneglycol.Especially, for the side reaction of reduction and saturated polyester to greatest extent, preferably silica dioxide granule is scattered in the ethylene glycol (EG).Can only use nano-size silica particles, maybe the nano-size silica particles with two or more types of different median sizes can be mixed mutually with identical median size.For formation contains the slurry of nano-size silica particles, can only use a kind of solvent, maybe two or more solvents can be mixed mutually.
The amount of nano-size silica particles is preferably 20ppm to 10wt%, and more preferably 50ppm to 6wt% is by the weight of saturated polyester.When the amount of nano-size silica particles was lower than 20ppm, the physicals of saturated polyester of the present invention was unsatisfactory.When the amount of nano-size silica particles surpasses 10wt%, can not obtain the good dispersion of nano-size silica particles in polymkeric substance, and because the transparent step-down of particle agglomeration saturated polyester.According to the present invention, silicon-dioxide has median size 3 to 100nm.When the median size of silica dioxide granule during greater than 100nm, transparent variation.When the median size of silica dioxide granule is lower than 3nm, because of the dispersiveness of the surface tension between the particle and transparent poor.
Be to strengthen the tone of resin, P contained compound such as trimethyl phosphite 99 (TMP), triethyl phosphate (TEP), triphenylphosphate (TPP) can be added with nano-scale silicon-dioxide.Consider the equivalent ratio with metal ion, regulate the amount of the P contained compound that adds, so that the phosphorus content in the polymkeric substance is 0.01 to 0.1wt%, by the weight of polymkeric substance.
As mentioned above, be dispersing nanometer size silica dioxide granule better, preferably these particles be scattered in water, ethylene glycol, butyleneglycol or its mixture in advance and form slurry.The concentration of nano-size silica particles in slurry is preferably 3 to 30wt%, and more preferably 5 to 20wt%, by slurry weight.When the concentration of nano-size silica particles in slurry is lower than 3wt%, add too many slurry, so cause side reaction.When the concentration of nano-size silica particles in slurry was higher than 30wt%, the dispersed variation of particulate also formed a large amount of coarse particless.Be the dispersiveness of enhanced granule, very little particle reduces slurry concentration.When particle size is big, can increase the concentration of particle in slurry.
When adding contains the slurry of nano-size silica particles during synthesizing polyester, be noted that agglomeration mutually of nano-size silica particles.According to the present invention, ethylene glycol (EG) is preferably 1.8 to 2.5 with the mol ratio (E/T) of dimethyl terephthalate (DMT) (DMT), and ethylene glycol (EG) is preferably 1.3 to 2.5 with the mol ratio (E/T) of terephthalic acid (TPA).There is not particular restriction for the method that nano-size silica particles is scattered in the polyester better, but because the slurry of these particles in water can cause side reaction in the DMT method, therefore preferably with these particles dispersed in ethylene glycol (EG) or butyleneglycol (BD).In TPA (terephthalic acid) method,, when reacting, do not have problems although slurry is moisture.Yet, consider that the dispersed DMT method of particulate is better than the TPA method.
The description of preferred embodiment
The present invention will illustrate in greater detail with reference to the following examples and comparative example.Provide these embodiment only to be used for illustration purpose, and do not think to limit the scope of the invention.
Embodiment 1
(DMT0 and 64 weight part ethylene glycol (EG) drop in the reactor, and the dispersion in 3 weight part ethylene glycol under agitation adds wherein with 0.03 weight part ANTIMONY TRIOXIDE SB 203 99.8 PCT and 0.06 weight part, four hydration manganous acetates with 100 weight part dimethyl terephthalate (DMT).This mixture heating up to 130 to 230 ℃ of temperature, and is carried out transesterification 4 hours to form BHT (B-1).The slurry of silica dioxide granule in ethylene glycol of the median size 50nm of 10wt% passed through through the strainer of size of mesh 0.5 μ m, obtain slurry (S-1).When the temperature of (B-1) rises to about 235 ℃, the diluent of 0.03 weight part trishydroxymethyl phosphoric acid ester (TMP) in 2 weight part ethylene glycol dropped in the reactor, then to wherein slowly adding 20 weight part slurries (S-1).This BHT is passed through through the strainer of size of mesh 3 μ m.With filtrate at 50 minutes internal heating to 235 to 285 ℃ of temperature, carry out polycondensation 3 hours with preparation polymkeric substance (P-1-1), this polymkeric substance has the performance that provides in the following table 1.This polymkeric substance is cut into sheet stock.Add the sheet stock of cutting in the general solid state polymerization reactor and carry out solid-state polymerization with preparation polymkeric substance (P-1-2), this polymkeric substance has the performance that following table 1 provides.Use the heat-resisting PET bottle blow moulding machine, make the heat-resisting bottle of 500cc (P-1-3) by (P-1-2).
Embodiment 2
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 1, different is that 1 weight part nano-sized particles slurry (S-1) is added among the BHT down for 235 ℃ in temperature, and carries out polycondensation.
Embodiment 3
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 1, different is replaces the silica dioxide granule of median size 50nm to form slurry (S-1) silica dioxide granule of median size 15nm.
Embodiment 4
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 1, different is that the 1 weight part nano-sized particles slurry (S-1) that will form in embodiment 3 adds among the BHT down for 235 ℃ in temperature, and carries out polycondensation.
Embodiment 5
100 weight part terephthalic acids and 75 weight part ethylene glycol are dropped in the reactor.This mixture heating up to 30 to 230 ℃ of temperature, and is carried out esterification 6 hours to form BHT.With 175 weight part EG and TPA (mol ratio: slurry 2.0) added BHT in 2 hours after, this is reflected at keeps further carrying out 1.5 hours under 230 ℃ of the temperature of reaction.175 weight part BHT are passed through through the strainer of size of mesh 3.0 μ m, and filtrate is transferred in the polycondensation reactor.To add by the phosphoric acid of polymer weight 0.02wt% in the polycondensation reactor, will add wherein by the diluent of ANTIMONY TRIOXIDE SB 203 99.8 PCT in a small amount of ethylene glycol of polymer weight 0.015wt% then.The silica dioxide granule of median size 15nm is scattered in the 10wt% ethylene glycol forms slurry.The strainer of this slurry through size of mesh 0.5 μ m passed through, form slurry (S-2).This slurry of 20 weight parts is added down among the BHT 230 ℃ of temperature, when BHT at 50 minutes internal heating to 230 to 285 ℃ of temperature, carry out polycondensation 3 hours with the preparation polymkeric substance, this polymkeric substance has the performance that provides in the following table 1.This polymkeric substance is cut into sheet stock (P-5-1).Add the sheet stock of cutting in the general solid state polymerization reactor and carry out solid-state polymerization with preparation polymkeric substance (P-5-2), this polymkeric substance has the performance that following table 1 provides.Use the heat-resisting PET bottle blow moulding machine, make the heat-resisting bottle of 500cc (P-5-3) by (P-5-2).
Embodiment 6
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 5, different is that 1 weight part nano-sized particles slurry (S-2) is added among the BHT down for 235 ℃ in temperature, and carries out polycondensation.
Embodiment 7
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 5, different is replaces the silica dioxide granule of median size 15nm to be used to form slurry (S-2) silica dioxide granule of median size 3nm.
Embodiment 8
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 7, different is that the 0.05 weight part nano-sized particles slurry (S-2) that will form in embodiment 7 adds among the BHT down for 235 ℃ in temperature, and carries out polycondensation.
Embodiment 9
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 5, the silica dioxide granule that different is contains median size 100nm with 50 weight parts replaces the slurry (S-2) of the silica dioxide granule of median size 15nm, adds among the BHT down and carries out polycondensation 230 ℃ of temperature.
Embodiment 10
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 5, the silica dioxide granule that different is contains median size 100nm with 0.05 weight part replaces the slurry (S-2) of the silica dioxide granule of median size 15nm, adds among the BHT down and carries out polycondensation 230 ℃ of temperature.
Comparative example 1
100 weight part terephthalic acids and 75 weight part ethylene glycol are dropped in the reactor.This mixture under agitation is heated to 230 ℃ of temperature, and carries out esterification 6 hours to form BHT.With 175 weight part EG and TPA (mol ratio: slurry 2.0) added BHT in 2 hours after, this is reflected at keeps further carrying out 1.5 hours under 230 ℃ of the temperature of reaction.175 weight part BHT are passed through through the strainer of size of mesh 3.0 μ m, and filtrate is transferred in the polycondensation reactor.To add by the phosphoric acid of polymer weight 0.02wt% in the polycondensation reactor, will add wherein by the diluent of ANTIMONY TRIOXIDE SB 203 99.8 PCT in a small amount of ethylene glycol of polymer weight 0.015wt% then.When BHT at 50 minutes internal heating to 230 to 285 ℃ of temperature, carry out polycondensation 3 hours with preparation polymkeric substance (P-11-1), this polymkeric substance has the performance that provides in the following table 1.This polymkeric substance is cut into sheet stock.Add the sheet stock of cutting in the general solid state polymerization reactor and carry out solid-state polymerization with preparation polymkeric substance (P-11-2), this polymkeric substance has the performance that following table 1 provides.Use the heat-resisting PET bottle blow moulding machine, make the heat-resisting bottle of 500cc (P-11-3) by (P-11-2).
Comparative example 2
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 5, different is replaces the silica dioxide granule of median size 15nm to be used to form slurry (S-2) silica dioxide granule of median size 20nm.
Comparative example 3
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with comparative example 2, the silica dioxide granule that different is contains median size 200nm with 1 weight part replaces the slurry (S-2) of the silica dioxide granule of median size 20nm, adds among the BHT down and carries out polycondensation 230 ℃ of temperature.
Comparative example 4
Prepare polymkeric substance and heat-resisting PET bottle by the mode identical with embodiment 5, the silicon-dioxide that different is with median size 100nm by polymer weight, is used to form slurry (S-2) with concentration 100ppm.In this embodiment.Because therefore the silica dioxide granule in the polymkeric substance can not carry out solid-state polymerization to have the mutual agglomeration of the about 3mm impurity of size form.
The polymkeric substance of making in embodiment and the comparative example and the physicals of heat-resisting PET bottle provide in table 1.
Table 1
| Saturated polyester | Physicals | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Testing method |
| Liquid polymerization | IV | N | 0.627 | 0.633 | 0.630 | 0.630 | 0.627 | 0.630 | 0.620 | ASTM- D-4603 |
| Color L | - | 64.1 | 59.1 | 62.1 | 57.4 | 59.3 | 54.6 | 56.1 | JIS-Z- 8730 | |
| Color b | - | -1.4 | -2.2 | -2.4 | -2.4 | -3.9 | -4.4 | -2.4 | JIS-Z- 8730 | |
| DSC(Tm) | ℃ | 254.3 | 252.4 | 252.4 | 251.8 | 247.6 | 248.9 | 250.2 | ASTM- D-3418 | |
| -COOH | eq/ton | 13 | 17 | 14 | 19 | 17 | 22 | 23 | N/25Na OH titration | |
| The mist value | ％ | 6.4 | 1.9 | 3.9 | 1.2 | 4.2 | 1.5 | 2.9 | ASTM- D-1003 | |
| SiO 2Particle diameter | nm | 50 | 50 | 15 | 15 | 15 | 15 | 3 | ||
| SiO 2Content | Weight % | 2.0 | 0.1 | 2.0 | 0.1 | 2.0 | 0.1 | 10.0 | EPA 200.7 | |
| Solid-state polymerization | IV | n | 0.78 | 0.77 | 0.79 | 0.78 | 0.78 | 0.78 | 0.80 | ASTM- D-4603 |
| Color L | - | 86.9 | 87.1 | 87.9 | 87.3 | 87.7 | 87.4 | 86.5 | JIS-Z- 8730 | |
| Color b | - | -0.6 | -1.1 | -1.6 | -1.5 | -3.0 | -3.4 | -1.5 | JIS-Z- 8730 | |
| Degree of crystallinity | ％ | 54.1 | 53.6 | 54.5 | 53.9 | 54.7 | 54.1 | 53.8 | ASTM- D-1505 | |
| Heat-resisting bottle | Thermotolerance | ℃ | 98 | 91 | 100 | 98 | 100 | 98 | 100 | |
| O 2Gas tightness | Cc/ filling/sky | 0.038 | 0.045 | 0.016 | 0.038 | 0.018 | 0.037 | 0.010 | ||
| The mist value | - | 15.1 | 8.4 | 10.2 | 7.4 | 10.6 | 7.9 | 8.5 | ||
| Minimum degree of crystallinity | ％ | 41 | 38 | 44 | 42 | 44 | 42 | 45 | ASTM- D-1505 |
Table 1 (continuing)
| Saturated polyester | Physicals | Unit | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Testing method |
| Liquid polymerization | IV | n | 0.637 | 0.633 | 0.630 | 0.630 | 0.627 | 0.630 | 0.630 | ASTM-D- 4603 |
| Color L | - | 54.1 | 69.1 | 69.1 | 57.1 | 75.4 | 60.6 | 57.7 | JIS-Z- 8730 | |
| Color b | - | -2.4 | -2.2 | -2.4 | -2.4 | -3.9 | -4.4 | -2.6 | JIS-Z- 8730 | |
| DSC (Tm) | ℃ | 250.3 | 250.4 | 250.6 | 250.2 | 247.6 | 248.9 | 250.2 | ASTM-D- 3418 | |
| -COOH | eq /ton | 23 | 27 | 23 | 29 | 17 | 22 | 30 | The N/25NaOH titration | |
| The mist value | ％ | 0.8 | 10.9 | 1.6 | 0.7 | 81.0 | 15.0 | 55.0 | ASTM-D- 1003 | |
| SiO 2Particle diameter | nm | 3 | 100 | 100 | - | 200 | 200 | 2 | ||
| SiO 2Content | Weight % | 0.005 | 5.0 | 0.005 | 0.0 | 5.0 | 0.01 | 0.01 | EPA 200.7 | |
| Solid-state polymerization | IV | N | 0.80 | 0.77 | 0.79 | 0.80 | 0.78 | 0.78 | - | ASTM-D- 4603 |
| Color L | - | 86.9 | 87.6 | 87.3 | 86.5 | 89.7 | 87.7 | - | JIS-Z- 8730 | |
| Color b | - | -1.6 | -1.1 | -1.6 | -1.5 | -3.0 | -3.4 | - | JIS-Z- 8730 | |
| Degree of crystallinity | ％ | 54.1 | 53.6 | 54.5 | 53.8 | 54.7 | 54.1 | - | ASTM-D- 1505 | |
| AA | ppm | 0.7 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | - | ASTM-D- 4509 | |
| Heat-resisting bottle | Thermotolerance | ℃ | 93 | 100 | 91 | 90 | 91 | 91 | - | |
| O 2Gas tightness | Cc/ filling/sky | 0.040 | 0.038 | 0.045 | 0.046 | 0.045 | 0.046 | - | ||
| The mist value | - | 6.8 | 31.4 | 20.2 | 6.4 | 89.6 | 65.2 | - | ||
| Minimum degree of crystallinity | ％ | 38 | 42 | 37 | 35 | 42 | 37 | - | ASTM-D- 1505 |
Measure thermotolerance and O in the following manner
2Gas tightness.
-thermotolerance-
The thermotolerance of bottle is represented by heat resisting temperature.At first heat water to preset temperature, and add in the bottle at once into initial heat resisting temperature.The morphological stability of assessment bottle.
-O
2Gas tightness-
Make bottle stop oxygen with epoxy.Nitrogen is charged in the bottle with specific speed, measure contained oxygen concentration in the nitrogen,, calculate the amount of oxygen that permeates by bottle in a day based on this concentration.
As mentioned above, according to the present invention, provide to have excellent heat resistance and high airtight (as O
2) saturated polyester of property.Therefore, saturated polyester of the present invention can be used as the various bottles of packed drink or food.
Although disclose the preferred embodiment of the invention that is used for illustration purpose, those skilled in the art will recognize not leaving under the disclosed scope of the invention of claims and the spirit and carry out various improvement, increase and replacement.
Claims (8)
1. saturated polyester that is used for plastic containers that comprises nano-size silica particles, this nano-size silica particles has median size 3 to 100nm, and its amount is 20ppm to 10wt%, by the weight of saturated polyester.
2. the saturated polyester that is used for plastic containers as claimed in claim 1, wherein saturated polyester is by adding nano-size silica particles during transesterification or esterification, then will be as the aromatic dicarboxylic acid of parent material and ethylene glycol polycondensation and prepare.
3. the saturated polyester that is used for plastic containers as claimed in claim 1, wherein saturated polyester is a polyethylene terephthalate.
4. the saturated polyester that is used for plastic containers as claimed in claim 1, wherein silica dioxide granule obtains as follows: at first silication sodium and water reaction are produced water glass, water glass is passed through cation exchange resin column, remove the sodium oxide with cationic exchange resin adsorption, obtain fine silica particle and crystalline growth fine silica particle thus.
5. method for preparing the saturated polyester that is used for plastic containers, comprise the steps: during transesterification or esterification, to add the nano-size silica particles of median size 3 to 100 nanometers, then will be as the aromatic dicarboxylic acid and the ethylene glycol polycondensation of parent material.
6. method as claimed in claim 5 wherein adds silica dioxide granule with the slurry form that contains 3 to 30wt% silica dioxide granules.
7. method as claimed in claim 6, the solvent that wherein is used to form slurry is an ethylene glycol.
8. method as claimed in claim 5, wherein the amount of the silica dioxide granule of Jia Ruing is 20ppm to 10wt%, by the weight of saturated polyester.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021505519A CN1193058C (en) | 2002-11-13 | 2002-11-13 | Saturated polyester with good heat resistance and imporosity used for plastic container and its preparing method |
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| CNB021505519A CN1193058C (en) | 2002-11-13 | 2002-11-13 | Saturated polyester with good heat resistance and imporosity used for plastic container and its preparing method |
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| CN1500702A CN1500702A (en) | 2004-06-02 |
| CN1193058C true CN1193058C (en) | 2005-03-16 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100378167C (en) * | 2004-09-15 | 2008-04-02 | 中国科学院合肥物质科学研究院 | polymer/silicon dioxide nano particle composite material and preparation method thereof |
| CN100412132C (en) * | 2005-03-04 | 2008-08-20 | 中国科学院合肥物质科学研究院 | Polyester bottle and preparation method thereof |
| CN101058634B (en) * | 2006-04-22 | 2011-06-08 | 东丽纤维研究所（中国）有限公司 | Polytrimethlene terephthalate resin with excellent moisture absorption and producing method |
| CN102516509A (en) * | 2011-11-16 | 2012-06-27 | 南京兰埔成实业有限公司 | Method for preparing polyester slices for optical film and optical film |
| CN114193686A (en) * | 2021-11-08 | 2022-03-18 | 南京兰埔成新材料有限公司 | Preparation method of precoated polyester film for high-end backlight display |
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