EP2160436A1 - Transparent polyester film comprising baso<sb>4</sb>particles - Google Patents
Transparent polyester film comprising baso<sb>4</sb>particlesInfo
- Publication number
- EP2160436A1 EP2160436A1 EP08759172A EP08759172A EP2160436A1 EP 2160436 A1 EP2160436 A1 EP 2160436A1 EP 08759172 A EP08759172 A EP 08759172A EP 08759172 A EP08759172 A EP 08759172A EP 2160436 A1 EP2160436 A1 EP 2160436A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- polyester film
- polyester
- film according
- barium sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002245 particle Substances 0.000 title claims abstract description 62
- 229920006267 polyester film Polymers 0.000 title claims abstract description 39
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 74
- 229920000728 polyester Polymers 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- -1 polyethylene terephthalate Polymers 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000009998 heat setting Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims 2
- 230000001681 protective effect Effects 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052787 antimony Inorganic materials 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 18
- 239000000654 additive Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000004594 Masterbatch (MB) Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920006309 Invista Polymers 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000012963 UV stabilizer Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 125000005487 naphthalate group Chemical group 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 210000003934 vacuole Anatomy 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 229920006097 Ultramide® Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-L naphthalene-1,5-dicarboxylate Chemical compound C1=CC=C2C(C(=O)[O-])=CC=CC2=C1C([O-])=O DFFZOPXDTCDZDP-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
Definitions
- the invention relates to a single- or multilayer, oriented polyester film which comprises BaSO 4 particles, which have a special coating, whereby the bonding of the particles is improved in the polyester. This leads to a film with high transparency.
- Silica and its mixed oxides with aluminum also have other disadvantages. These particles react with the polyester during polymer production and during processing and result in a raw material production undesirable viscosity increase and in the processing often to the formation of stripes in the final product. Due to the increase in viscosity z.
- B. extrusion Masterbatche ie the particles are incorporated by means of a multi-screw extruder into the Poymer
- silica basis only with relatively low particle concentrations ( ⁇ 3 wt .-%) are produced or they have a lower quality (ie there are large Agglomerates of the particles which later become visible in the film as specks or clog the polymer filters); see EP-A-1 364 982.
- This object is achieved by a single-layer or multilayer, oriented polyester film which contains barium sulfate particles which have a special coating (coating).
- This coating improves the incorporation of the (coated) barium sulfate particles into the polyester (polyester matrix), resulting in a film with high transparency as a result.
- the film according to the invention can simultaneously have one, several or all of the properties mentioned:
- the transparency of the film is between 70 and 99.5%
- the film has a roughness of at least 10 to 400 nm on at least one side
- the coated barium sulfate has an average particle size of between 0.7 and 7 ⁇ m
- the barium sulfate is coated with an inorganic layer
- the barium sulfate is present in an amount of 0.005 to 20% by weight in the film (based on the total weight of the film)
- the thickness of the polyester film is between 0.5 and 500 ⁇ m
- the film can be produced economically and has h) in both film directions an E-modulus of greater than 500 N / mm 2 .
- the invention also encompasses the use of barium sulfate coated according to the invention for the production of polyester raw material and transparent polyester films.
- the transparency of the film is preferably between 70 and 99.5%. It has proven to be advantageous if the transparency is greater than 80%, preferably greater than 85% and particularly preferably greater than 90%.
- the haze of the film is usually in the thickness range between 0.5 and 50 microns at ⁇ 10%, preferably at ⁇ 5% and particularly preferably at ⁇ 2.5%.
- the haze of the film is usually in the thickness range between 51 and 200 microns at ⁇ 35%, preferably at ⁇ 25% and particularly preferably at ⁇ 10%.
- the haze of the film is usually in the thickness range between 201 and 500 microns at ⁇ 60%, preferably at ⁇ 50% and particularly preferably at ⁇ 40%.
- the roughness of the film is preferably at least one side between 10 and 400 nm. In order to ensure good windability of the film, values between 20 and 300 nm and especially values between 25 and 250 nm have proved favorable.
- the mean size d 50 of the coated barium sulfate particles is preferably between 0.7 ⁇ m and 7 ⁇ m.
- the average particle size (d 50 ) is in particular between 1, 0 and 6 microns and more preferably between 1, 2 to 3.5 microns. Smaller particles than 0.7 microns lead to too low surface roughness and would therefore have to be dosed in very high concentrations and then lead u. U. too high turbidity. Particles with a d ⁇ o above 7 microns prove to be not sufficiently involved with coating in the polymer matrix, which also leads to a high turbidity and also to a significant abrasion of the particles in further processing.
- the thickness of the film is preferably> 0.5 and ⁇ 500 .mu.m and in particular from 7 to 250 .mu.m and preferably from 10 to 100 .mu.m.
- Economic manufacturability includes the fact that the film can be oriented biaxially without breaks in its production and that no visible color change occurs even when using 40 to 80% of its own regenerated material and that the film tends less to streak in production than a comparable one Foil with SKVParticles.
- the good mechanical properties include, inter alia, a high modulus of elasticity in the longitudinal direction (MD) and transverse direction (TD) of greater than or equal to 500 N / mm 2 , preferably greater than or equal to 2000 N / mm 2 and particularly preferably greater than or equal to 4000 N / mm 2 .
- the film according to the invention in any film direction has a shrinkage of greater than 25% at 200 0 C.
- the shrinkage is equal to 10% at 200 0 C less than /, in particular less than / equal to 4%. This is favorable, since the film can be processed so well without wrinkling in other processing steps at elevated temperature (metallization, lamination, etc.).
- the film according to the invention contains as the main polymer constituent (preferably from 55 to 100% by weight, in particular from 70 to 100% by weight and more preferably from 90 to 100% by weight) of polyester.
- polyester is understood to mean homopolyesters, copolyesters, blends of various polyesters, these being able to be used both as pure raw materials and as polyester materials containing recycled material.
- Polyesters contain repeating units derived from dicarboxylic acids (100 mol%) and diols (also 100 mol%).
- the polyesters according to the invention are preferably based on terephthalic acid or 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid and on ethylene glycol or 1,4-butanediol as the diol (such as, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or polyethylene-2,6-one). naphthalate (PEN)).
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene-2,6-one
- the polyesters according to the invention contain from 10 to 100 mol% terephthalate (preferably> 50 and more preferably> 90 mol% terephthalate) and / or from 10 to 100 mol% 2,6-naphthalate as dicarboxylic acid components, the total amount of dicarboxylic acid components 100 mol%.
- the polyester of the present invention may preferably be 0 to 50 mol% of 2,6-naphthalate (when the main component is terephthalate), 0 to 50 mol% of terephthalate (if naphthalate is used as the main component), 0 to 20 mol % Isophthalate (preferably 0.5 to 10 mol%) and 10 to 60 mol% of 4,4'-diphenyldicarboxylate.
- Other dicarboxylic acid components such as 1,5-naphthalenedicarboxylate should optionally not exceed a proportion of 30 mol%, preferably 10 mol%, in particular 2 mol%.
- Embodiments with at least 0.5 mol% of isophthalic acid, preferably at least 1 mol% of isophthalic acid are particularly preferred because they are less brittle and better adapt to changes in shape during later processing.
- the polyester according to the invention generally contains from 10 to 100 mol% of ethylene glycol (EG), the total amount of diol components being 100 mol%. If mixtures of different diols are used, it is advantageous not to exceed the proportion of diethylene glycol of 10 mol%, and preferably to use 0.5 to 5 mol%.
- Other diol components such as cyclohexanedimethanol, 1, 3-propanediol, 1, 4-butanediol should expediently not exceed a proportion of 50 mol% and are preferably in a proportion of less than 30 mol%, more preferably less than 10 mol -%.
- the stated polyesters can also be used as mixtures. PET is particularly preferred.
- the film may contain up to 45% by weight, preferably up to 30% by weight, more preferably up to 20% by weight, based on the total weight of the film, of other polymers such as polyetherimides (e.g. . B. Ultem ® 1000 from GE Plastics Europe, NL) polycarbonates (for. example, Makrolon ® from Bayer, DE), polyolefins such as COC (z. B. Topas ® from Ticona, Germany), polyamides (Ultramid ® from BASF, DE) and others.
- polyetherimides e.g. . B. Ultem ® 1000 from GE Plastics Europe, NL
- polycarbonates for. example, Makrolon ® from Bayer, DE
- polyolefins such as COC (z. B. Topas ® from Ticona, Germany)
- polyamides Ultramid ® from BASF, DE
- polyesters are prepared by literature methods from said diols and dicarboxylic acids or Dicarbonklareestem.
- the preparation of the polyesters can be carried out both by the transesterification process with the customary catalysts such as Zn, Ca, Li and Mn salts or by the direct esterification process.
- Polyesters of the invention are commercially available.
- the Bariumsulfatpelle can be prepared by known methods such as. B. in WO 00/76919 described or it can commercially available products such as the ® Blanc Fix series from Sachtleben, DE 1 are used. These particles can be coated by known methods preferably with an inorganic coating. Such processes are described inter alia in EP-AO 459 552 (column 3 and examples) or DE-A-103 33 029 ([0027] - [0037] and examples 1-3) and DE-A-10 2006 031 630, wherein the SoI-GeI method is preferred.
- Suitable coatings are oxides or mixtures thereof or mixed oxides of Si, Al, Sn, Fe, In, Zr, Ce and Sb, oxides of Si and Al being preferred, mixed oxides of Si and Al or pure silicon oxides being particularly preferred , in particular SiO 2 and Al 2 O 3 or mixtures thereof / mixed oxides.
- the proportion of these oxides (coating) in the total weight of the coated particles is usually below 15 wt .-%, preferably below 3 wt .-% and particularly preferably below 2 wt .-%.
- a low proportion of the coating in the total weight of the particles has a favorable effect on the haze of the film, since the refractive index of BaSO 4 thus maintains a higher weight.
- the coated barium sulfate particles are added to the film in an amount of preferably 0.005 to 20 wt .-%. Usually, the content is between 0.01 and 5 wt .-% (in each case based on the total weight of the film).
- Typical antiblocking agents are inorganic and / or organic particles, for example silica (natural, precipitated or pyrogenic), calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate (not inorganically coated), lithium phosphate, calcium phosphate, magnesium phosphate, titanium dioxide (rutile or anatase), kaolin ( hydrated or calcined), alumina, aluminum silicate, lithium fluoride, calcium, barium, zinc or manganese salts of the dicarboxylic acids or crosslinked polymer particles, e.g. Polystyrene or polymethyl methacrylate particles, preferably the coated barium sulfate is combined with silica as the antiblocking agent.
- silica naturally, precipitated or pyrogenic
- calcium carbonate magnesium carbonate
- barium carbonate calcium sulfate
- barium sulfate not inorganically coated
- lithium phosphate calcium phosphate
- magnesium phosphate titanium dioxide
- the other particulate additives have an average size (d 50 value) of usually 0.01 to 15 .mu.m, preferably 0.03 to 10 .mu.m and particularly preferably 0.05 to 5 microns.
- the proportion of particles having a d 50 value of greater than or equal to 3 ⁇ m is less than or equal to 2000 ppm and particularly preferably less than or equal to 1000 ppm.
- the amount in wt .-% of coated barium sulfate is greater than the sum of the other fillers / particles in wt .-%, particularly preferred are embodiments in which the filler to at least 85 wt .-% of the coated barium sulfate consists. It is also possible to select mixtures of two or more of the abovementioned particle systems or mixtures of particle systems having the same chemical composition but different particle size. The particles are added to the polyester advantageously before melting.
- the film has a monolayer or multilayer structure, with multilayer constructions being preferred. Particularly preferred are at least three-layered structures.
- the coated barium sulfate is preferably added to only one or both outer layers.
- the possibly present other particles are preferably metered only in the outer layers.
- Particles in internal layers preferably originate from self-regenerated material of the respective film.
- the proportion of coated barium sulfate in at least one outer layer is between 0.01 and 20 wt .-% and particularly preferably between 0.1 and 5 wt .-% (based on the total weight of the corresponding outer layer).
- the weight of the coated barium sulfate-containing layer is preferably at least 2 wt .-% of the total film weight, more preferably at least 5 wt .-% of the total film weight.
- the proportion of all particulate additives, including the coated barium sulfate is usually less than 5 wt .-%, preferably less than 1 wt .-% and particularly preferably less than 0.5 wt .-%, based on the total weight of the film.
- the inventive film can keep corresponds other additives such as dyes, UV stabilizers, flame retardants, hydrolysis and / or antioxidants, in particular UV stabilizers Tinuvin ® series of Messrs. Ciba SC, CH, are preferred.
- the film can be coated to adjust other properties. Typical coatings are in particular adhesion-promoting, antistatic, slip-improving or dehesive-acting layers. It is advisable to apply these additional layers to the film via in-line coating by means of aqueous dispersions after the longitudinal and before the transverse stretching.
- the additives ie the coated barium sulfate particles and optionally present further fillers and other additives (such as UV stabilizers) are preferably introduced into the polymer by means of a commercially available twin-screw extruder.
- the polyester is introduced according to the invention in granular form together with the particles / additives in the extruder and extruded, then quenched in a water bath and then granulated.
- the additives can also be added directly during the polyester production. For dyes and UV stabilizers, this method is less preferred because of the added thermal stress.
- the additives are usually added after the transesterification or directly before the polycondensation (for example via the transport line between transesterification and polycondensation vessel) as a glycolic dispersion. The addition can also be done before the transesterification.
- the addition is preferably carried out at the beginning of the polycondensation. However, a later addition is also possible.
- the glycolic dispersions are filtered prior to the addition of a PGF PROGAF 57 ® (Hayward, Indiana, US) filter.
- PGF PROGAF 57 ® Hyward, Indiana, US
- the present invention also provides a process for producing the film.
- the production is carried out by an extrusion process. It has proven to be particularly advantageous to add all additives such as particles, UV stabilizers, flameproofing agents, hydrolysis stabilizers and antioxidants in the amounts mentioned in the form of masterbatches prior to extrusion.
- polyester films can be prepared by known methods from a polyester raw material and optionally other raw materials as a single or multilayer film.
- the masterbatches and the other raw materials can be extruded directly without the use of pre-drying when using twin-screw and multi-screw extruders.
- drying at 120 to 150 ° C is recommended for at least 1 hour.
- the melts corresponding to the individual layers of the film are coextruded through a flat die and quenched as a largely amorphous prefilm on a chill roll.
- This film is then reheated and stretched (oriented) in at least one direction or in the longitudinal and transverse direction or in the transverse and longitudinal direction or in the longitudinal direction, in the transverse direction and again in the longitudinal direction and / or transverse direction.
- the film temperatures in the stretching process are generally 10 to 60 ° C above the glass transition temperature T 9 of the polyester used, the draw ratio of the longitudinal stretching is preferably from 2 to 6, in particular from 3 to 4.5, that of the transverse extension at 2 to 5, in particular at 3 to 4.5, and that of the optionally performed second longitudinal and transverse extension at 1, 1 to 5.
- the first longitudinal stretching can also be carried out simultaneously with the transverse extension (simultaneous stretching). This is followed by the heat-setting of the film at oven temperatures of about 180 to 260 ° C., preferably from 220 to 250 ° C.
- the film is then cooled and wound.
- a biaxially oriented film is preferred.
- the heat-setting takes place at temperatures of 220 to 250 ° C. and the film is relaxed at this temperature by at least 1%, preferably at least 2%, in the transverse direction.
- the heat-setting takes place at 220 to 250 ° C., and the film is relaxed at this temperature by at least 1%, preferably at least 2%, in the transverse direction and then again at Temperatures between 180 and 150 0 C in the cooling phase again by at least 1%, preferably at least 2%, relaxed in the transverse direction.
- the film is stretched at least by a factor of 3 in the MD and TD directions, the stretching taking place in a simultaneous frame.
- the monolayer or multilayer films according to the invention have the required good mechanical properties.
- the modulus of elasticity in at least one film direction is preferably greater than or equal to 500 N / mm 2 .
- the film has no shrinkage of more than 25% at 200 ° C. in either direction (neither MD nor TD).
- coated barium sulfate particles can also be incorporated in masterbatches, in particular in extrusion masterbatches, in concentrations above 3% by weight and even above 7% by weight, substantial savings in raw material costs compared to SiO 2 -filled raw materials are possible.
- the film is suitable for almost all known polyester film applications such as packaging applications, for metallization, for motor film, etc., and in particular for all applications that have good optical properties of the film, such. B. high transparency, need.
- the modulus of elasticity, tear strength, elongation at break and F 5 value are measured in the longitudinal and transverse directions according to ISO 527-1-2 with the aid of a tensile strain gauge (type 010 from Zwick / DE).
- the thermal shrinkage is determined on square film samples with an edge length of 10 cm.
- the samples are measured precisely (edge length Lo), 15 min heat-treated at 200 0 C in a convection oven and then measured precisely at room temperature (edge length L).
- edge length L The shrinkage results from the equation
- the determination of the mean diameter d 50 is carried out by laser on a Malvern Master Sizer (Malvern Instruments Ltd., GB) according to the standard method. Other measuring devices are z. Horiba LA 500 (HORIBA Europe GmbH, DE) or Sympathec Helos (Sympathec GmbH, DE), which use the same measuring principle. The samples are then placed in a cuvette with water and then placed in the meter. The measuring process is automatic and also includes the mathematical determination of the d 5 o value.
- the dso value is determined from the (relative) cumulative curve of the particle size distribution. The point of intersection of the 50% ordinate value with the cumulative curve immediately gives the desired d 50 value on the abscissa axis (see FIG. Measurement of turbidity
- the measurement is carried out on the Hazegard Hazemeter XL-211 from BYK Gardner (s.
- the meter should be turned on 30 minutes before the measurement. It is important to ensure that the light beam passes through the ball centric to the outlet opening.
- each 5 samples are cut out with a size of 100 x 100 mm.
- the longitudinal and transverse directions are marked on the edge, since the measurements are made in both machine directions.
- the turbidity is obtained by averaging the respective 5 individual values (longitudinal and transverse).
- the yellow value G (YID) is the deviation from the colorlessness in the direction "yellow” and is measured according to DIN 6167.
- the transparency is measured according to ASTM-D 1033-77. roughness
- the roughness R a of the film is determined according to DIN 4768.
- Polyester chips are mixed according to the ratios given in the examples and melted without predrying in twin-screw extruders.
- the molten polymer strands are brought together in a coextrusion die and drawn off via a draw-off roll (roll temperature 20 0 C).
- the film is stretched by a factor of 3.9 in the machine direction at 116 ° C. (film temperature in the drawing nip) and in a frame at 110 ° C. a transverse extension of a factor of 3.8 is carried out.
- the film is heat set at 229 0 C and relaxed in the transverse direction by 1, 5% at temperatures of 225 0 C and a second time to 1, 5% at temperatures from 180 to 150 0 C.
- the production speed (final film speed) is 300 m / min.
- PET polyethylene terephthalate
- coated barium sulfate was metered together with the polyester raw material T94 from Invista, DE, into the feed zone of a Werner and Pfleiderer (DE) twin-screw extruder and extruded and granulated. Preparation of the coated barium sulfate:
- the silicon dioxide was metered together with the polyester raw material T94 from Invista, DE, into the feed zone of a Werner and Pfleiderer twin-screw extruder and extruded and granulated.
- Extrusionsmasterbatch with 10 wt .-% BaSO 4 (Blanc Fixe N, average particle size 0 50 1, 7 microns, the company Solvay Chemicals) in polyethylene terephthalate (PET).
- the uncoated barium sulfate was dosed together with the polyester raw material T94 Invista in the feed zone of a Werner and Pfleiderer twin-screw extruder and extruded and granulated.
- Coats A and C each with 2 microns, as stated above, prepared.
- Coats A and C each with 2 microns, as stated above, prepared. Coatings A and C: 1, 5% MB2 and 98.5% R1
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Abstract
The invention relates to a polyester film having high transparency (70 to 99.5%), comprising barium sulfate particles having an average particle size of 0.7 to 7 µm provided with an inorganic coating. The coating is made of oxides, mixed oxides or mixtures of oxides of Si, Al, Sn, Fe, In and Sb, allowing the barium sulfate particles to be better embedded in the polyester matrix and thus minimizing the turbidity of the film. Mixed oxides of SiO2 und AI2O3are preferred. The preferred polyester is PET. <sub/>
Description
Transparente Polyesterfolie mit BaSO4-PartikelnTransparent polyester film with BaSO 4 particles
Die Erfindung betrifft eine ein- oder mehrschichtige, orientierte Polyesterfolie, die BaSO4-Partikel enthält, welche ein spezielles Coating aufweisen, wodurch die Einbindung der Partikel in den Polyester verbessert wird. Dies führt zu einer Folie mit hoher Transparenz.The invention relates to a single- or multilayer, oriented polyester film which comprises BaSO 4 particles, which have a special coating, whereby the bonding of the particles is improved in the polyester. This leads to a film with high transparency.
Die Herstellung von gestreckten Polyesterfolien ist bekannt, ebenso wie die Verwendung von BaSO4 als Weißpigment in solchen Folien (vgl. EP-A-1 728 815).The preparation of stretched polyester films is known, as is the use of BaSO 4 as a white pigment in such films (see EP-A-1 728 815).
Ebenso bekannt ist, dass Siliziumdioxid und Aluminiumoxid sowie deren Mischoxide eine gute Einbindung in Polyesterfolien haben. Solche Partikel werden daher häufig zur Oberflächenmodifikation von Polyesterfolien eingesetzt (vgl. EP-A-1 176 005).It is also known that silicon dioxide and aluminum oxide as well as their mixed oxides have a good incorporation into polyester films. Such particles are therefore frequently used for surface modification of polyester films (cf EP-A-1 176 005).
Durch die gute Einbindung von Siliziumdioxid- und Aluminiumoxid-Partikeln sowie deren Mischoxiden entstehen im Streckprozess wenige oder zumindest nur kleine Vakuolen, die das Licht streuen und so zu einer Eintrübung der Polyesterfolie führen. Bariumsulfatpartikel hingegen haben eine eher schlechtere Einbindung in die Polyestermatrix, wodurch im Streckprozess Vakuolen entstehen, die durch ihre Licht- Streuung zu einer Eintrübung und bei höheren Konzentrationen (z. B. > 1 %) zu einer weiß-opaken Folie führen. Neben ihrer Einbindung ist jedoch auch der Brechungsindex der Partikel selbst von Bedeutung, welcher bei SiOx-Partikeln in der Regel um 1 ,5 (zumeist 1 ,46 - 1 ,54) liegt und bei Aluminiumoxiden zumeist > 1 ,7 ist. Dies liegt unterhalb bzw. oberhalb des Mittelwertes der Brechungsindizes von gestreckten Polyesterfolien (1 ,57 - 1 ,63). Je näher der Brechungsindex der Partikel jedoch bei dem des Polyesters liegt, desto geringer ist sein Trübungs- bzw. Brechungsbeitrag. Hier liegt Bariumsulfat mit Werten um 1 ,6 genau im Bereich der Polyesterfolie, kann aber aufgrund der schlechten Einbindung nicht gut in transparenten Polyesterfolien eingesetzt werden.Due to the good incorporation of silica and alumina particles and their mixed oxides little or at least only small vacuoles are formed in the stretching process, which scatter the light and thus lead to clouding of the polyester film. Barium sulfate particles, on the other hand, have a rather poor incorporation into the polyester matrix, which causes vacuoles in the stretching process which cloud their light scattering and lead to a white-opaque film at higher concentrations (eg> 1%). In addition to their integration, however, the refractive index of the particles themselves is of importance, which in SiOx particles usually by 1, 5 (usually 1, 46 - 1, 54) and in the case of aluminum oxides is usually> 1, 7. This is below or above the mean value of the refractive indices of stretched polyester films (1, 57-1, 63). However, the closer the refractive index of the particles is to that of the polyester, the lower is its turbidity contribution or refraction contribution. Here, barium sulfate with values around 1.6 is exactly in the range of the polyester film, but due to the poor incorporation can not be used well in transparent polyester films.
Siliziumdioxid sowie dessen Mischoxide mit Aluminium weisen zudem weitere Nachteile auf. Diese Partikel reagieren während der Polymerherstellung und während der Verarbeitung mit dem Polyester und führen in der Rohstoffherstellung zu einem
unerwünschten Viskositätsanstieg und in der Verarbeitung häufig zur Bildung von Streifen im Endprodukt. Aufgrund des Viskositätsanstiegs können z. B. Extrusions- masterbatche (d. h. die Partikel werden mittels eines Mehrschneckenextruders in das Poymer eingearbeitet) auf Siliziumdioxidbasis nur mit relativ geringen Partikel- konzentrationen (< 3 Gew.-%) hergestellt werden bzw. sie weisen eine geringere Qualität auf (d. h. es treten große Agglomerate der Partikel auf, die später in der Folie als Stippen sichtbar werden oder die Polymerfilter verstopfen); siehe dazu EP- A-1 364 982.Silica and its mixed oxides with aluminum also have other disadvantages. These particles react with the polyester during polymer production and during processing and result in a raw material production undesirable viscosity increase and in the processing often to the formation of stripes in the final product. Due to the increase in viscosity z. B. extrusion Masterbatche (ie the particles are incorporated by means of a multi-screw extruder into the Poymer) on silica basis only with relatively low particle concentrations (<3 wt .-%) are produced or they have a lower quality (ie there are large Agglomerates of the particles which later become visible in the film as specks or clog the polymer filters); see EP-A-1 364 982.
Aufgabe der vorliegenden Erfindung ist es daher, eine transparente Polyesterfolie bereitzustellen, welche die oben beschriebenen Nachteile nicht aufweist.It is therefore an object of the present invention to provide a transparent polyester film which does not have the disadvantages described above.
Gelöst wird diese Aufgabe durch eine ein- oder mehrschichtige, orientierte Polyesterfolie, die Bariumsulfatpartikel enthält, welche ein spezielles Coating (Beschich- tung) aufweisen. Durch diese Beschichtung wird die Einbindung der (beschichteten) Bariumsulfatpartikel in den Polyester (Polyestermatrix) verbessert, was im Ergebnis zu einer Folie mit hoher Transparenz führt.This object is achieved by a single-layer or multilayer, oriented polyester film which contains barium sulfate particles which have a special coating (coating). This coating improves the incorporation of the (coated) barium sulfate particles into the polyester (polyester matrix), resulting in a film with high transparency as a result.
Weitere bevorzugte Eigenschaften der erfindungsgemäßen Folie sind nachfolgend unter a) - h) aufgeführt, wobei jede mögliche Kombination oder Unterkombination dieser Eigenschaften von der vorliegenden Erfindung umfasst wird; d. h. die erfindungsgemäße Folie kann gleichzeitig eine, mehrere oder alle der genannten Eigenschaften aufweisen:Further preferred properties of the film according to the invention are listed below under a) - h), wherein any possible combination or sub-combination of these properties is encompassed by the present invention; d. H. the film according to the invention can simultaneously have one, several or all of the properties mentioned:
a) Die Transparenz der Folie liegt zwischen 70 und 99,5 %, b) die Folie weist mindestens einseitig eine Rauheit von 10 - 400 nm auf, c) das beschichtete Bariumsulfat hat eine mittlere Partikelgröße zwischen 0,7 und 7 μm, d) das Bariumsulfat ist mit einer anorganischen Schicht beschichtet, e) das Bariumsulfat ist in einer Menge von 0,005 bis 20 Gew.-% in der Folie enthalten (bezogen auf das Gesamtgewicht der Folie), f) die Dicke der Polyesterfolie liegt zwischen 0,5 und 500 μm, g) die Folie lässt sich wirtschaftlich herstellen und hat
h) in beiden Folienrichtungen ein E-Modul von größer als 500 N/mm2.a) the transparency of the film is between 70 and 99.5%, b) the film has a roughness of at least 10 to 400 nm on at least one side, c) the coated barium sulfate has an average particle size of between 0.7 and 7 μm, d) the barium sulfate is coated with an inorganic layer, e) the barium sulfate is present in an amount of 0.005 to 20% by weight in the film (based on the total weight of the film), f) the thickness of the polyester film is between 0.5 and 500 μm, g) the film can be produced economically and has h) in both film directions an E-modulus of greater than 500 N / mm 2 .
Die Erfindung umfasst auch die Verwendung von erfindungsgemäß beschichtetem Bariumsulfat zur Herstellung von Polyesterrohstoff und transparenten Polyester- folien.The invention also encompasses the use of barium sulfate coated according to the invention for the production of polyester raw material and transparent polyester films.
Die Transparenz der Folie liegt bevorzugt zwischen 70 und 99,5 %. Es hat sich dabei als günstig erwiesen, wenn die Transparenz größer als 80 %, bevorzugt größer als 85 % und besonders bevorzugt größer als 90 % ist.The transparency of the film is preferably between 70 and 99.5%. It has proven to be advantageous if the transparency is greater than 80%, preferably greater than 85% and particularly preferably greater than 90%.
Die Trübung der Folie liegt im Dickenbereich zwischen 0,5 und 50 μm üblicherweise bei < 10 %, bevorzugt bei < 5 % und besonders bevorzugt bei < 2,5 %.The haze of the film is usually in the thickness range between 0.5 and 50 microns at <10%, preferably at <5% and particularly preferably at <2.5%.
Die Trübung der Folie liegt im Dickenbereich zwischen 51 und 200 μm üblicherweise bei < 35 %, bevorzugt bei < 25 % und besonders bevorzugt bei < 10 %.The haze of the film is usually in the thickness range between 51 and 200 microns at <35%, preferably at <25% and particularly preferably at <10%.
Die Trübung der Folie liegt im Dickenbereich zwischen 201 und 500 μm üblicherweise bei < 60 %, bevorzugt bei < 50 % und besonders bevorzugt bei < 40 %.The haze of the film is usually in the thickness range between 201 and 500 microns at <60%, preferably at <50% and particularly preferably at <40%.
Die Rauheit der Folie liegt mindestens einseitig bevorzugt zwischen 10 und 400 nm. Um eine gute Wickelbarkeit der Folie sicherzustellen, haben sich Werte zwischen 20 und 300 nm und besonders Werte zwischen 25 und 250 nm als günstig erwiesen.The roughness of the film is preferably at least one side between 10 and 400 nm. In order to ensure good windability of the film, values between 20 and 300 nm and especially values between 25 and 250 nm have proved favorable.
Die mittlere Größe d50 der beschichteten Bariumsulfatpartikel liegt bevorzugt zwischen 0,7 μm und 7 μm. Zum Erreichen der gewünschten Rauigkeiten liegt die mittlere Teilchengröße (d50) insbesondere zwischen 1 ,0 und 6 μm und besonders bevorzugt zwischen 1 ,2 bis 3,5 μm. Kleinere Partikel als 0,7 μm führen zu einer zu geringen Oberflächenrauheit und müssten daher in sehr hohen Konzentrationen dosiert werden und führen dann u. U. zu einer zu hohen Trübung. Partikel mit einem dδo oberhalb von 7 μm erweisen sich auch mit Beschichtung als nicht ausreichend in die Polymermatrix eingebunden, was ebenfalls zu einer hohen Trübung und zudem zu einem deutlich Abrieb der Partikel bei der Weiterverarbeitung führt.
Die Dicke der Folie beträgt bevorzugt > 0,5 und < 500 μm und insbesondere von 7 bis 250 μm und vorzugsweise von 10 bis 100 μm.The mean size d 50 of the coated barium sulfate particles is preferably between 0.7 μm and 7 μm. To achieve the desired roughness, the average particle size (d 50 ) is in particular between 1, 0 and 6 microns and more preferably between 1, 2 to 3.5 microns. Smaller particles than 0.7 microns lead to too low surface roughness and would therefore have to be dosed in very high concentrations and then lead u. U. too high turbidity. Particles with a d δ o above 7 microns prove to be not sufficiently involved with coating in the polymer matrix, which also leads to a high turbidity and also to a significant abrasion of the particles in further processing. The thickness of the film is preferably> 0.5 and <500 .mu.m and in particular from 7 to 250 .mu.m and preferably from 10 to 100 .mu.m.
Zu einer wirtschaftlichen Herstellbarkeit zählt, dass sich die Folie bei ihrer Herstellung biaxial ohne Abrisse orientieren lässt und es auch bei einem Einsatz von 40 bis 80 % Eigenregenerat nicht zu einer sichtbaren Farbveränderung kommt und dass die Folie in der Produktion weniger zur Streifenbildung neigt als eine vergleichbare Folie mit SKVPartikeln.Economic manufacturability includes the fact that the film can be oriented biaxially without breaks in its production and that no visible color change occurs even when using 40 to 80% of its own regenerated material and that the film tends less to streak in production than a comparable one Foil with SKVParticles.
Zu den guten mechanischen Eigenschaften zählen unter anderem ein hoher E-Modul in Längsrichtung (MD) und Querrichtung (TD) von größer/gleich 500 N/mm2, bevorzugt größer/gleich 2000 N/mm2 und besonders bevorzugt größer/gleich 4000 N/mm2.The good mechanical properties include, inter alia, a high modulus of elasticity in the longitudinal direction (MD) and transverse direction (TD) of greater than or equal to 500 N / mm 2 , preferably greater than or equal to 2000 N / mm 2 and particularly preferably greater than or equal to 4000 N / mm 2 .
In einer bevorzugten Ausführungsform weist die Folie gemäß der Erfindung in keiner Folienrichtung (weder in MD noch in TD) einen Schrumpf von größer 25 % bei 200 0C auf. Vorzugsweise ist der Schrumpf bei 200 0C kleiner/gleich 10 %, insbesondere kleiner/gleich 4 %. Dies ist günstig, da die Folie sich so gut ohne Faltenbildung auch in weiteren Verarbeitungsschritten bei erhöhter Temperatur (Metallisierung, Kaschierung etc.) verarbeiten lässt.In a preferred embodiment, the film according to the invention in any film direction (either in MD or TD) has a shrinkage of greater than 25% at 200 0 C. Preferably, the shrinkage is equal to 10% at 200 0 C less than /, in particular less than / equal to 4%. This is favorable, since the film can be processed so well without wrinkling in other processing steps at elevated temperature (metallization, lamination, etc.).
Die erfindungsgemäße Folie enthält als Hauptpolymerbestandteil (bevorzugt zu 55 bis 100 Gew.-%, insbesondere zu 70 bis 100 Gew.-% und besonders bevorzugt zu 90 bis 100 Gew.-%) Polyester.The film according to the invention contains as the main polymer constituent (preferably from 55 to 100% by weight, in particular from 70 to 100% by weight and more preferably from 90 to 100% by weight) of polyester.
Erfindungsgemäß versteht man unter Polyester Homopolyester, Copolyester, - Blends verschiedener Polyester, wobei diese sowohl als reine Rohstoffe als auch als Rezyklat enthaltende Polyesterrohstoffe eingesetzt werden können.
Polyester enthalten Wiederholungseinheiten, die sich von Dicarbonsäuren (100 Mol-%) und Diolen (ebenfalls 100 Mol-%) ableiten. Die erfindungsgemäßen Polyester basieren bevorzugt auf Terephthalsäure oder 2,6-Naphthalindicarbonsäure als Dicarbonsäure und auf Ethylenglykol oder 1 ,4-Butandiol als Diol (wie z. B. PoIy- ethylenterephthalat (PET), Polybutylenterephthalat (PBT) oder Polyethylen-2,6- naphthalat (PEN)).According to the invention, polyester is understood to mean homopolyesters, copolyesters, blends of various polyesters, these being able to be used both as pure raw materials and as polyester materials containing recycled material. Polyesters contain repeating units derived from dicarboxylic acids (100 mol%) and diols (also 100 mol%). The polyesters according to the invention are preferably based on terephthalic acid or 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid and on ethylene glycol or 1,4-butanediol as the diol (such as, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or polyethylene-2,6-one). naphthalate (PEN)).
Insbesondere enthalten die erfindungsgemäßen Polyester 10 bis 100 Mol-% Tereph- thalat (bevorzugt > 50 und besonders bevorzugt > 90 Mol-% Terephthalat) und/ oder 10 bis 100 Mol-% 2,6-Naphthalat als Dicarbonsäurekomponenten, wobei die Gesamtmenge an Dicarbonsäurekomponenten 100 Mol-% ausmacht. Als weitere Dicarbonsäurekomponenten kann der erfindungsgemäße Polyester bevorzugt 0 bis 50 Mol-% 2,6-Naphthalat (wenn als Hauptkomponente Terephthalat eingesetzt wurde), 0 bis 50 Mol-% Terephthalat (wenn als Hauptkomponente Naphthalat ver- wendet wurde), 0 bis 20 Mol-% Isophthalat (bevorzugt 0,5 bis 10 Mol-%) sowie 10 bis 60 Mol-% 4,4'-Diphenyldicarboxylat enthalten. Andere Dicarbonsäurekomponenten wie 1 ,5-Naphthalindicarboxylat sollen gegebenenfalls einen Anteil von 30 Mol-%, bevorzugt 10 Mol-%, insbesondere 2 Mol-%, nicht überschreiten. Ausführungsformen mit mindestens 0,5 Mol-% Isophthalsäure, bevorzugt mindestens 1 Mol-% Isophthalsäure, sind besonders bevorzugt, da diese weniger spröde sind und sich bei der späteren Verarbeitung besser Formänderungen anpassen.In particular, the polyesters according to the invention contain from 10 to 100 mol% terephthalate (preferably> 50 and more preferably> 90 mol% terephthalate) and / or from 10 to 100 mol% 2,6-naphthalate as dicarboxylic acid components, the total amount of dicarboxylic acid components 100 mol%. As other dicarboxylic acid components, the polyester of the present invention may preferably be 0 to 50 mol% of 2,6-naphthalate (when the main component is terephthalate), 0 to 50 mol% of terephthalate (if naphthalate is used as the main component), 0 to 20 mol % Isophthalate (preferably 0.5 to 10 mol%) and 10 to 60 mol% of 4,4'-diphenyldicarboxylate. Other dicarboxylic acid components such as 1,5-naphthalenedicarboxylate should optionally not exceed a proportion of 30 mol%, preferably 10 mol%, in particular 2 mol%. Embodiments with at least 0.5 mol% of isophthalic acid, preferably at least 1 mol% of isophthalic acid, are particularly preferred because they are less brittle and better adapt to changes in shape during later processing.
Als Diolkomponente enthält der erfindungsgemäße Polyester im allgemeinen 10 bis 100 Mol-% Ethylenglykol (EG), wobei die Gesamtmenge an Diolkomponenten 100 Mol-% ausmacht. Werden Mischungen verschiedener Diole eingesetzt, ist es vorteilhaft, den Anteil an Diethylenglykol von 10 Mol-% nicht zu überschreiten und vorzugsweise 0,5 bis 5 Mol-% einzusetzen. Andere Diolkomponenten wie Cyclo- hexandimethanol, 1 ,3-Propandiol, 1 ,4-Butandiol sollten zweckmäßigerweise einen Anteil von 50 Mol-% nicht überschreiten und liegen bevorzugt bei einem Anteil von weniger als 30 Mol-%, besonders bevorzugt bei weniger als 10 Mol-%.As a diol component, the polyester according to the invention generally contains from 10 to 100 mol% of ethylene glycol (EG), the total amount of diol components being 100 mol%. If mixtures of different diols are used, it is advantageous not to exceed the proportion of diethylene glycol of 10 mol%, and preferably to use 0.5 to 5 mol%. Other diol components such as cyclohexanedimethanol, 1, 3-propanediol, 1, 4-butanediol should expediently not exceed a proportion of 50 mol% and are preferably in a proportion of less than 30 mol%, more preferably less than 10 mol -%.
Die angeführten Polyester können auch als Mischungen eingesetzt werden. PET ist insbesondere bevorzugt.
Neben den genannten Hauptpolymerbestandteilen kann die Folie in weiteren Ausführungsformen bis zu 45 Gew.-%, bevorzugt bis zu 30 Gew.-%, besonders bevorzugt bis zu 20 Gew.-%, bezogen auf das Gesamtgewicht der Folie, andere Polymere wie Polyetherimide (z. B. Ultem® 1000 von GE Plastics Europe, NL) Polycarbonate (z. B. Makrolon® von Bayer, DE), Polyolefine wie COCs (z. B. Topas® von Ticona, DE), Polyamide (Ultramid® von BASF, DE) u. a. enthalten.The stated polyesters can also be used as mixtures. PET is particularly preferred. In addition to the main polymer constituents mentioned, in further embodiments the film may contain up to 45% by weight, preferably up to 30% by weight, more preferably up to 20% by weight, based on the total weight of the film, of other polymers such as polyetherimides (e.g. . B. Ultem ® 1000 from GE Plastics Europe, NL) polycarbonates (for. example, Makrolon ® from Bayer, DE), polyolefins such as COC (z. B. Topas ® from Ticona, Germany), polyamides (Ultramid ® from BASF, DE) and others.
Allgemein werden die Polyester nach literaturbekannten Verfahren aus den genannten Diolen und Dicarbonsäuren oder Dicarbonsäureestem hergestellt. Die Herstellung der Polyester kann sowohl nach dem Umesterungsverfahren mit den üblichen Katalysatoren wie Zn-, Ca-, Li- und Mn-Salzen oder nach dem Direkt- veresterungsverfahren erfolgen. Erfindungsgemäße Polyester sind im Handel erhältlich.In general, the polyesters are prepared by literature methods from said diols and dicarboxylic acids or Dicarbonsäureestem. The preparation of the polyesters can be carried out both by the transesterification process with the customary catalysts such as Zn, Ca, Li and Mn salts or by the direct esterification process. Polyesters of the invention are commercially available.
Die Bariumsulfatpartikel können nach bekannten Verfahren hergestellt werden wie z. B. in WO 00/76919 beschrieben bzw. es können kommerziell erhältliche Produkte wie die der ®Blanc Fix Reihe der Firma Sachtleben, DE1 eingesetzt werden. Diese Partikel können nach bekannten Verfahren bevorzugt mit einem anorganischen Coating überzogen werden. Solche Verfahren sind u. a. in EP-A-O 459 552 (Spalte 3 und Beispiele) oder DE-A-103 33 029 ([0027] - [0037] und Beispiele 1-3) und DE-A- 10 2006 031 630 beschrieben, wobei das SoI-GeI Verfahren bevorzugt ist.The Bariumsulfatpartikel can be prepared by known methods such as. B. in WO 00/76919 described or it can commercially available products such as the ® Blanc Fix series from Sachtleben, DE 1 are used. These particles can be coated by known methods preferably with an inorganic coating. Such processes are described inter alia in EP-AO 459 552 (column 3 and examples) or DE-A-103 33 029 ([0027] - [0037] and examples 1-3) and DE-A-10 2006 031 630, wherein the SoI-GeI method is preferred.
Als Coatings kommen Oxide oder deren Mischungen oder Mischoxide von Si, AI, Sn, Fe, In, Zr, Ce und Sb in Frage, wobei Oxide von Si und AI bevorzugt sind und besonders bevorzugt Mischoxide von Si und AI oder reine Siliziumoxide zum Einsatz kommen, insbesondere Siθ2 und AI2O3 bzw. deren Mischungen/Mischoxide. Der Anteil dieser Oxide (Coating) am Gesamtgewicht der beschichteten Partikel liegt üblicherweise unter 15 Gew.-%, bevorzugt unter 3 Gew.-% und besonders bevorzugt unter 2 Gew.-%. Ein niedriger Anteil der Beschichtung am Gesamtgewicht der Partikel wirkt sich günstig auf die Trübung der Folie aus, da der Brechungsindex von BaSO4 so ein höheres Gewicht behält. Unter einem Gewichtsanteil von 0,1 Gew.-% für das Coating ist eine flächendeckende Beschichtung der Partikel sehr schwierig,
und es kommt u. U. zu Einbußen bei der Einbindung der Partikel in den Polyester und dadurch erneut zu einem Trübungsanstieg bei der resultierenden Folie. Günstig ist ein Anteil der Beschichtung von > 0,3 Gew.-% und besonders günstig von > 0,7 Gew.-%.Suitable coatings are oxides or mixtures thereof or mixed oxides of Si, Al, Sn, Fe, In, Zr, Ce and Sb, oxides of Si and Al being preferred, mixed oxides of Si and Al or pure silicon oxides being particularly preferred , in particular SiO 2 and Al 2 O 3 or mixtures thereof / mixed oxides. The proportion of these oxides (coating) in the total weight of the coated particles is usually below 15 wt .-%, preferably below 3 wt .-% and particularly preferably below 2 wt .-%. A low proportion of the coating in the total weight of the particles has a favorable effect on the haze of the film, since the refractive index of BaSO 4 thus maintains a higher weight. At a weight fraction of 0.1% by weight for the coating, blanket coating of the particles is very difficult. and it comes u. U. to losses in the integration of the particles in the polyester and thereby again to a turbidity increase in the resulting film. A proportion of the coating of> 0.3 wt .-% and particularly favorable of> 0.7 wt .-% is favorable.
Die beschichteten Bariumsulfatpartikel werden der Folie in einer Menge von bevorzugt 0,005 bis 20 Gew.-% zugesetzt. Üblicherweise liegt der Gehalt zwischen 0,01 und 5 Gew.-% (jeweils bezogen auf das Gesamtgewicht der Folie).The coated barium sulfate particles are added to the film in an amount of preferably 0.005 to 20 wt .-%. Usually, the content is between 0.01 and 5 wt .-% (in each case based on the total weight of the film).
Neben den Bariumsulfatpartikeln kann die erfindungsgemäße Folie weitere partikuläre Additive wie z. B. Antiblockmittel enthalten. Typische Antiblockmittel sind anorganische und/oder organische Partikel, beispielsweise Siliciumdioxid (natürlich, gefällt oder pyrogen), Calciumcarbonat, Magnesiumcarbonat, Bariumcarbonat, Calciumsulfat, Bariumsulfat (nicht anorganisch gecoated), Lithiumphosphat, Calciumphosphat, Magnesiumphosphat, Titandioxid (Rutil oder Anatas), Kaolin (hydratisiert oder kalziniert), Aluminiumoxid, Aluminiumsilikat, Lithiumfluorid, Calcium-, Barium-, Zink- oder Mangansalze der eingesetzten Dicarbonsäuren oder vernetzte Polymerpartikel, z. B. Polystyrol oder Polymethylmethacrylatpartikel, vorzugsweise wird das gecoatete Bariumsulfat mit Siliciumdioxid als Antiblockmittel kombiniert.In addition to the Bariumsulfatpartikeln the film according to the invention further particulate additives such. B. antiblocking agents. Typical antiblocking agents are inorganic and / or organic particles, for example silica (natural, precipitated or pyrogenic), calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate (not inorganically coated), lithium phosphate, calcium phosphate, magnesium phosphate, titanium dioxide (rutile or anatase), kaolin ( hydrated or calcined), alumina, aluminum silicate, lithium fluoride, calcium, barium, zinc or manganese salts of the dicarboxylic acids or crosslinked polymer particles, e.g. Polystyrene or polymethyl methacrylate particles, preferably the coated barium sulfate is combined with silica as the antiblocking agent.
Die sonstigen partikulären Additive haben eine mittlere Größe (d50-Wert) von üblicherweise 0,01 bis 15 μm, bevorzugt 0,03 bis 10 μm und besonders bevorzugt 0,05 bis 5 μm. In einer bevorzugten Ausführungsform liegt der Anteil von Partikeln mit einem dso-Wert von größer/gleich 3 μm bei kleiner/gleich 2000 ppm und besonders bevorzugt bei kleiner/gleich 1000 ppm.The other particulate additives have an average size (d 50 value) of usually 0.01 to 15 .mu.m, preferably 0.03 to 10 .mu.m and particularly preferably 0.05 to 5 microns. In a preferred embodiment, the proportion of particles having a d 50 value of greater than or equal to 3 μm is less than or equal to 2000 ppm and particularly preferably less than or equal to 1000 ppm.
In einer bevorzugten Ausführungsform ist die Menge in Gew.-% an gecoatetem Bariumsulfat größer als die Summe der anderen Füllstoffe/Partikel in Gew.-%, besonders bevorzugt sind Ausführungen, in denen der Füllstoff zu mindestens 85 Gew.-% aus dem beschichteten Bariumsulfat besteht.
Es können auch Mischungen von zwei oder mehreren der oben genannten Partikelsysteme oder Mischungen von Partikelsystemen mit gleicher chemischer Zusammensetzung, aber unterschiedlicher Partikelgröße gewählt werden. Die Partikel werden dem Polyester zweckmäßigerweise schon vor dem Aufschmelzen zugesetzt.In a preferred embodiment, the amount in wt .-% of coated barium sulfate is greater than the sum of the other fillers / particles in wt .-%, particularly preferred are embodiments in which the filler to at least 85 wt .-% of the coated barium sulfate consists. It is also possible to select mixtures of two or more of the abovementioned particle systems or mixtures of particle systems having the same chemical composition but different particle size. The particles are added to the polyester advantageously before melting.
Die Folie hat einen ein- oder mehrschichtigen Aufbau, wobei mehrschichtige Aufbauten bevorzugt sind. Besonders bevorzugt sind dabei mindestens dreischichtige Aufbauten. Das beschichtete Bariumsulfat wird dabei bevorzugt nur einer oder beiden Außenschichten zugegeben. Auch die eventuell vorhandenen anderen Partikel werden bevorzugt nur in die Außenschichten dosiert. Partikel in innen liegenden Schichten stammen bevorzugt aus Eigenregenerat der jeweiligen Folie. Bevorzugt liegt der Anteil von beschichtetem Bariumsulfat in mindestens einer Außenschicht zwischen 0,01 und 20 Gew.-% und besonders bevorzugt zwischen 0,1 und 5 Gew.-% (bezogen auf das Gesamtgewicht der entsprechenden Außenschicht). Das Gewicht der beschichtetes Bariumsulfat enthaltenden Schicht liegt bevorzugt bei mindestens 2 Gew.-% des Gesamtfoliengewichtes, besonders bevorzugt bei mindestens 5 Gew.-% des Gesamtfoliengewichtes.The film has a monolayer or multilayer structure, with multilayer constructions being preferred. Particularly preferred are at least three-layered structures. The coated barium sulfate is preferably added to only one or both outer layers. The possibly present other particles are preferably metered only in the outer layers. Particles in internal layers preferably originate from self-regenerated material of the respective film. Preferably, the proportion of coated barium sulfate in at least one outer layer is between 0.01 and 20 wt .-% and particularly preferably between 0.1 and 5 wt .-% (based on the total weight of the corresponding outer layer). The weight of the coated barium sulfate-containing layer is preferably at least 2 wt .-% of the total film weight, more preferably at least 5 wt .-% of the total film weight.
In mehrschichtigen Aufbauten liegt der Anteil aller partikulären Additive, inkl. des gecoateten Bariumsulfats, üblicherweise unter 5 Gew.-%, bevorzugt unter 1 Gew.-% und besonders bevorzugt unter 0,5 Gew.-%, bezogen auf das Gesamtgewicht der Folie. Die erfindungsgemäße Folie kann weitere Additive wie Farbstoffe, UV-Stabilisatoren, Flammschutzmittel, Hydrolysestabilisatoren und/oder Antioxidantien ent- halten, wobei insbesondere UV-Stabilisatoren der Tinuvin®-Reihe der Fa. Ciba SC, CH, bevorzugt sind.In multilayer constructions, the proportion of all particulate additives, including the coated barium sulfate, is usually less than 5 wt .-%, preferably less than 1 wt .-% and particularly preferably less than 0.5 wt .-%, based on the total weight of the film. The inventive film can keep corresponds other additives such as dyes, UV stabilizers, flame retardants, hydrolysis and / or antioxidants, in particular UV stabilizers Tinuvin ® series of Messrs. Ciba SC, CH, are preferred.
Ebenso kann die Folie zur Einstellung weiterer Eigenschaften beschichtet werden. Typische Beschichtungen sind insbesondere haftvermittelnd, antistatisch, schlupf- verbessernd oder dehäsiv wirkende Schichten. Es bietet sich an, diese zusätzlichen Schichten über In-line-coating mittels wässriger Dispersionen nach der Längs- und vor der Querstreckung auf die Folie aufzubringen.
Die Additive, also die beschichteten Bariumsulfatpartikel und die gegebenenfalls vorhandenen weiteren Füllstoffe und sonstigen Additive (wie UV-Stabilisatoren) werden bevorzugt mittels eines handelsüblichen Zweischneckenextruders in das Polymer eingebracht. Dabei wird der Polyester gemäß der Erfindung in Granulatform zusammen mit den Partikeln/Additiven in den Extruder eingebracht und extrudiert, anschließend in einem Wasserbad abgeschreckt und dann granuliert.Likewise, the film can be coated to adjust other properties. Typical coatings are in particular adhesion-promoting, antistatic, slip-improving or dehesive-acting layers. It is advisable to apply these additional layers to the film via in-line coating by means of aqueous dispersions after the longitudinal and before the transverse stretching. The additives, ie the coated barium sulfate particles and optionally present further fillers and other additives (such as UV stabilizers) are preferably introduced into the polymer by means of a commercially available twin-screw extruder. In this case, the polyester is introduced according to the invention in granular form together with the particles / additives in the extruder and extruded, then quenched in a water bath and then granulated.
Die Additive können aber auch direkt bei der Polyesterherstellung zugegeben werden. Für Farbstoffe und UV-Stabilisatoren ist dieses Verfahren, wegen des zusätzlichen thermischen Stresses weniger bevorzugt. Üblicherweise werden die Additive im Falle des DMT-Verfahrens (DMT = Dimethylterephthalat) nach der Umesterung bzw. direkt vor der Polykondensation (z. B. über die Transportleitung zwischen Umesterungs- und Polykondensationskessel) als glykolische Dispersion zugegeben. Die Zugabe kann aber auch schon vor der Umesterung erfolgen. Im Falle des TPA-Ve rfahrens (TPA= Terephthalic Acid) erfolgt die Zugabe bevorzugt zu Beginn der Polykondensation. Eine spätere Zugabe ist jedoch auch möglich. Es hat sich bei diesem Verfahren als günstig erwiesen, wenn die glykolischen Dispersionen vor der Zugabe über einen PROGAF PGF 57® (Hayward, Indiana, US)-Filter filtriert werden. Dieses Verfahren ist für Rohstoffe, die SiO2 Partikel enthalten, bevorzugt, da sich diese nur schlecht im Extrusionsmasterbatchverfahren einarbeiten lassen.However, the additives can also be added directly during the polyester production. For dyes and UV stabilizers, this method is less preferred because of the added thermal stress. In the case of the DMT process (DMT = dimethyl terephthalate), the additives are usually added after the transesterification or directly before the polycondensation (for example via the transport line between transesterification and polycondensation vessel) as a glycolic dispersion. The addition can also be done before the transesterification. In the case of the TPA method (TPA = terephthalic acid), the addition is preferably carried out at the beginning of the polycondensation. However, a later addition is also possible. It has proven advantageous in this method, the glycolic dispersions are filtered prior to the addition of a PGF PROGAF 57 ® (Hayward, Indiana, US) filter. This method is preferred for raw materials containing SiO 2 particles, since these can be incorporated poorly in the extrusion masterbatch process.
Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung der Folie. Allgemein erfolgt die Herstellung durch ein Extrusionsverfahren. Als besonders vorteilhaft hat es sich erwiesen, alle Additive wie Partikel, UV-Stabilisatoren, Flamm- Schutzmittel, Hydrolysestabilisatoren und Antioxidantien in den genannten Mengen in Form von Masterbatchen vor der Extrusion zuzugeben.The present invention also provides a process for producing the film. In general, the production is carried out by an extrusion process. It has proven to be particularly advantageous to add all additives such as particles, UV stabilizers, flameproofing agents, hydrolysis stabilizers and antioxidants in the amounts mentioned in the form of masterbatches prior to extrusion.
Bevorzugt bei der Masterbatchtechnologie ist, dass additivhaltige Polyesterrohstoffe mit ungefüllten billigen Rohstoffen kombiniert werden können. Die Kosten sind dabei zwar bedingt abhängig vom Füllgrad, aber der größte Kostenschritt ist das Vorhandensein von Additiv an sich. Daher ist es wirtschaftlich vorteilhaft, ein möglichst hochgefülltes Masterbatch mit einem ungefüllten Polyester zu kombinieren.
Die Polyesterfolien können nach bekannten Verfahren aus einem Polyesterrohstoff und gegebenenfalls weiteren Rohstoffen als ein- oder mehrschichtige Folie hergestellt werden.Preferred in masterbatch technology is that additive-containing polyester raw materials can be combined with unfilled cheap raw materials. Although the costs are conditionally dependent on the degree of filling, but the largest cost step is the presence of additive itself. Therefore, it is economically advantageous to combine a highly filled masterbatch with an unfilled polyester. The polyester films can be prepared by known methods from a polyester raw material and optionally other raw materials as a single or multilayer film.
Die Masterbatche sowie die übrigen Rohstoffe können bei Verwendung von Zwei- und Mehrschneckenextrudern ohne Vortrocknung direkt extrudiert werden. Bei Einschneckenextrudern empfiehlt sich eine Trocknung bei 120 bis 150 0C für mindestens 1 Stunde.The masterbatches and the other raw materials can be extruded directly without the use of pre-drying when using twin-screw and multi-screw extruders. For single-screw extruders, drying at 120 to 150 ° C is recommended for at least 1 hour.
Bei dem bevorzugten Coextrusionsverfahren zur Herstellung der Folie werden die den einzelnen Schichten der Folie entsprechenden Schmelzen durch eine Flachdüse coextrudiert und als weitgehend amorphe Vorfolie auf einer Kühlwalze abgeschreckt. Diese Folie wird anschließend erneut erhitzt und in mindestens einer Richtung bzw. in Längs- und Querrichtung bzw. in Quer- und Längsrichtung bzw. in Längs-, in Quer- und nochmals in Längsrichtung und /oder Querrichtung verstreckt (orientiert). Die Folientemperaturen im Streckprozess liegen im allgemeinen 10 bis 60 °C über der Glasübergangstemperatur T9 des verwendeten Polyesters, das Streckverhältnis der Längsstreckung liegt bevorzugt bei 2 bis 6, insbesondere bei 3 bis 4,5, das der Querstreckung bei 2 bis 5, insbesondere bei 3 bis 4,5, und das der gegebenenfalls durchgeführten zweiten Längs- und Querstreckung bei 1 ,1 bis 5. Die erste Längsstreckung kann auch gleichzeitig mit der Querstreckung (Simultanstreckung) durchgeführt werden. Es folgt die Thermofixierung der Folie bei Ofentemperaturen von ca. 180 bis 260 0C, vorzugsweise von 220 bis 250 0C. Anschließend wird die Folie abgekühlt und gewickelt. Eine biaxial orientierte Folie ist bevorzugt.In the preferred coextrusion process for the production of the film, the melts corresponding to the individual layers of the film are coextruded through a flat die and quenched as a largely amorphous prefilm on a chill roll. This film is then reheated and stretched (oriented) in at least one direction or in the longitudinal and transverse direction or in the transverse and longitudinal direction or in the longitudinal direction, in the transverse direction and again in the longitudinal direction and / or transverse direction. The film temperatures in the stretching process are generally 10 to 60 ° C above the glass transition temperature T 9 of the polyester used, the draw ratio of the longitudinal stretching is preferably from 2 to 6, in particular from 3 to 4.5, that of the transverse extension at 2 to 5, in particular at 3 to 4.5, and that of the optionally performed second longitudinal and transverse extension at 1, 1 to 5. The first longitudinal stretching can also be carried out simultaneously with the transverse extension (simultaneous stretching). This is followed by the heat-setting of the film at oven temperatures of about 180 to 260 ° C., preferably from 220 to 250 ° C. The film is then cooled and wound. A biaxially oriented film is preferred.
In einer bevorzugten Ausführungsform findet die Thermofixierung bei Temperaturen von 220 bis 250 0C statt und die Folie wird bei dieser Temperatur um mindestens 1 %, bevorzugt mindestens 2 %, in Querrichtung relaxiert.In a preferred embodiment, the heat-setting takes place at temperatures of 220 to 250 ° C. and the film is relaxed at this temperature by at least 1%, preferably at least 2%, in the transverse direction.
In einer weiteren bevorzugten Ausführungsform findet die Thermofixierung bei 220 bis 250 0C statt, und die Folie wird bei dieser Temperatur um mindestens 1 %, bevorzugt mindestens 2 %, in Querrichtung relaxiert und anschließend nochmals bei
Temperaturen zwischen 180 und 150 0C in der Abkühlphase um wiederum mindestens 1 %, bevorzugt mindestens 2 %, in Querrichtung relaxiert.In a further preferred embodiment, the heat-setting takes place at 220 to 250 ° C., and the film is relaxed at this temperature by at least 1%, preferably at least 2%, in the transverse direction and then again at Temperatures between 180 and 150 0 C in the cooling phase again by at least 1%, preferably at least 2%, relaxed in the transverse direction.
In einer weiteren bevorzugten Ausführungsform wird die Folie mindestens um den Faktor 3 in MD- und TD-Richtung gestreckt, wobei die Streckung in einem Simultanrahmen stattfindet. Die Thermofixierung findet bei 220 bis 250 0C statt, und die Folie wird bei dieser Temperatur um mindestens 1 % in Längs- und Querrichtung relaxiert (MD = Maschinen- oder Längsrichtung, TD= Querrichtung).In a further preferred embodiment, the film is stretched at least by a factor of 3 in the MD and TD directions, the stretching taking place in a simultaneous frame. The heat-setting takes place at 220 to 250 ° C., and the film is relaxed at this temperature by at least 1% in the longitudinal and transverse directions (MD = machine direction or longitudinal direction, TD = transverse direction).
Die erfindungsgemäßen ein- oder mehrschichtigen Folien weisen die geforderten guten mechanischen Eigenschaften auf. So ist der E-Modul in mindestens einer Folienrichtung bevorzugt größer/gleich 500 N/mm2.The monolayer or multilayer films according to the invention have the required good mechanical properties. Thus, the modulus of elasticity in at least one film direction is preferably greater than or equal to 500 N / mm 2 .
Die Folie weist in keiner Folienrichtung (weder in MD noch in TD) einen Schrumpf von größer 25 % bei 200 °C auf.The film has no shrinkage of more than 25% at 200 ° C. in either direction (neither MD nor TD).
Dadurch, dass sich die beschichteten Bariumsulfatpartikel auch in Konzentrationen oberhalb von 3 Gew.-% und sogar oberhalb von 7 Gew.-% in Masterbatche, insbesondere auch in Extrusionsmasterbatche, einarbeiten lassen, sind erhebliche Rohstoffkosteneinsparungen gegenüber Siθ2-gefüllten Rohstoffen möglich.As a result of the fact that the coated barium sulfate particles can also be incorporated in masterbatches, in particular in extrusion masterbatches, in concentrations above 3% by weight and even above 7% by weight, substantial savings in raw material costs compared to SiO 2 -filled raw materials are possible.
Die Folie eignet sich für fast alle bekannten Polyesterfolienanwendungen wie Verpackungsanwendungen, für die Metallisierung, für Motorfolie etc. und im besonderen Maße für alle Anwendungen, die gute optische Eigenschaften der Folie, wie z. B. hohe Transparenz, benötigen.The film is suitable for almost all known polyester film applications such as packaging applications, for metallization, for motor film, etc., and in particular for all applications that have good optical properties of the film, such. B. high transparency, need.
Die Messung der einzelnen Eigenschaften gemäß der Beschreibung und in den Beispielen erfolgt nach den folgenden Normen bzw. Verfahren:The measurement of the individual properties according to the description and in the examples is carried out according to the following standards and procedures:
Messmethodenmeasurement methods
DIN = Deutsches Institut für NormungDIN = German Institute for Standardization
ISO = Internat. Organization for StandardizationISO = boarding. Organization for Standardization
ASTM = American Society for Testing and Materials
Mechanische EigenschaftenASTM = American Society for Testing and Materials Mechanical properties
Der E-Modul, die Reißfestigkeit, Reißdehnung und der F5-Wert werden in Längsund Querrichtung nach ISO 527-1-2 mit Hilfe eines Zug-Dehnungsmessers (Typ 010 der Fa. Zwick/DE) gemessen.The modulus of elasticity, tear strength, elongation at break and F 5 value are measured in the longitudinal and transverse directions according to ISO 527-1-2 with the aid of a tensile strain gauge (type 010 from Zwick / DE).
Schrumpfshrink
Der thermische Schrumpf wird an quadratischen Folienmustern mit einer Kantenlänge von 10 cm bestimmt. Die Proben werden genau ausgemessen (Kantenlänge Lo), 15 min bei 200 0C in einem Umlufttrockenschrank getempert und anschließend bei Raumtemperatur genau ausgemessen (Kantenlänge L). Der Schrumpf ergibt sich aus der GleichungThe thermal shrinkage is determined on square film samples with an edge length of 10 cm. The samples are measured precisely (edge length Lo), 15 min heat-treated at 200 0 C in a convection oven and then measured precisely at room temperature (edge length L). The shrinkage results from the equation
Schrumpf [%] = 100 . (L0- L) / L0 Shrinkage [%] = 100. (L 0 -L) / L 0
Messung des mittleren Durchmessers (Teilchengröße) d50 Measurement of the mean diameter (particle size) d 50
Die Bestimmung des mittleren Durchmessers d50 wird mittels Laser auf einem Malvern Master Sizer (Malvern Instruments Ltd., GB) nach der Standardmethode durchgeführt. Andere Messgeräte sind z. B. Horiba LA 500 (HORIBA Europe GmbH, DE) oder Sympathec Helos (Sympathec GmbH, DE), welche das gleiche Messprinzip verwenden. Die Proben werden dazu in eine Küvette mit Wasser gegeben und diese dann in das Messgerät gestellt. Der Messvorgang ist automatisch und beinhaltet auch die mathematische Bestimmung des d5o-Wertes.The determination of the mean diameter d 50 is carried out by laser on a Malvern Master Sizer (Malvern Instruments Ltd., GB) according to the standard method. Other measuring devices are z. Horiba LA 500 (HORIBA Europe GmbH, DE) or Sympathec Helos (Sympathec GmbH, DE), which use the same measuring principle. The samples are then placed in a cuvette with water and then placed in the meter. The measuring process is automatic and also includes the mathematical determination of the d 5 o value.
Der dso-Wert wird dabei definitionsgemäß aus der (relativen) Summenkurve der Partikelgrößenverteilung bestimmt. Der Schnittpunkt des 50 %-Ordinatenwertes mit der Summenkurve liefert auf der Abszissenachse sofort den gewünschten d50-Wert (vgl. dazu Figur 1).
Messung der TrübungBy definition, the dso value is determined from the (relative) cumulative curve of the particle size distribution. The point of intersection of the 50% ordinate value with the cumulative curve immediately gives the desired d 50 value on the abscissa axis (see FIG. Measurement of turbidity
Die Messung erfolgt an dem Hazegard Hazemeter XL-211 der Fa. BYK Gardner (s.The measurement is carried out on the Hazegard Hazemeter XL-211 from BYK Gardner (s.
Figur 2). Das Messgerät ist 30 min vor der Messung einzuschalten. Es ist darauf zu achten, dass der Lichtstrahl durch die Kugel zentrisch an die Austrittsöffnung geht.Figure 2). The meter should be turned on 30 minutes before the measurement. It is important to ensure that the light beam passes through the ball centric to the outlet opening.
Herstellung, Form und Anzahl der ProbenProduction, shape and number of samples
Aus der zu untersuchenden Folie werden je 5 Proben mit einer Größe von 100 x 100 mm ausgeschnitten. Die Längs- und Querrichtung werden am Rand gekennzeichnet, da die Messungen in beiden Maschinenrichtungen erfolgen.From the film to be examined each 5 samples are cut out with a size of 100 x 100 mm. The longitudinal and transverse directions are marked on the edge, since the measurements are made in both machine directions.
Messung der TrübungMeasurement of turbidity
Schalter 1 „OPEN" drückenPress switch 1 "OPEN"
Schalter 2 auf „X10" einstellen und mit dem „Zero"-Knopf Digitalanzeige aufSet switch 2 to "X10" and use the "Zero" knob to set digital display
0.00 kalibrieren - Umschalten des Schalters 1 auf „Referenz" und des Schalters 2 auf „X1"0.00 calibrate - switch of switch 1 to "reference" and switch 2 to "X1"
Mit dem „Calibrate"-Knopf Digitalanzeige auf 100 bringenUse the "Calibrate" button to bring the digital display to 100
Probe in Längsrichtung einlegenInsert sample lengthwise
Die Digitalanzeige mit dem „Calibrate"-Knopf auf 100 kalibrierenCalibrate the digital readout to 100 using the "Calibrate" button
Schalter 1 auf „OPEN" stellen - Anzeigewert für die Trübung in Längsrichtung ablesenSet switch 1 to "OPEN" - Read off the display value for the turbidity in the longitudinal direction
Probe in Querrichtung drehenTurn the sample in the transverse direction
Anzeigewert für die Trübung in Querrichtung ablesenRead off the display value for the turbidity in the transverse direction
Auswertung Die Trübung erhält man durch die Mittelung der jeweiligen 5 Einzelwerte (längs und quer).Evaluation The turbidity is obtained by averaging the respective 5 individual values (longitudinal and transverse).
Gelbwertyellowness
Der Gelbwert G (YID) ist die Abweichung von der Farblosigkeit in Richtung "Gelb" und wird gemäß DIN 6167 gemessen.The yellow value G (YID) is the deviation from the colorlessness in the direction "yellow" and is measured according to DIN 6167.
Transparenztransparency
Die Transparenz wird nach ASTM-D 1033-77 gemessen.
RauigkeitThe transparency is measured according to ASTM-D 1033-77. roughness
Die Rauigkeit Ra der Folie wird nach DIN 4768 bestimmt.The roughness R a of the film is determined according to DIN 4768.
Folienherstellungfilm production
Polyester-Chips werden gemäß den in den Beispielen angegebenen Verhältnissen gemischt und ohne Vortrocknung jeweils in Zweischneckenextrudern aufgeschmolzen. Die geschmolzenen Polymerstränge werden in einer Coextrusionsdüse zusammengeführt und über eine Abzugswalze (Temperatur der Walze 20 0C) abgezogen. Der Film wird um den Faktor 3,9 in Maschinenrichtung bei 116 0C (Folientemperatur im Streckspalt) gestreckt und in einem Rahmen bei 110 0C eine Querstreckung um den Faktor 3,8 durchgeführt. Anschließend wird die Folie bei 229 0C thermofixiert und in Querrichtung um 1 ,5 % bei Temperaturen von 225 0C und ein weiteres Mal um 1 ,5 % bei Temperaturen zwischen 180 und 150 0C relaxiert. Die Produktions- geschwindigkeit (Endfoliengeschwindigkeit) beträgt 300 m/min.Polyester chips are mixed according to the ratios given in the examples and melted without predrying in twin-screw extruders. The molten polymer strands are brought together in a coextrusion die and drawn off via a draw-off roll (roll temperature 20 0 C). The film is stretched by a factor of 3.9 in the machine direction at 116 ° C. (film temperature in the drawing nip) and in a frame at 110 ° C. a transverse extension of a factor of 3.8 is carried out. Subsequently, the film is heat set at 229 0 C and relaxed in the transverse direction by 1, 5% at temperatures of 225 0 C and a second time to 1, 5% at temperatures from 180 to 150 0 C. The production speed (final film speed) is 300 m / min.
BeispieleExamples
In den Beispielen kommen die folgenden Rohstoffe zum Einsatz:The following raw materials are used in the examples:
Masterbatch MB1Masterbatch MB1
Extrusionsmasterbatch mit 10 Gew.-% BaSO4 (BaSO4 = Blanc Fixe® N, mittlere Partikelgröße d5o = 1 J μm, der Firma Solvay Chemicals wurde mit einer Schicht aus SiO2 90 % und AI2O3 10 % überzogen, wobei der Anteil an SiO2MI2O3 bei 1 ,8 Gew.-%, bezogen auf das Bariumsulfat, lag, so dass der Anteil an Bariumsulfat etwa 98 Gew.-% betrug) in Polyethylenterephthalat (PET). Das beschichtete Bariumsulfat wurde dabei zusammen mit dem Polyesterrohstoff T94 der Firma Invista, DE, in die Einzugszone eines Werner und Pfleiderer (DE) -Zweischneckenextruders dosiert und extrudiert und granuliert.
Herstellung des beschichteten Bariumsulfats:Extrusion masterbatch (10 wt .-% BaSO 4 BaSO 4 = Blanc Fixe ® N, mean particle size d 5 o = 1 J microns, Solvay Chemicals was coated with a layer of SiO 2 90%, Al 2 O 3 10%, wherein the proportion of SiO 2 MI 2 O 3 at 1, 8 wt .-%, based on the barium sulfate, so that the proportion of barium sulfate was about 98 wt .-%) in polyethylene terephthalate (PET). The coated barium sulfate was metered together with the polyester raw material T94 from Invista, DE, into the feed zone of a Werner and Pfleiderer (DE) twin-screw extruder and extruded and granulated. Preparation of the coated barium sulfate:
2000 g BaSO4 (Blanc Fixe® N) wurden mit einem Balkenrührer in etwa 5 I TE- Wasser (TE: teilentsalzt) eingerührt. Die Suspension wurde auf 80 0C erhitzt und mittels NaOH und Schwefelsäure auf einen pH-Wert von 6,5 gebracht. Anschließend wurden bei 80 CC zu der Suspension 150 ml Wasserglaslösung (entsprechend 380 g SiO2/l) bei konstantem pH-Wert (pH = 6,5 +- 0,5; Regelung durch Zugabe von H2SO4) zugegeben. Nach erfolgter Zugabe wurde bei pH = 6,8 und 80 0C 20 min gerührt und dann mit NaOH auf einen pH von 7,0 eingestellt. Anschließend wurden 25 ml Natriumaluminat-Lösung (Gehalt entspricht 300 g AI2O3 pro Liter) bei konstantem pH-Wert langsam (8 ml/min) zugegeben. Der pH-Wert wurde mit Hilfe von Schwefelsäure während der Zugabe bei konstant pH = 7 gehalten. Nach erfolgter Zugabe wurde bei pH = 7 und 80 °C zwei Stunden gerührt. Danach wurde das Material abgenutscht, der Filterkuchen bis zu einer Filtratleitfähigkeit unter 100 μS/cm gewaschen und bei 105 0C im Trockenschrank getrocknet. Anschließend wird das Produkt noch 30 min in einem Muffelofen bei 500 0C getempert.2000 g of BaSO 4 (Blanc Fixe® N) were stirred with a bar stirrer into about 5 l of TE water (TE: partially desalted). The suspension was heated to 80 ° C. and brought to pH 6.5 using NaOH and sulfuric acid. Subsequently, 150 ml of waterglass solution (corresponding to 380 g of SiO 2 / l) were added to the suspension at 80 ° C. at constant pH (pH = 6.5 + -0.5, control by addition of H 2 SO 4 ). After the addition was stirred at pH = 6.8 and 80 0 C for 20 min and then adjusted with NaOH to a pH of 7.0. Subsequently, 25 ml of sodium aluminate solution (content equivalent to 300 g of Al 2 O 3 per liter) were added slowly at constant pH (8 ml / min). The pH was maintained at constant pH = 7 with the aid of sulfuric acid during the addition. After the addition was stirred at pH = 7 and 80 ° C for two hours. Thereafter, the material was filtered off with suction, the filter cake washed to a filtrate conductivity below 100 μS / cm and dried at 105 0 C in a drying oven. Subsequently, the product is tempered for 30 minutes in a muffle furnace at 500 0 C.
Masterbatch MB2Masterbatch MB2
Extrusionsmasterbatch mit 10 Gew.-% SiO2 (Silysia® 320, mittlere Partikelgröße d50 = 2,5 μm, der Firma Fuji Sylysia, JP) in Polyethylenterephthalat (PET). Das Silicium- dioxid wurde dabei zusammen mit dem Polyesterrohstoff T94 der Firma Invista, DE, in die Einzugszone eines Werner und Pfleiderer-Zweischneckenextruders dosiert und extrudiert und granuliert.Extrusionsmasterbatch with 10 wt .-% SiO 2 (Silysia ® 320, average particle size d 50 = 2.5 microns, the company Fuji Sylysia, JP) in polyethylene terephthalate (PET). The silicon dioxide was metered together with the polyester raw material T94 from Invista, DE, into the feed zone of a Werner and Pfleiderer twin-screw extruder and extruded and granulated.
Masterbatch MB3Masterbatch MB3
Extrusionsmasterbatch mit 10 Gew.-% BaSO4 (Hombright® S, mittlere Partikelgröße d50 = 0,5 μm, der Firma Sachtleben Chemie GmbH) in Polyethylenterephthalat (PET). Die Partikel waren mit einer AI (IM) und Si (IV) anorganischen Beschichtung überzogen, wobei der Anteil an Bariumsulfat nur etwa 95 Gew.-% betrug. Das beschichtete Bariumsulfat wurde dabei zusammen mit dem Polyesterrohstoff T94 der Firma Invista in die Einzugszone eines Werner und Pfleiderer- Zweischneckenextruders dosiert und extrudiert und granuliert.
Masterbatch MB4Extrusionsmasterbatch with 10 wt .-% BaSO 4 (Hombright ® S, average particle size d 50 = 0.5 microns, the company Sachtleben Chemie GmbH) in polyethylene terephthalate (PET). The particles were coated with an AI (IM) and Si (IV) inorganic coating, the barium sulfate content being only about 95% by weight. The coated barium sulfate was dosed together with the polyester raw material T94 Invista in the feed zone of a Werner and Pfleiderer twin-screw extruder and extruded and granulated. Masterbatch MB4
Extrusionsmasterbatch mit 10 Gew.-% BaSO4 (Blanc Fixe N, mittlere Partikelgröße 050 =1 ,7 μm, der Firma Solvay Chemicals) in Polyethylenterephthalat (PET). Das unbeschichtete Bariumsulfat wurde dabei zusammen mit dem Polyesterrohstoff T94 der Firma Invista in die Einzugszone eines Werner und Pfleiderer- Zweischneckenextruders dosiert und extrudiert und granuliert.Extrusionsmasterbatch with 10 wt .-% BaSO 4 (Blanc Fixe N, average particle size 0 50 = 1, 7 microns, the company Solvay Chemicals) in polyethylene terephthalate (PET). The uncoated barium sulfate was dosed together with the polyester raw material T94 Invista in the feed zone of a Werner and Pfleiderer twin-screw extruder and extruded and granulated.
Rohstoff R1Raw material R1
100 Gew.-% Polyethylenterephthalat RT49 der Firma Invista, DE100% by weight of polyethylene terephthalate RT49 from Invista, DE
Beispiel 1example 1
Es wurde eine 12 μm ABC-Folie mit einer Dicke der Basisschicht (B) von 8 μm undIt was a 12 microns ABC film with a thickness of the base layer (B) of 8 microns and
Deckschichten A und C mit je 2 μm, wie oben angegeben, hergestellt.Coats A and C each with 2 microns, as stated above, prepared.
Deckschichten A und C: 2 % MB1 und 98 % R1 Rohstoffmischung Basisschicht B: 100 % R1Coats A and C: 2% MB1 and 98% R1 Blend Base Layer B: 100% R1
Herstellung problemfrei. Keine Streifenbildung innerhalb 24 h Produktion . Ein Abriss in 48 h.Production problem-free. No streaking within 24 hours of production. A demolition in 48 h.
Trübung 1 ,8 %. Transparenz 90,5 %. E-Modul in Längsrichtung 4800 N/mm2.Turbidity 1, 8%. Transparency 90.5%. E-module in the longitudinal direction 4800 N / mm 2 .
E-Modul in Querrichtung 5050 N/mm2. Schrumpf bei 200 0C = 3,1 % in Längsrichtung und 0,3 % in Querrichtung. Rauheit Ra = 40 nmE-module in transverse direction 5050 N / mm 2 . Shrinkage at 200 ° C. = 3.1% in the longitudinal direction and 0.3% in the transverse direction. Roughness R a = 40 nm
Vergleichsbeispiel 1Comparative Example 1
Es wurde eine ABC-Folie mit einer Dicke der Basisschicht (B) von 8 μm undIt was an ABC film with a thickness of the base layer (B) of 8 microns and
Deckschichten A und C mit je 2 μm, wie oben angegeben, hergestellt. Deckschichten A und C: 1 ,5 % MB2 und 98,5 % R1Coats A and C each with 2 microns, as stated above, prepared. Coatings A and C: 1, 5% MB2 and 98.5% R1
Rohstoffmischung Basisschicht B: 100 % R1Raw material mixture base layer B: 100% R1
Wirtschaftliche Herstellung nicht möglich. Viele Abrisse (< 10 pro Tag), u. a. durchEconomical production not possible. Many breaks (<10 per day), u. a. by
Druckschwankungen in den Extrudern, welche das MB2 enthalten. Folie streifig und wolkig. Trübung 3,8 %. Transparenz 87 %. E-Modul in Längsrichtung 4750 N/mm2. E-Modul in Querrichtung 4910 N/mm2. Schrumpf bei 200 0C = 3,2 % in Längsrichtung undPressure fluctuations in the extruders containing the MB2. Foil streaky and cloudy. Haze 3.8%. Transparency 87%. E-module in the longitudinal direction 4750 N / mm 2 . Modulus of elasticity in transverse direction 4910 N / mm 2 . Shrinkage at 200 ° C = 3.2% in the longitudinal direction and
0,32 % in Querrichtung. Rauheit R3 = 43 nm
Vergleichsbeispiel 20.32% in the transverse direction. Roughness R 3 = 43 nm Comparative Example 2
Es wurde eine 12 μm ABC-Folie mit einer Dicke der Basisschicht (B) von 8 μm und Deckschichten A und C mit je 2 μm, wie oben angegeben, hergestellt. Deckschichten A und C: 2 % MB3 und 98 % R1 Rohstoffmischung Basisschicht B: 100 % R1A 12 μm ABC film with a thickness of the base layer (B) of 8 μm and cover layers A and C with 2 μm each, as stated above, was produced. Coats A and C: 2% MB3 and 98% R1 Blend Base Layer B: 100% R1
Herstellung problemfrei. Keine Streifenbildung innerhalb 24 h Produktion . Ein Abriss in 48 h. Die Aufwicklung der Folie war jedoch aufgrund der niedrigen Oberflächenrauheit schwierig, und es kam zu Faltenbildung und Längsrillen. Trübung 1 ,1 %. Transparenz 91 %. E-Modul in Längsrichtung 4830 N/mm2. E-Modul in Querrichtung 5010 N/mm2. Schrumpf bei 200 0C = 3,2 % in Längsrichtung und 0,3 % in Querrichtung. Rauheit R3 = 9 nmProduction problem-free. No streaking within 24 hours of production. A demolition in 48 h. However, the winding of the film was difficult due to the low surface roughness, and wrinkling and longitudinal grooves occurred. Turbidity 1, 1%. Transparency 91%. E-module in the longitudinal direction 4830 N / mm 2 . Modulus of elasticity in transverse direction 5010 N / mm 2 . Shrinkage at 200 ° C = 3.2% in the longitudinal direction and 0.3% in the transverse direction. Roughness R 3 = 9 nm
Vergleichsbeispiel 3Comparative Example 3
Es wurde eine ABC-Folie mit einer Dicke der Basisschicht (B) von 8 μm und Deckschichten A und C mit je 2 μm, wie oben angegeben, hergestellt.An ABC film with a thickness of the base layer (B) of 8 μm and cover layers A and C with 2 μm each, as stated above, was produced.
Deckschichten A und C: 2 % MB4 und 98 % R1Coatings A and C: 2% MB4 and 98% R1
Rohstoffmischung Basisschicht B: 100 % R1Raw material mixture base layer B: 100% R1
Herstellung problemfrei. Keine Streifenbildung innerhalb 24 h Produktion . Ein Abriss in 48 h. Es kam jedoch beim Aufwickeln und beim Abschneiden der Ränder zu einer vermehrten Abriebbildung in Form von weißem Staub.Production problem-free. No streaking within 24 hours of production. A demolition in 48 h. However, when the edges were wound up and cut off, there was an increase of abrasion in the form of white dust.
Trübung 11 %. Transparenz 84 %. E-Modul in Längsrichtung 4845 N/mm2. E-Modul in Querrichtung 4930 N/mm2. Schrumpf bei 200 0C = 3,2 % in Längsrichtung undHaze 11%. Transparency 84%. E-module in the longitudinal direction 4845 N / mm 2 . Transverse modulus 4930 N / mm 2 . Shrinkage at 200 ° C = 3.2% in the longitudinal direction and
0,3 % in Querrichtung. Rauheit Ra = 54 nm0.3% in the transverse direction. Roughness R a = 54 nm
* * * * ** * * * *
Claims
1. Orientierte Polyesterfolie enthaltend mit einer anorganischen Beschichtung versehene Bariumsulfatpartikel.1. Oriented polyester film containing barium sulfate particles provided with an inorganic coating.
2. Polyesterfolie nach Anspruch 1 , dadurch gekennzeichnet, dass die Beschichtung Oxide, Mischoxide oder Mischungen von Oxiden von Si, AI, Sn, Fe, In und/oder Sb enthält oder daraus besteht.2. Polyester film according to claim 1, characterized in that the coating oxides, mixed oxides or mixtures of oxides of Si, Al, Sn, Fe, In and / or Sb contains or consists thereof.
3. Polyesterfolie nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Beschichtung Siliciumoxid oder Aluminiumoxid enthält oder daraus besteht.3. Polyester film according to claim 1 or 2, characterized in that the coating contains or consists of silica or alumina.
4. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Beschichtung Mischoxide oder Mischungen von Siliciumoxid und Aluminiumoxid enthält oder daraus besteht.4. Polyester film according to one or more of claims 1 to 3, characterized in that the coating contains mixed oxides or mixtures of silica and alumina or consists thereof.
5. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Beschichtung Mischoxide oder Mischungen von SiO2 und AI2O3 enthält oder daraus besteht.5. Polyester film according to one or more of claims 1 to 4, characterized in that the coating contains mixed oxides or mixtures of SiO 2 and Al 2 O 3 or consists thereof.
6. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die beschichteten Bariumsulfatpartikel eine mittlere Teilchengröße (d50) zwischen 0,7 und 7 μm aufweisen.6. Polyester film according to one or more of claims 1 to 5, characterized in that the coated barium sulfate particles have an average particle size (d 50 ) between 0.7 and 7 microns.
7. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Anteil der Beschichtung am Gesamtgewicht der beschichteten Bariumsulfatpartikel kleiner 15 Gew.-% beträgt.7. Polyester film according to one or more of claims 1 to 6, characterized in that the proportion of the coating in the total weight of the coated barium sulfate particles is less than 15 wt .-%.
8. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der Anteil der Beschichtung am Gesamtgewicht der beschichteten Bariumsulfatpartikel kleiner 3 Gew.-% beträgt. 8. Polyester film according to one or more of claims 1 to 7, characterized in that the proportion of the coating in the total weight of the coated barium sulfate particles is less than 3 wt .-%.
9. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Folie 0,005 bis 20 Gew.-% an beschichteten Bariumsulfatpartikeln enthält.9. Polyester film according to one or more of claims 1 to 8, characterized in that the film contains 0.005 to 20 wt .-% of coated barium sulfate particles.
10. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Folie einen Polyester enthält, der Terephthalsäure- und/oder Naphthalin-2,6-dicarbonsäure-Einheiten aufweist.10. Polyester film according to one or more of claims 1 to 9, characterized in that the film contains a polyester having terephthalic acid and / or naphthalene-2,6-dicarboxylic acid units.
11. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Folie Polyethylenterephthalat enthält.11. Polyester film according to one or more of claims 1 to 10, characterized in that the film contains polyethylene terephthalate.
12. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass die Folie mehrschichtig ist.12. Polyester film according to one or more of claims 1 to 11, characterized in that the film is multi-layered.
13. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Folie einen ABC-Schichtaufbau aufweist, wobei A und C Außen- oder Deckschichten sind und B die Basisschicht ist.13. Polyester film according to one or more of claims 1 to 12, characterized in that the film has an ABC layer structure, wherein A and C are outer or outer layers and B is the base layer.
14. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die Außenschichten und die Basisschicht der Folie den gleichen Polyester enthalten.14. Polyester film according to one or more of claims 1 to 13, characterized in that the outer layers and the base layer of the film contain the same polyester.
15. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass bei einer mindestens 3-schichtigen Folie nur die Außenschichten oder nur eine Außenschicht die beschichteten Bariumsulfatpartikel enthält.15. Polyester film according to one or more of claims 1 to 14, characterized in that in an at least 3-layered film only the outer layers or only one outer layer containing the coated barium sulfate particles.
16. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass bei einer mindestens 3-schichtigen Folie eine oder beide Außenschichten 0,1 bis 3 Gew.-% beschichtete Bariumsulfatpartikel enthalten.16. The polyester film as claimed in one or more of claims 1 to 15, wherein, in the case of an at least 3-layered film, one or both outer layers contain from 0.1 to 3% by weight of coated barium sulfate particles.
17. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass die Folie eine Transparenz zwischen 70 und 99,5 % aufweist.17. Polyester film according to one or more of claims 1 to 16, characterized in that the film has a transparency between 70 and 99.5% having.
18. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass die Folie im Dickenbereich 0,5 bis 50 μm eine Trübung von kleiner 2,5 % aufweist.18. Polyester film according to one or more of claims 1 to 17, characterized in that the film in the thickness range 0.5 to 50 microns has a haze of less than 2.5%.
19. Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 18, dadurch gekennzeichnet, dass die Folie mindestens einseitig eine Rauheit von 10 bis 400 nm aufweist.19. Polyester film according to one or more of claims 1 to 18, characterized in that the film has at least on one side a roughness of 10 to 400 nm.
20. Verfahren zur Herstellung einer Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 19, umfassend die Schritte a) Herstellen einer ein- oder mehrschichtigen Folie durch Extrusion oder20. A process for producing a polyester film according to one or more of claims 1 to 19, comprising the steps of a) producing a single- or multilayer film by extrusion or
Coextrusion, b) Strecken der Folie und c) Thermofixieren der gestreckten Folie.Coextrusion, b) stretching the film and c) heat-setting the stretched film.
21. Verfahren nach Anspruch 20, dadurch gekennzeichnet, dass die Folie bei der Thermofixierung in Querrichtung um mindestens 1 % relaxiert wird.21. The method according to claim 20, characterized in that the film is relaxed in the heat setting in the transverse direction by at least 1%.
22. Verwendung einer Polyesterfolie nach einem oder mehreren der Ansprüche 1 bis 19 als Verpackungsmaterial, als Schutzfolie oder zur Herstellung von Verpackungsmaterial.22. Use of a polyester film according to one or more of claims 1 to 19 as a packaging material, as a protective film or for the production of packaging material.
23. Verwendung von Bariumsulfatpartikeln nach einem oder mehreren der Ansprüche 1 bis 8 zur Herstellung eines Polyesterrohstoffs oder einer Polyesterfolie mit einer Transparenz zwischen 70 und 99,5 %.23. Use of barium sulfate particles according to one or more of claims 1 to 8 for the preparation of a polyester raw material or a polyester film having a transparency between 70 and 99.5%.
* * * ** * * *
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007028349A DE102007028349A1 (en) | 2007-06-20 | 2007-06-20 | Transparent polyester film with BaSO4 particles |
PCT/EP2008/004656 WO2008155050A1 (en) | 2007-06-20 | 2008-06-11 | Transparent polyester film comprising baso4 particles |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2160436A1 true EP2160436A1 (en) | 2010-03-10 |
Family
ID=39745395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08759172A Withdrawn EP2160436A1 (en) | 2007-06-20 | 2008-06-11 | Transparent polyester film comprising baso<sb>4</sb>particles |
Country Status (7)
Country | Link |
---|---|
US (1) | US20110171424A1 (en) |
EP (1) | EP2160436A1 (en) |
JP (1) | JP2010530449A (en) |
KR (1) | KR20100020470A (en) |
CN (1) | CN101743268A (en) |
DE (1) | DE102007028349A1 (en) |
WO (1) | WO2008155050A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007050728A1 (en) | 2007-10-22 | 2009-04-23 | Sachtleben Chemie Gmbh | Additive for polymers and process for its preparation |
JP2009209315A (en) * | 2008-03-06 | 2009-09-17 | Teijin Dupont Films Japan Ltd | Polyester film |
KR101527521B1 (en) * | 2013-10-15 | 2015-06-09 | 주식회사 효성 | A multi-functional polyester film and preparation method thereof |
JP6471853B2 (en) * | 2015-01-26 | 2019-02-20 | 澁谷工業株式会社 | incubator |
KR102237886B1 (en) | 2017-03-08 | 2021-04-07 | 오츠카 가가쿠 가부시키가이샤 | Friction material composition, friction material and friction member |
BR112019024801B1 (en) * | 2017-07-17 | 2022-04-12 | Ab Ludvig Svensson | greenhouse screen |
KR20190090224A (en) * | 2018-01-24 | 2019-08-01 | 도레이첨단소재 주식회사 | Highly transparent optical film |
Family Cites Families (16)
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US4981369A (en) | 1988-10-20 | 1991-01-01 | Murata Mfg. Co., Ltd. | Frost and dew sensor |
DE4017044A1 (en) | 1990-05-26 | 1991-11-28 | Metallgesellschaft Ag | ELECTRICALLY CONDUCTIVE BARIUM SULFATE AND METHOD FOR THE PRODUCTION THEREOF |
JPH0788948A (en) * | 1993-09-27 | 1995-04-04 | C I Kasei Co Ltd | Molding method for antistatic synthetic resin sheet material |
DE4431735C2 (en) * | 1994-09-06 | 1997-09-04 | Metallgesellschaft Ag | Process for the production of an inorganic treated filler for polymers from BaSO¶4¶ as well as the use of inorganic treated barium sulfate |
US20030108730A1 (en) * | 2000-02-14 | 2003-06-12 | John Francis | Opaque polyester film as substrate with white coatings on both sides |
DE19926216A1 (en) | 1999-06-09 | 2001-02-22 | Metallgesellschaft Ag | Process for producing barium sulfate, barium sulfate and use of barium sulfate |
DE10036407A1 (en) | 2000-07-26 | 2002-02-07 | Mitsubishi Polyester Film Gmbh | Multi-layer, transparent, biaxially oriented polyester film |
US7094814B2 (en) * | 2000-09-01 | 2006-08-22 | Toda Kogyo Corporation | Coloring composition for color filter containing colorant and color filter using the same |
KR101056605B1 (en) * | 2003-03-27 | 2011-08-11 | 도다 고교 가부시끼가이샤 | Transparent coloring composition and color filter |
DE10333029A1 (en) | 2003-07-21 | 2005-02-17 | Merck Patent Gmbh | Nanoparticulate UV protectants used in cosmetic, sunscreen, dermatological or other protective uses (e.g. as textile or packaging coatings) comprise a metal oxide with a silicon dioxide coating |
DE102004032596A1 (en) * | 2004-07-06 | 2006-02-16 | Mitsubishi Polyester Film Gmbh | Multilayer, matt, thermoformable, IR-reflective polyester film |
US7799124B2 (en) * | 2005-04-07 | 2010-09-21 | E.I. Du Pont De Nemours And Company | Process for treating inorganic particles via sintering of sinterable material |
DE502006001168D1 (en) * | 2005-06-01 | 2008-09-04 | Mitsubishi Polyester Film Gmbh | White opaque film with low transparency and improved dielectric strength |
US20090060960A1 (en) * | 2005-07-18 | 2009-03-05 | Petra Biehl | Preparation containing barium sulfate |
DE102006031630A1 (en) | 2005-07-18 | 2007-03-15 | Sachtleben Chemie Gmbh | Composition for topical application, useful as a cosmetic or dermatological product, contains finely divided barium sulfate |
DE102006051657A1 (en) * | 2006-11-02 | 2008-05-08 | Mitsubishi Polyester Film Gmbh | Multilayer, white, laser-cut and laser-writable polyester film |
-
2007
- 2007-06-20 DE DE102007028349A patent/DE102007028349A1/en not_active Withdrawn
-
2008
- 2008-06-11 KR KR1020097025730A patent/KR20100020470A/en not_active Application Discontinuation
- 2008-06-11 EP EP08759172A patent/EP2160436A1/en not_active Withdrawn
- 2008-06-11 JP JP2010512568A patent/JP2010530449A/en not_active Withdrawn
- 2008-06-11 WO PCT/EP2008/004656 patent/WO2008155050A1/en active Application Filing
- 2008-06-11 CN CN200880020890A patent/CN101743268A/en active Pending
- 2008-06-11 US US12/664,679 patent/US20110171424A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2008155050A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR20100020470A (en) | 2010-02-22 |
WO2008155050A1 (en) | 2008-12-24 |
US20110171424A1 (en) | 2011-07-14 |
JP2010530449A (en) | 2010-09-09 |
DE102007028349A1 (en) | 2008-12-24 |
CN101743268A (en) | 2010-06-16 |
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