EP1005420A1 - Feuils multicouches mats translucides a base de polypropylene presentant une orientation biaxiale, leur procede de preparation et leur utilisation - Google Patents

Feuils multicouches mats translucides a base de polypropylene presentant une orientation biaxiale, leur procede de preparation et leur utilisation

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Publication number
EP1005420A1
EP1005420A1 EP98939044A EP98939044A EP1005420A1 EP 1005420 A1 EP1005420 A1 EP 1005420A1 EP 98939044 A EP98939044 A EP 98939044A EP 98939044 A EP98939044 A EP 98939044A EP 1005420 A1 EP1005420 A1 EP 1005420A1
Authority
EP
European Patent Office
Prior art keywords
matte
film
aph
polypropylene
agent
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Withdrawn
Application number
EP98939044A
Other languages
German (de)
English (en)
Inventor
Cumhur BÜYÜKAKINCI
Turgut Selbasti
Zakir Rzaev
Ekrem Karpat
Oktay Aral
Özlem VATANSEVER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polinas Plastik Sanayi VE Ticaret AS
Original Assignee
Polinas Plastik Sanayi VE Ticaret AS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Polinas Plastik Sanayi VE Ticaret AS filed Critical Polinas Plastik Sanayi VE Ticaret AS
Publication of EP1005420A1 publication Critical patent/EP1005420A1/fr
Withdrawn legal-status Critical Current

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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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0024—Matt surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0029—Translucent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/414—Translucent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/043—HDPE, i.e. high density polyethylene
    • 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
    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate

Definitions

  • the present invention concerns the field of plastics fabrication and uses, specifically, biaxially oriented polypropylene multilayer matte-translucent films.
  • the packaging food and non-food industry, agriculture, industrial markets, art, etc. has a high demand for biaxially oriented thin films of different types such as matte, colorless, antifog, antibacterial, photosensitivity, biodegradable, heat- sealable, non heat-sealable, mono- and multilayer, laminated, metallizated and other films and materials.
  • Matte appearance films can be produced by using conventional film-forming polymers such as polyesters, polyamides, polyolefins, vinyl chloride polymers, styrene polymers, etc. and different methods for preparation of matte surfaces.
  • Matte surface film for artist's overlays comprises a translucent polymer base film coated with a dried film of matting lacquer comprising: (1) a film-forming plastic resin on the base of styrene-maleate resin and ethyl cellulose, (2) a polystyrene, polyester and polyvinylchloride base film, (3) a relatively soft matting agent - non elastomeric polyethylene particles, (4) relatively hard matting agent such as silica and calcium carbonate, and (5) a mixture of organic solvents [Pat. 4719141, USA (1988)].
  • matting lacquer comprising: (1) a film-forming plastic resin on the base of styrene-maleate resin and ethyl cellulose, (2) a polystyrene, polyester and polyvinylchloride base film, (3) a relatively soft matting agent - non elastomeric polyethylene particles, (4) relatively hard matting agent such as silica and calcium carbonate, and (5) a mixture of organic
  • PET polyethylene terephtalate
  • TiO titanium dioxide
  • Matte surface polymer film useful for preparation of drawing papers, magnetic recording tape leader, wallpaper, capacitor insulators, labels, etc. were prepared from polyester-PET (80 parts), polystyrene (10 parts) and polymethylmethacrylate (10 parts) by stretching 150 % mono- or biaxially and optionally, laminated on one side of the polyester films. The film obtained has good mechanical strength and writing ability [Pat. 63-193920, Japan (1974)]. Matte polyamide film contains itaconic acid-methyl acrylate-vinylidene chloride terpolymer (0.1-10 parts) as a matting agent ands have good antiblocking properties without sacrificing heat sealability [ Chem. Abstr., 80 (12), 6065 lz].
  • Biaxially stretched anisotropic films comprising ethylene-propylene copolymer or blends of polypropylene and polyethylene (1-10 %) were prepared by extruding at 260°C and sprayed onto a casting roll at 30°C, stretched longitudinally 5.6 times at 145°C and transversely 9.3 times at 157°C [Pat. 1936963, Germany (1971)].
  • Pat. 4135096 (Germany), Pat. 88048244 (UK) and 88199666 (UK)].
  • Pat. 4135096 Germany
  • Japan patent relates to a matte packaging film comprising polypropylene and Al borate as translucency-providing agent which was prepared from mixture of 90 parts of polypropylene and 10 parts of Alborex Y (AL borate whisker) by extruding through a temperature-die.
  • the translucent film with 30 ⁇ m thickness have an adequate surface unevenness [Pat. 06-212037, Japan (1994)].
  • the object of Pat. EP-A-O 367613 was a multilayer film containing a vacuole polypropylene base layer and an incribable outer layer made from a mixture or blend of HDPE with polyolefins.
  • the title film has a density of 0.69 g/cm 3 , opaque appearance and non-transparent to light properties. Additionally, it was preferred to incorporate a SiO 2 -filler into the outer layer to improve the incribability. This layer was also very matte, which gives the film a paper-like appearance. Therefore, SiO 2 containing matte surface proves to be unsatisfactory on the printing.
  • Biaxially oriented multilayer ( ⁇ 3 layers) polyolefin films including polypropylene and HDPE, and having low coefficient friction, excellent optical transparency, good wettability, high sheen and low haze were invented in the patents of 4419411 (USA), 4578316 (USA) and 89/10839 (WO).
  • 5478643, USA (1995) was a 21.5 ⁇ m thickness matte multilayer ( ⁇ 3 layers) polypropylene film for use in a metallization process which contains one base polypropylene layer (19 ⁇ m thickness) with migrating additives such as N,N-bis-hydroxyethyl) (C 10- 0 )alkylamine (0.22 %) and stearamide (0.25 %) and each outer layer (1.25 ⁇ m thickness) including a mixture or blend of polypropylene, ethylene-propylene copolymer and/or ethylene-propylene-butylene terpolymer, and HDPE, blend of HDPE with said propylene copolymer or terpolymer.
  • migrating additives such as N,N-bis-hydroxyethyl) (C 10- 0 )alkylamine (0.22 %) and stearamide (0.25 %)
  • each outer layer (1.25 ⁇ m thickness) including a mixture or blend of polypropylene, ethylene-prop
  • This outer layer was distinguished by a characteristic matte surface or appearance and was suitable for use as a transfer metallization film. All layers of said film contained 0.12 % by weight of pentacrythrityl tetrakis[4-(3,5-di-tret- butyl-4-hydroxyphenyl) propionate] as a stabilizer and 0.05 % by weight of calsium stearate as a neutralizer.
  • the film resulted was then co-extruded the melts corresponding to the individual layers through a flat-film die, taked the film off over a take-off roll at 40-100°C, biaxially stretched at a longitudinal stretching ratio about 4:1 to 7:1 and a transverse stretching ratio about 8:1 to 10:1, heat setting and corona treated (one or both outer layer).
  • the film prepared has following average characteristics: thickness 10-50 ⁇ m, density 0.90-0.92 g/cm 3 , sheen (85° angle) 29-42, haze 52-70 %, roughness 2.3-3.2 ⁇ m, coefficient of friction 0.3-0.5, surface tension (after storage for 6 months) 38-39 mN/m, and very good matte appearance (visual assessment).
  • the film consists HDPE, polypropylene and ethylene- propylene-butylene terpolymer; the film in the both cases have a matte appearance.
  • Difference and deficiency of said film are the following: the film mainly were recommended for use in metallization process; co-extruder system used allows only to prepare maximum 3-layer film; the film not contains a matting agent such as a carbonyl containing alternating or random copolymer, and also have comparative high values of sheen, and low values of surface tension (Table 1).
  • Pat. 5489454, USA (1996) describes a biaxially oriented, shrinkable, heat- sealing 3-layer (10-50 ⁇ m thickness) polyolefin film with a matte appearance, good passage through the machine and antistatic and shrink properties, which simultaneously forms very tight, effective bil-low- and fold-free wrapping, and also was provided a co-extruding process for its production.
  • both the base layers (polypropylene or polypropylene mixture) and outer layer(s) (mixture or blend of propylene copolymer or terpolymer and HDPE) contain 0.1-0.2 % SiO , CaCO 3 and/or incompatible organic polymers such as polyamides, polyesters, polycarbonates, benzoguanamine-formaldehyde resins as antiblocking agents, 0.05-2.0 % phenolic stabilizers, 0.05-0.25 % high aliphatic acid amide and polydimethyldisiloxanees as lubricants, 0.05-0.3 % glycerol monostearate as antistatic agent.
  • organic polymers such as polyamides, polyesters, polycarbonates, benzoguanamine-formaldehyde resins as antiblocking agents, 0.05-2.0 % phenolic stabilizers, 0.05-0.25 % high aliphatic acid amide and polydimethyldisiloxanees as lubricants,
  • the film resulted was stretched in the longitudinal direction preferably from about 4:1 to 9:1 at 80-120°C and in the transverse direction from about 6:1 to 8:1 at 130-155°C.
  • the films with different compositions has the following characteristics: sheen (85° angle) 30-38, haze 62-68 %, roughness 2.6- 3.0 ⁇ m, coefficient of friction 0.3-0.4, surface tension 39 mN/m, minimum heat- sealing temperature 105-115°C, longitudinal and transverse shrinkage at 90°C 4- 6 % and 3-5 % at 120°C 11-14 % and 16-20 % respectively.
  • All layers contained conventional stabilizer and neutralizer.
  • the base layer furthermore contained aliphatic alkylamine as antistatic agent.
  • extruded four-layer film was taken off a first take-off roll and further trio of rolls. The film was then cooled, subsequently stretched longitudinally and transversely, set and corona treated.
  • the films resulted has matte appearance with gloss (85° angle, D side) 29- 84, coefficient of friction 0.4-0.6, whiteness (D side) 65-81, opacity (D side) 67- 70 and density 0.69-0.94 %.
  • the multilayer film according to this patent invention was distinguished by a multiplicity of advantageous properties and was recommended for wide variety of applications such as an attractive matte lamination film, an opaque packaging film in high-speed packaging machines, an opaque film in wrapping film, and a base film for adhesive tape or for aqueous barrier coating systems.
  • the film was also suitable for the production of plastic labels and laminates with paper, cardboard, metals, and metalized plastic films.
  • Table 1 The comprise of properties these films with properties of films according to present invention (Table 1) shown that the films of said invention have high value of gloss of matte side.
  • the film contain only HDPE as matting agent and terpolymer with E- and B-units differing from composition of terpolymer using in present invention.
  • High shrinkage polyolefin multilayer films were disclosed in the following early patent publications: EP-A-O 436196, EP-A-O 350859, DE-A 1954467 and DE-A 3215120.
  • the films according to these patents has very high sheen values and very low haze. Therefore these shrink films were unsatisfactory with respect to their passage through the machines, and their properties during winding, further processing and slitting.
  • Pat. 5494717, USA (1996) relates to a biaxially oriented matte polypropylene film of high shrinkage which comprises a three-layers of X/ZX structure, i.e., one base layer Z containing a polypropylene or propylene polymer mixture and two outer layers X containing mixture or blend of polypropylene, ethylene-propylene copolymer ethylene-propylene-butylene terpolymer and HDPE.
  • both the base and outer(s) layers include conventional additives such as known antiblocking and antistatic agents, stabilizers, neutralizers and lubricants.
  • the films prepared after biaxially oriented and corona treated has sheen 29-40 (85° angle), has 58-70 %, roughness 2.3-3.2 ⁇ m, coefficient of friction 0.3-0.5, surface tension 38-39 mN/m, longitudinal and transverse shrinkage at 120°C 29-36 % and 41-47 % respectively.
  • EP-A-O 479101 (1992) discloses a biaxially oriented polypropylene film (25 ⁇ m thickness) for twist-wrapping which was prepared from mixture of isotactic polypropylene (71.6 %), hydrogenated cyclopentadiene resin with softening point 140°C (28 %), ethoxylated amine (0.2 %) as an antistatic agent, erucicamide (0.2 %) as a slip agent, and polydimethylsiloxane (0.5 %) as a surfactant by co-extruding and drawn longitudinally 6.5 -fold at 110°C and transversely 7.3 -fold at 150°C.
  • corona treated biaxially oriented polypropylene film contains antiblocking agent; difference and deficiency of this film as compared with films of present invention are following: non-filled transparent films contain polydimetylsiloxane as surfactant, and hydrogenated cyclopentadiene resin and have relatively low elongation and high values of shrinkage. These twist wrapping films has unsatisfactory appearance, processing properties and in particular scratch resistance.
  • the aim of Pat. 5496600, USA (1996) was the attempt to remove these deficiencies.
  • Said patent describes a three-layer biaxially oriented polypropylene matte film having advantageous properties such as a characteristic matte sheen at less than 80, very good printability and twist properties, uniform matte appearance and excellent scratch resistance and using as a twist wrapping film.
  • the title film contains homo-, co- and terpolymer of propylene, and HDPE or blend of HDPE with said polyolefins, and also petroleum, terpen and other hydrocarbon resins, including dicyclopentadiene polymer, as amorphous matting agents.
  • the film also has a permanent set of greater than about 50 %, in the longitudinal and transverse directions and approximately isotropic mechanical properties.
  • Heat-setting, biaxially stretched and corona treated film has overall thickness 10-80 ⁇ m, density 0.90-0.95 g/cm 3 , sheen 29-42, has 58-70 %, roughness 2.3-3.2 ⁇ m, coefficient of friction 0.3-0.5, surface tension 38-39 mN/m, permanent set 62-64 % and 60-63 % in the longitudinal and transverse directions respectively, and scratch resistance ( ⁇ haze) 20-22.
  • these films as compared with films of present invention have high sheen of matte side, and high values of longitudinal and transverse shrinkage at 120°C (Table 1).
  • the films of present invention as compared with commercial matte film also have advantageous properties (Table 1).
  • One object of the present invention is to improve the production process of said films by using tandem extruder system supplied with three co-extruders, recycling line for the film forming in the transverse stretching stage and corona discharge, and also modified variant of chill-roll treatments of films in the biaxially orientation process allowing to form homogen matte films with improved surface properties and dimensional stability.
  • Another aspect of the present invention to use new polymer system, i.e. mixture or blend of HDPE with carbonyl containing homo- and copolymers such as polymethyl(metha)acrylates, alternating or random copolymers of vinyl monomers or -olefins (C 2 - ⁇ o) with anhydrides or esters of unsaturated mono- or dicarbonic acids as mattering agent in the skin matte layer of said films.
  • An offered A/B/C/D/C multilayer film of the present invention is biaxially oriented matte-translucent polypropylene based film structure comprising 15-50 ⁇ m ⁇ 5 layers from (A) Pat.
  • the technological aspect of manufactured process of said films is distinguished from known processing used in the production of matte films by the fact that tandem extruder system with two main extruders supplied with three satellite co-extruders, recycling line and corona discharge.
  • the process is carried out by three chill-roll treatments and two step of longitudinal orientation allowing to prepare good homogenized matte film with improving surface properties and dimensional stability.
  • One or both surface of biaxially oriented films prepared are treated in a known manner by air corona discharge.
  • the use of said recycling line for film waste forming in the transverse stretching stage allows to lower film cost by 3.5 %.
  • the extruded five-layer film is taken off over the corresponding process steps through a chill roll and cooled, and cast film profile is controlled by ⁇ -Gauge equipment.
  • the film is subsequently stretched longitudinally at two steps and stretched transversely. After biaxially orientation, the film is set and air corona-treated on one or two sides.
  • Extrusion extrusion temperature 200-260°C, first chill roll temperature 35-45°C
  • Longitudinal stretching stretching roll temperature of first step 150-160°C and second step 140-150°C, longitudinal stretching ratio 5:1 - 6:1 for first step and 1:1 - 1:2 for second step
  • Transverse stretching temperature of heat-up zones 170-185°C, temperature of stretching zones 160- 170°C, transverse stretching ratio 9:1 - 10:1
  • Recycling edges of the biaxially orientated film is recycled and fed to the line again; Setting: setting temperature 165-170 °C; Air corona discharge: voltage 15-25 kV and frequency 20-30 kHz.
  • a B/C/D/E structure film with a thickness of 17.5 ⁇ m comprising (A) 3.0 ⁇ m skin matte-translucent layer from 47.9 % by weight of ethylene(E)-propylene(P)- butylene(B) terpolymer with E-unit content of 3.5 % and B-unit content of 5.5 % (density 0.90 g/cm 3 , MFI 8.0 g/10 min, m.p. 143.6°C, vicat softening point
  • matte-translucent skin layer comprises a E- P-B terpolymer with E-unit content of 3.5 % and B-unit content of 5.5 %, thickness of (C) core layer is 45.5 ⁇ m;
  • E) 0.5 ⁇ m outer layer is matte containing a E-P-B terpolymer with E-unit content of 4.2 % and B-unit content of 9.0 % and with composition as in (A) layer.
  • thickness of (C) core layer is 25.5 ⁇ m and contains ethoxylated amine as an antistatic agent.
  • 3.0 ⁇ m / 26 ⁇ m / 0.5 ⁇ m / 0.5 ⁇ m film prepared has composition and properties showing in Tables 2, 3 and 4 respectively.
  • Example 7 The film with a thickness of 30 ⁇ m and A/C/D/E structure without (B) inner layer having the composition as in Example 5 repeated with following changes: (E) shining outer layer contains a E-P-B terpolymer with E-unit content of 1.5 % and B-unit content of 15 %, erucicamide as a slip agent. After biaxially stretching, setting and air corona discharged in the given conditions 3 ⁇ m / 26 ⁇ m / 0.5 ⁇ m / 0.5 ⁇ m film prepared has composition and properties showing in Tables 2, 3 and 4 respectively.
  • Example 8 Example 8
  • the film with a thickness of 15 ⁇ m and A/C/E structure having the composition as in Example 1 without (B) and (D) inner layers.
  • 3.0 ⁇ m / 1 l ⁇ m / l.O ⁇ m film prepared has composition and properties showing in Tables 2, 3 and
  • St-MA alternating styrene-maleic anhydride copolymer
  • Example 10 The film with a thickness of 17.5 ⁇ m and A/B/C/D/E structure as in Example 1 repeated with following changes: (A) matte-translucent skin layer comprised a E- P-B terpolymer with E-unit content of 4.2 % and B-unit content of 9.0 % containing said slip and antiblocking agents (density 0.885 g/cm '3 , MFI 7.3 g/10 min, m.p.
  • matte-translucent skin layer comprised a E- P-B terpolymer with E-unit content of 3.5 % and B-unit content of 5.5 % and 10:1 mixture or blend of HDPE / ⁇ -diisobutylene-maleic anhydride alternating copolymer (softening point 195°C, acid number 665 mg KOH/g, ⁇ m 0.13 dl/g at 20°C in methylethyl ketone).
  • setting and air corona treatment 3.0 ⁇ m /1.5 ⁇ m / 43 ⁇ m / l.O ⁇ m / 1.5 ⁇ m film prepared has composition and properties showing in Tables 2, 3 and 4 respectively.
  • Density is determined in according to ISO 1183 and/or ASTM D-1505.
  • Melting Flow Index is measured in according to ASTM 1238 / L at 230°C and load of 21.6 N. Melting point (m.p.) is measured by DSC method, maximum point of the melting curve, at heating rate ⁇ Q°C/min is corresponded to m.p. value.
  • Vicat softening point is determined in according to ASTM D-1525.
  • Izod impact strength is measured in according to ISO 180 /1A.
  • Sheen of the film is measured in accordance with ASTM D-2103, the angle of incidence is set at 85°. Haze of the film is measured in accordance with ASTM D- 1003.
  • Coefficient of friction of the film is determined in accordance with ASTM D- 1984. Shrinkage of the film is measured in accordance with ASTM D-1204. The test sample is shrink at 90 and 120°C for a period at 15 min. Longitudinal shrinkage
  • HDPE Polyethylene
  • EA Erucicamide

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

euil mat translucide multicouche présentant une orientation biaxiale et une utilité pour du papier photographique stratifié, des reproductions et des couvertures de menus, des stratifiés classiques, des produits hygiéniques, des emballages de produits alimentaires ou cosmétiques, ainsi que dans des machines d'emballage très rapides, en tant que pellicules de base d'une bande adhésive matte et, en général, pour toutes mises en applications d'emballage ou de conditionnement. Ce feuil présente une épaisseur de 15-50 νm≤ 5 couches comprenant (A) une couche matte translucide de peau de 1,5-3 νm contenant terpolymère d'éthylène (E)-propylène (P)-butylène (B) possédant une teneur en 1,5-4,9 % d'unités E et une teneur de 5,5-15 % en unités B, polypropylène, soit polyéthylène haute densité (HDPE), soit un mélange répondant à un rapport de 10:(0,5-1,5) de HDPE et de polyméthyl(métha)acrylates, un copolymère alterné ou aléatoire de monomère de vinyle (styrène, alkyl(métha)acrylates etc.) ou des α-oléfines C2-C10 et des anhydrides ou des esters d'acides mono- ou dicarboniques insaturés en tant qu'agent de matité, de la silice synthétique en tant qu'agent antibloquant, érucicamide en tant qu'agent de glissement et phosphite d'allyle (APH) en tant qu'antioxydant, stéarate de calcium en tant que neutralisant et tétrakis[méthylène(3,5-di-tert-butyl-4- hydroxy-hydro-cinnamate] méthane en tant que stabilisant, (B) soit une couche intérieure de polypropylène ≥0,5 νm contenant ledit antioxydant d'APH, ledit stabilisant, ledit neutralisant et/ou ledit agent de glissement, soit une couche intérieure ≥1,5 νm contenant la composition de la couche matte (A), (C) une couche centrale vierge ou marquée de polypropylène de 10-46 νm contenant 5-cholestène-3β-ol en tant qu'agent marqué, lesdits antioxydant d'APH, stabilisant et neutralisant et/ou ledit agent de glissement et amine éthoxylée en tant qu'agent antistatique, (D) une couche intérieure de polypropylène ≥1,5 νm contenant ledit antioxydant d'APH, ledit stabilisant et ledit neutralisant et (E) soit une couche extérieure brillante ≥0,5 νm contenant polypropylène, ledit agent antibloquant, l'antioxydant d'APH et le neutralisant, soit une couche extérieure matte ≥1,5 νm contenant la même composition que la couche (A). On a préparé ce feuil au moyen d'un système d'extrusion en tandem alimenté par trois ou quatre co-extrudeuses satellites, une filière plate, un rouleau froid et une ligne de recyclage. Après étirage biaxial et soumission à une effluve électrique dans des conditions données, ce feuil mat translucide présente une brillance (angle 85°) de 10-15 (côté peau mat) et 42-61 (côté extérieur brillant), un retrait longitudinal ≥0,5 % à 90 °C et ≥2,5 % à 120 °C et un retrait transversal ≥0,25 % à 90 °C et ≥1,5 % à 120 °C pendant une durée de 15 min, un aspect mat excellent, une tension de surface de 40-41 mN/ài(m) (après conservation de 6 mois), une stabilité dimensionnelle élevée et une température basse de scellement thermique ≤110 °C.
EP98939044A 1997-08-11 1998-08-10 Feuils multicouches mats translucides a base de polypropylene presentant une orientation biaxiale, leur procede de preparation et leur utilisation Withdrawn EP1005420A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
TR9700780 1997-08-11
TR97/00780A TR199700780A3 (tr) 1997-08-11 1997-08-11 Çift eksenli olarak yönlendirilmis polipropilen bazli mat-yari saydam çok katli film tabakalari, bunlarin üretim prosesi ve kullanimi.
PCT/TR1998/000017 WO1999007553A1 (fr) 1997-08-11 1998-08-10 Feuils multicouches mats translucides a base de polypropylene presentant une orientation biaxiale, leur procede de preparation et leur utilisation

Publications (1)

Publication Number Publication Date
EP1005420A1 true EP1005420A1 (fr) 2000-06-07

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EP98939044A Withdrawn EP1005420A1 (fr) 1997-08-11 1998-08-10 Feuils multicouches mats translucides a base de polypropylene presentant une orientation biaxiale, leur procede de preparation et leur utilisation

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Country Link
EP (1) EP1005420A1 (fr)
AU (1) AU8755098A (fr)
TR (2) TR199700780A3 (fr)
WO (1) WO1999007553A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534153B1 (en) 1999-12-09 2003-03-18 Exxonmobil Oil Corporation Matte surface film with improved matte appearance
US7273629B2 (en) * 2000-11-28 2007-09-25 Cryovac, Inc. Meat package with reduced leaker rates
WO2002083414A1 (fr) * 2001-04-18 2002-10-24 Polinas Plastik Sanayi Ve Ticaret A. S. Composition polyolefine pour films opaques multicouche, blancs d'aspect, orientes biaxialement
EP1601322B1 (fr) * 2003-03-11 2008-12-03 JOHNSON & JOHNSON GmbH Tampon revetu d'un film emballe
ES2396867T5 (es) * 2007-08-28 2017-10-13 Super Film Ambalaj Ve Sanayi Ve Ticaret A.S. Películas multicapa antiestáticas basadas en polipropileno biaxialmente orientado con recubrimiento en línea
WO2015004314A1 (fr) * 2013-07-12 2015-01-15 Upm Raflatac Oy Film multicouche pour étiquette et procédé permettant de fabriquer ce dernier
CN110699000A (zh) * 2019-10-11 2020-01-17 上海固柯胶带科技有限公司 用于半导体研磨和封装的膜材料

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Publication number Priority date Publication date Assignee Title
DE4135097A1 (de) * 1991-10-24 1993-04-29 Hoechst Ag Nicht siegelbare, matte, truebe biaxial orientierte polyolefin-mehrschichtfolie, verfahren zu ihrer herstellung und ihre verwendung
DE4309555A1 (de) * 1993-03-24 1994-09-29 Wolff Walsrode Ag Matte, biaxial gereckte Polypropylenfolie Verfahren zu ihrer Herstellung
DE4311422A1 (de) * 1993-04-07 1994-10-13 Hoechst Ag Opake, matte, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung

Non-Patent Citations (1)

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Title
See references of WO9907553A1 *

Also Published As

Publication number Publication date
TR200000421T2 (tr) 2001-07-23
AU8755098A (en) 1999-03-01
TR199700780A2 (xx) 1999-02-22
WO1999007553A1 (fr) 1999-02-18
WO1999007553A9 (fr) 1999-06-10
TR199700780A3 (tr) 1999-02-22

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