CA2142353A1 - Glossy and transparent ink-printable polyolefinic film composition - Google Patents
Glossy and transparent ink-printable polyolefinic film compositionInfo
- Publication number
- CA2142353A1 CA2142353A1 CA002142353A CA2142353A CA2142353A1 CA 2142353 A1 CA2142353 A1 CA 2142353A1 CA 002142353 A CA002142353 A CA 002142353A CA 2142353 A CA2142353 A CA 2142353A CA 2142353 A1 CA2142353 A1 CA 2142353A1
- Authority
- CA
- Canada
- Prior art keywords
- film
- layer
- weight percent
- ink
- polymeric additive
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
- B32B2307/70—Other properties
- B32B2307/75—Printability
-
- 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
- B32B2519/00—Labels, badges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/504—Backcoats
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/508—Supports
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
Abstract
Ink-printable films (10) comprising at least one outer ink-printable layer (11) consisting essentially of a polyolefin material containing a polymeric resin additive which enhances the ink printability property of the layer while not altering the optical properties of the film.
Description
WO 95/01397 ~. 2~2353 PCTIUS94/07279 GLOSSY AND TRANSPARENT INK-PRINTABLE
POLYOLEFINIC FILM COMPOSITION
Backqround of the Invention This invention relatesto polyolefinic polymer compositions having improved properties. In particular, this invention relates to improving the receptivity or adhesion of printing inks to the surface of shaped articles made from such polyolefinic polymer compositions.
Polyolefinic polymers, in particular ethylene polymers such as polyethylene are used for forming shaped articles such as sheets, films, tubes, bottles, containers, etc. therefrom.
However, polyethylene has, and consequently articles made thereof have, an extremely smooth hydrophobic surface which is unreceptive to most common types of printing inks and dyes and thus it is difficult to print the surface of polyethylene articles.
Various known methods have been used to make ethylene polymers more receptive to printing inks. For example, there are a number of surface treating techniques which have been developed to improve the receptivity of the polymer surface to printing inks including chemical treatment with oxidizing agents such as chlorine and strong acids and electronic, or corona discharge treatment of the polymer surface. Flame treatment of the surface of polyethylene has also been used to make the polyethylene more receptive to 20 printjng inks.
Another method used to improve the receptivity of the polymer surface to printing inks is to apply a coating or printable top layer on the surface of the polymer layer to beDrinted. Forexample,multilayerfilmshavebeendisclosedinthepriorartwhereinthetopprintable layer or printable skin layer of the film is described as being made from materials such 25 as ethylene acrylic acid, ethylene methyl acrylic acid, ethylene ethyl acrylate, ethylene methyl acrylate, acrylonitrile butadiene styrene, nylon, polybutylene, polystyrene, polyurethane, poiysulfone, polyvinylidene chloride, polypropylene, polycarbonate, polymethyl pentene, styrene maleic anhydride, styrene acrylonitrile, ionomers based on sodium or zinc salts of ethylene/methacrylic acid, acrylics, cellulosics, fluoroplastics, nitriles and thermoplastic 30 polyesters.
Still ar,vll ,er method used to improve the recepli~; Ly of a polymer surface toprinting inks is to form a novel poly,.,eric composition which has as one of its improved properties an enhanced receptivityto printing ink. Thus, articles, such as a monolayer film, made from said co",po,ilion would have the improved prope. ly of enhanced receptivity to 35 printing ink. For example, it is known to obtain an ethylene polymer co"-posilion having excellentreceptivitytoprinting inksaftersurfacetreatmentbyincor~o~dlin9 intheethylene polymer an N-substituted unsaturated carboxylic amide. It is also known to blend together a mixture of commercially available, high molecular weight polyethylene with a minor but WO 95/01397 - - PCT/US94/0727g Z1423~3 effective amount of an oxidized, low molecular weight, polyethylene wax to form a plastic molding composition and shaping the composition into an article by any of the known cG"""ercial methods, which article has a surface which is hydrophilic and receptive to printing i nks. Furthermore, polyolefi n compositions havi ng improved adhesion to water based inks 5 have been made by incorporating into the polyolefin an effective amount of a lactamide. '.
It is desired to provide yet another novel polymeric composition having enhancedreceptivity to printing ink by blending together an ethylene polymer with an effective amount of an ink printability enhancing agent.
Anobjectofthepresentinventionistoimpartthedesiredprintabilityand adhesion to printing inks to polyolefin compositions without adversely affecting the optical properties of the polyolefin.
Summary of the Invention One aspect of the present invention is directed to a composition which can be used to make a film that combines exceilent printability with excellent optical prope. lies. The compGsilion is obtained by blending into a polyolefin a minor portion of a polymeric additive which does not deteriorate the optical p(ope- lies of the polyolefin.
The co,..pG,ilion of the present invention includes a polyolefin material with apol~..,e. ic additive having double bonds or having double bonds and a polystyrene present in its chemical structure; or an anhydride modified polyolefin.
Another aspect of the present invention is directed to a film made of the above composition.
Still another aspect of the present invention is preparing a film including the steps of (a) forming the composition;
(b) making a film from the composition; and (c) applying an electrical discharge treatment to at least one of the surfaces of the film.
Brief Descriotion of the Drawinqs Figure 1 is an enlarged partial cross-sectional view of one embodiment of a film30 structure of the present invention.
Figure 2 is an enlarged partial cross-sectional view of another embodiment of a film structure of the present invention.
Figure 3 is an enlarged partial cross-sectional view of one embodiment of a prffsure-sensitive adhesive film structure useful for making labels in accordance with the 35 present invention.
Figure 4 is an enlarged partial cross-sectional view of another embodiment of a pressure-sensitive adhesive film structure useful for making labels in accordance with the present invention.
POLYOLEFINIC FILM COMPOSITION
Backqround of the Invention This invention relatesto polyolefinic polymer compositions having improved properties. In particular, this invention relates to improving the receptivity or adhesion of printing inks to the surface of shaped articles made from such polyolefinic polymer compositions.
Polyolefinic polymers, in particular ethylene polymers such as polyethylene are used for forming shaped articles such as sheets, films, tubes, bottles, containers, etc. therefrom.
However, polyethylene has, and consequently articles made thereof have, an extremely smooth hydrophobic surface which is unreceptive to most common types of printing inks and dyes and thus it is difficult to print the surface of polyethylene articles.
Various known methods have been used to make ethylene polymers more receptive to printing inks. For example, there are a number of surface treating techniques which have been developed to improve the receptivity of the polymer surface to printing inks including chemical treatment with oxidizing agents such as chlorine and strong acids and electronic, or corona discharge treatment of the polymer surface. Flame treatment of the surface of polyethylene has also been used to make the polyethylene more receptive to 20 printjng inks.
Another method used to improve the receptivity of the polymer surface to printing inks is to apply a coating or printable top layer on the surface of the polymer layer to beDrinted. Forexample,multilayerfilmshavebeendisclosedinthepriorartwhereinthetopprintable layer or printable skin layer of the film is described as being made from materials such 25 as ethylene acrylic acid, ethylene methyl acrylic acid, ethylene ethyl acrylate, ethylene methyl acrylate, acrylonitrile butadiene styrene, nylon, polybutylene, polystyrene, polyurethane, poiysulfone, polyvinylidene chloride, polypropylene, polycarbonate, polymethyl pentene, styrene maleic anhydride, styrene acrylonitrile, ionomers based on sodium or zinc salts of ethylene/methacrylic acid, acrylics, cellulosics, fluoroplastics, nitriles and thermoplastic 30 polyesters.
Still ar,vll ,er method used to improve the recepli~; Ly of a polymer surface toprinting inks is to form a novel poly,.,eric composition which has as one of its improved properties an enhanced receptivityto printing ink. Thus, articles, such as a monolayer film, made from said co",po,ilion would have the improved prope. ly of enhanced receptivity to 35 printing ink. For example, it is known to obtain an ethylene polymer co"-posilion having excellentreceptivitytoprinting inksaftersurfacetreatmentbyincor~o~dlin9 intheethylene polymer an N-substituted unsaturated carboxylic amide. It is also known to blend together a mixture of commercially available, high molecular weight polyethylene with a minor but WO 95/01397 - - PCT/US94/0727g Z1423~3 effective amount of an oxidized, low molecular weight, polyethylene wax to form a plastic molding composition and shaping the composition into an article by any of the known cG"""ercial methods, which article has a surface which is hydrophilic and receptive to printing i nks. Furthermore, polyolefi n compositions havi ng improved adhesion to water based inks 5 have been made by incorporating into the polyolefin an effective amount of a lactamide. '.
It is desired to provide yet another novel polymeric composition having enhancedreceptivity to printing ink by blending together an ethylene polymer with an effective amount of an ink printability enhancing agent.
Anobjectofthepresentinventionistoimpartthedesiredprintabilityand adhesion to printing inks to polyolefin compositions without adversely affecting the optical properties of the polyolefin.
Summary of the Invention One aspect of the present invention is directed to a composition which can be used to make a film that combines exceilent printability with excellent optical prope. lies. The compGsilion is obtained by blending into a polyolefin a minor portion of a polymeric additive which does not deteriorate the optical p(ope- lies of the polyolefin.
The co,..pG,ilion of the present invention includes a polyolefin material with apol~..,e. ic additive having double bonds or having double bonds and a polystyrene present in its chemical structure; or an anhydride modified polyolefin.
Another aspect of the present invention is directed to a film made of the above composition.
Still another aspect of the present invention is preparing a film including the steps of (a) forming the composition;
(b) making a film from the composition; and (c) applying an electrical discharge treatment to at least one of the surfaces of the film.
Brief Descriotion of the Drawinqs Figure 1 is an enlarged partial cross-sectional view of one embodiment of a film30 structure of the present invention.
Figure 2 is an enlarged partial cross-sectional view of another embodiment of a film structure of the present invention.
Figure 3 is an enlarged partial cross-sectional view of one embodiment of a prffsure-sensitive adhesive film structure useful for making labels in accordance with the 35 present invention.
Figure 4 is an enlarged partial cross-sectional view of another embodiment of a pressure-sensitive adhesive film structure useful for making labels in accordance with the present invention.
wo gS/OL3g7 . ~-;214~353 PCTIUS94/07279 Detailed Descri ~ti on of the ~ efe. ed Embodiments In its broadest scope the composition of the ~Dresent invention i ncl udes a polyolefinic polymer and a polymeric additive refe"èd to herein as an "ink printability enhancer" ("IPE"~.
The polyolefinic polymer includes for example low-density polyethylene (LDPc), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), a high-density polyethylene (HDPE), polypropylene (PP), propylene-ethylene copolymers, or mixtures of such materials or mixtures which contain such materials. To the polyolefinic polymer material is added the IPE polymeric additive.
The IPE is selected from a material which, in general, contains double bonds or double bonds and a polystyrene in the IPE's chemical structure or an anhydride modified polyolefin. Also, the IPE should not adversely affect the optical properties of composition. For example, the IPE should not increase haze by more than 5 percent (absolute units) as measured according to ASTM D-l 003 and/or should not decrease the 60 degree gloss by more than S
percent (absolute units) as measured according to ASTM D-2457.
Preferably, the IPE is selected from the group comprising styrenic block copolymers, modified poly¢ '~rins and polyolefin poly...~., containing some degree of unsaturation or mixtures thereof. The styrenic block copoly.-,o~, used as the IPE in the present invention include, for eAa~ 'e, styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS) 20 of a grade having lower than 40 weight percent styrene, styrene-ethylene-butylene-styrene (SEBS), styrene-isoprene (Sl), SlS/styrene-isoprene blend compositions and mixtures thereof.
The polymeric polyolefins using some degree of unsaturation include, for example, polybutadiene, ethylene-propylene-diene copoly,..er, (EPDM), poly'isop-ene, transpolyoctenamer and mixtures thereof. The modified polyolefins include, for example, 25 anhydride modified polyethylenes such as maleic anhydride containing olefin polymers and copolymers such as those polymers commercial Iy available under the trademark ADMER~
(trademark of Mitsui P~t~ u.l,e. "icals) and styrene maleic anhydride and mixtures thereof. The p. efer- ed IPE used in the prffent invention is SIS or mixtures containing SIS.In the composition, the IPE is present in an amount of from 3 weight percent to 50 30 weight percent, preferably from 5 weight percent to 30 weight pefcént; and more preferably from 7 weight percent to 25 weight percent, with the remainder of the co...posi Lion being the polyolefinic poly.-.er, that is, the composition generally contains from'50 weight percent to 97 weight percent, prëfel ably from 70 weight percent to 95 weight pefcenl, and more preferably from 75 weight percent to 93 weight percent polyolefin.
Otheradditivescanalsobeblended intothecc......... posilion. Otheroptional additivesthatcanbeaddedtotheco--,pû,ilionofthepresentinventionincludeforexample,antioxidants, antiblocks, antistatic additives, processing aids, inorganic fillers, UV stabilizers, slip additives and pigments.
The polyolefinic polymer includes for example low-density polyethylene (LDPc), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), a high-density polyethylene (HDPE), polypropylene (PP), propylene-ethylene copolymers, or mixtures of such materials or mixtures which contain such materials. To the polyolefinic polymer material is added the IPE polymeric additive.
The IPE is selected from a material which, in general, contains double bonds or double bonds and a polystyrene in the IPE's chemical structure or an anhydride modified polyolefin. Also, the IPE should not adversely affect the optical properties of composition. For example, the IPE should not increase haze by more than 5 percent (absolute units) as measured according to ASTM D-l 003 and/or should not decrease the 60 degree gloss by more than S
percent (absolute units) as measured according to ASTM D-2457.
Preferably, the IPE is selected from the group comprising styrenic block copolymers, modified poly¢ '~rins and polyolefin poly...~., containing some degree of unsaturation or mixtures thereof. The styrenic block copoly.-,o~, used as the IPE in the present invention include, for eAa~ 'e, styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS) 20 of a grade having lower than 40 weight percent styrene, styrene-ethylene-butylene-styrene (SEBS), styrene-isoprene (Sl), SlS/styrene-isoprene blend compositions and mixtures thereof.
The polymeric polyolefins using some degree of unsaturation include, for example, polybutadiene, ethylene-propylene-diene copoly,..er, (EPDM), poly'isop-ene, transpolyoctenamer and mixtures thereof. The modified polyolefins include, for example, 25 anhydride modified polyethylenes such as maleic anhydride containing olefin polymers and copolymers such as those polymers commercial Iy available under the trademark ADMER~
(trademark of Mitsui P~t~ u.l,e. "icals) and styrene maleic anhydride and mixtures thereof. The p. efer- ed IPE used in the prffent invention is SIS or mixtures containing SIS.In the composition, the IPE is present in an amount of from 3 weight percent to 50 30 weight percent, preferably from 5 weight percent to 30 weight pefcént; and more preferably from 7 weight percent to 25 weight percent, with the remainder of the co...posi Lion being the polyolefinic poly.-.er, that is, the composition generally contains from'50 weight percent to 97 weight percent, prëfel ably from 70 weight percent to 95 weight pefcenl, and more preferably from 75 weight percent to 93 weight percent polyolefin.
Otheradditivescanalsobeblended intothecc......... posilion. Otheroptional additivesthatcanbeaddedtotheco--,pû,ilionofthepresentinventionincludeforexample,antioxidants, antiblocks, antistatic additives, processing aids, inorganic fillers, UV stabilizers, slip additives and pigments.
WO 95/OL397 ~4Z;~53 PCTtUSg4/07279 The amount of optional additive that can be used in the present composition willvary depending on the properties desired and effect desired. Usually one or more optional additives may be present in the composition in an amount of from 0.00 1 weight percent to 15 weight percent for each additive individually. For exampie, when a nucleator or clarifying 5 agent is used, the composition can include from 0.1 to 0.5 weight percent of the nucleator ~r ciarifying agent. If, for example, a lower gloss prope. ly is desired but still maintaining ink printability, a filler such as calcium carbonate, talcum, silicon dioxide, chalk or other filler may be used, and the amount can be from 1 to 6 weight percent. If, for example, transparency is not desired, a pigment may be used in an amount of from 0.1 weight percent to 15 weight 10 percent and still maintain the property of ink printability. Processing aids that may be blended in the composition may include, for example, Viton~ from Du Pont, Dynamar~ from 3M or Ucarsil~ PA from Union Carbide which are all preferably added below 1 weight percent.
The polyolefin, IPE and other optional additives can be blended by well known techniques into the art such as by tumble blending or separately feeding into an extruder 1 5 hopper.
The cG."posilion of the present invention can be used to make several forms, including, for example, film, sheet orshaped articles by known pfocesses. For making shaped articles, the processes include, for example, blow molding, compression molding, and injection molding. For sheet and film manufacture, extrusion processes such as cast or blow pnxesses 20 may be used. In Modern Plastics Encyclopedia, 1969-70 edition, sheet is defined (page 52C) as a flat section of a ll,e-",oplastic resin with the length considerably greaterthan the width and 10 mils or greater in thickness. Film is defined (page 43) as an optional term for sheet having a nominal thickness notgreaterthan 0.010 inches. As an illustration of the present invention, a monolayer film and a multilayer film product will be described herein below using the 25 composition of the present invention.
A monolayer film can be made by various con~cnlional film forming processes including for example, a cast film process, a blown film process, oriented film process and other extrusion processes or coating p~ ocesses. A multilayer film may be made by processes c~",i"only used for manufacturing a multilayer film including, for example, coextrusion, 30 extrusion-coating, calendering and lamination. For making a multilayer film, coextrusion is p.e~e"ed,becausethenthemultilayerfilmproductcanbeobtainedinonestep.
While the co.,.po,ilion of the present invention can be used to make a monolayerfilm, the present invention will be des~,ibed herein with reference to a multilayer film, a p,efer-ed embodiment of the present invention. In its broadest scope the multilayer film 35 comprises a coextruded film structure containing at least one of its external or outer layers madeofthecG...posilionofthepresentinvention. AnyfilmstructuresuchasA/B,AtB/Aor A/B/C layered structures is possible, provided that at least one of the outer layers or skin layers of the multilayer film is made of the present composition.
The polyolefin, IPE and other optional additives can be blended by well known techniques into the art such as by tumble blending or separately feeding into an extruder 1 5 hopper.
The cG."posilion of the present invention can be used to make several forms, including, for example, film, sheet orshaped articles by known pfocesses. For making shaped articles, the processes include, for example, blow molding, compression molding, and injection molding. For sheet and film manufacture, extrusion processes such as cast or blow pnxesses 20 may be used. In Modern Plastics Encyclopedia, 1969-70 edition, sheet is defined (page 52C) as a flat section of a ll,e-",oplastic resin with the length considerably greaterthan the width and 10 mils or greater in thickness. Film is defined (page 43) as an optional term for sheet having a nominal thickness notgreaterthan 0.010 inches. As an illustration of the present invention, a monolayer film and a multilayer film product will be described herein below using the 25 composition of the present invention.
A monolayer film can be made by various con~cnlional film forming processes including for example, a cast film process, a blown film process, oriented film process and other extrusion processes or coating p~ ocesses. A multilayer film may be made by processes c~",i"only used for manufacturing a multilayer film including, for example, coextrusion, 30 extrusion-coating, calendering and lamination. For making a multilayer film, coextrusion is p.e~e"ed,becausethenthemultilayerfilmproductcanbeobtainedinonestep.
While the co.,.po,ilion of the present invention can be used to make a monolayerfilm, the present invention will be des~,ibed herein with reference to a multilayer film, a p,efer-ed embodiment of the present invention. In its broadest scope the multilayer film 35 comprises a coextruded film structure containing at least one of its external or outer layers madeofthecG...posilionofthepresentinvention. AnyfilmstructuresuchasA/B,AtB/Aor A/B/C layered structures is possible, provided that at least one of the outer layers or skin layers of the multilayer film is made of the present composition.
wo gS/01397 Xi~23~;3 PCT/USg4l0727g In Figure 1, there is shown a tvvo-layer film 10, comprising an outer layer 1 1 made of the blend composition of the present invention and an inner adjacent layer 12 of one or more polymers. Layer 12 can be made of any polymer resin which will adhere to the outer layer 11 including, for example, EVA, EAA, EMA, EMAA, EBA, ionomers, modified polyolefins, and 5 polyolefin materials such as LDPE, MDPE, HDPE, LLDPE, PP or blends thereof. .
One of the advantages of using the composition of the present invention as one of the layers in a film structure (layer 11 in Figure 1), is the recyclability of the layer. Any regrind, scrap or unused excess material can be reprocessed by reintroducing the material, as recycle, back into the layer made of the present composition or back into another layer of the 10 film without significantly affecting the properties of the film. When recycle material is used, generally from one percent by weight to 50 percent by weight of the recycle material can be added back into the layer.
With, efe-ence to Figure 2, there is shown one p. erer, ed embodiment of a multilayer film structure 2û of the present invention, in this case a three-layer structure, 15 including two outer layers or skin layers 21 with a core layer 22 sandwiched between the t~,vo skin layers 21.
The skin layers 21 are made of the aforementioned composition of the present invention. The core layer 22 can be made of any of the same resins for layer 1 1 and p, ~ te, ably a polyolefin material such as LDPE, MDPE, HDPE, LLDPE, PP or blends thereof.
Also, any of the aforementioned optional additives used for the composition of layer 1 1 can be used in any of the other layers 12 or 21 of the film.
The overall thickness of the film of the present invention can be from 5 microns to 200 microns, prere,ably from 50 to 150 microns. P(ererably~ the skin layer is from 2 percent to 25 percent of the total thickness of the film, preferably from S percent to 20 percent of the 25 total thickness of the film Optionally, at least one of the surfaces of the film, intended to be printed, istreated by a corona discharge treatment to bring the film's surface tension above 40 milli newton per meter (mN/m), p- eferably above 50 mN/m as measured according to ASTM D-2578 The corona discharge treatment is applied to at least one surface of the film. The corona 30 discharge treatment is well known in the art and described for example in surface prope, ~ies andtesting,Plastics&~oly."~.s,April 1969,pages138-142. Whilecoronatreatment,alone, increasesthesurfacetensionofthefilmlayertreatedtoimprovethespreadingoftheinkon the film surface, it is believed thatthe composition of the present invention, in conjunction with corona l,edlment or any other surface treatment of the film, further advantageously 35 enhancff the adhesion of the ink on the film without significant loss of optical prope, lies of the film.
In accordance with another embodiment of the present invention, the monolayer or multilayer films can be used as stock material for manufacturing labels, signs, displays, tags, _5_ wo gS/0~ 14~53 PCT/US94/07279 posters, stickers. For ex3m`plë, the film label stock can be used for making in-mold labels, pressure-sensitive labels and wrap around labels, sleeves and shrink sleeves.
One embodiment of this invention of particular interest relates to polyolefinic films useful for making glossy, or glossy and transparent, and ink-printable pressure-sensitive 5 labels. The clear polyolefinic films made of medium to high density polyethylene fiim and pressure-sensitive labels made from polyethylene film are typically used in labeling bottles.
While it is known to produce labels of polyolefins films, as aforementioned, thepoor printability of the polyolefin fil m usually requi res the application of an ink-pri ntable layer on top of the polyolefin film to impart improved printability to the polyolefin film.
Multilayered label films are commonly produced by coating a poiyolefin film with an ink-printable acrylic polymer, or coextruding or laminating the polyolefin film with a layer of ink-printable polymer. The composition of the present invention can be used to produce in one step polymeric films based on olefinic polymerswithout use of a top coat or ink printable layer. A monolayer film made from the present composition provides excellent printability without a significant loss of other fi l m prope~ lies such as optical properties such as low haze and high gloss.
While a monolayer film can be produced from the cc.-,-posilion of the present invention, for economical reasons, a pref~- ed embodiment of the present invention is to make a multilayer film wherein one of the outer layers or skin layers of the film is made of the 20 CG---pG~i lion of the present invention.
A pressure-sensitive film stock 30 is illustrated i n Figure 3 which i ncludes a single skin layer 11 on the outer side of a core layer 12 and a pressure-sensitive adhesive layer 31 directlyadjacenttheinnersideofthecorelayer 12. Thepressure-sensitiveadhesiveusedfor layer 31 may be any conventional pressure-sensitive adhesive such as acylic and styrene 25 butadiene. The film stock 30 is preferably used for the manufacture of pressure-sensitive labels.
Figure 4 shows another embodiment of a multilayer pressure-sensitive film stock 40includingtwoskinlayers21withacorelayer22andanadhesivelayer31 attachedtoatleastone of the skin layers 21.
In carrying out the process for making the film of the present invention, generally,firstafilmcGI~posilionisformedwhereinthecc"~posi~ioncc."~p~isesatleastone polyolefinmaterialandatleastonepolymericadditivewhichenhancestheinkprintability property of the composition while not adverseiy affecting the optical properties of the cc",.posilion. Then, a film from the composition is formed, for example, by coextrusion 35 techniques. An electrical discharge treatment may be applied to at least one surface of the resultant film to raise the surface tension of the resultant film.
Asafo(elllelllioned~ with the use of a skin layer utilizing the composition of the present invention, the ink printability of a multilayer film is enhanced. The skin layer of the 7 ' ~ PCTIUS94/07279 -- ;~14235~3 multiiayer film can be printed with various printi ng systems. For example, print techniques useful herein, include silk screen printing, rotogravure, letter press, offset, flexographic printing, stipple printing, cold fixing laser printing, copperplate printing.
Various types of inks can also be selected for use in the present invention 5 including, for example, one and two component inks, oxidatively or UV-drying inks, dissolve .
ordispersedor lOO% inksystems. Manycombinationsoffilm/printing,ink/printingtechniques are possible.
General Procedure In the Examples which follow, the general procedure used to manufacture the 10 film of the present invention is as follows:
Charge"l"ofafilmformingresinispreparedcomprisingXweightpercentofa polymeric resin re ~e~ ,ed to below as Resin A", Y percent of a polymeric additive referred to below as Additive B" and Z percent of one or more polyolefin resins refe. ed to below as .
Resin Co",po,iLion C".
Then Charge "Il" of a film forming resin composition comprising one or more polyolefin resins is prepared.
Both the "I" and ll" Charges are fed into extruders and coextruded to form a three-layered film with a l/ll/l layer structure. The total thickness of the film structure is T and the thickness of each layer of Charge I is T1.
An elerical "coronan discharge treatment is applied on one or both surfaces of the film to raise its surface tension.
The resulting film has excellent optical properties (similar haze and gloss as films consisting essentiallyof polyolefin), and hasexcellent ink-printabilitywithoutthe need to add any substrate onto the film's surface.
For econo",ical or practical reasons, it is prefe,c.ble to produce a multilayer film with the Charge I being at least one of the skin layers, but monolayer films comprising only the Charge I can also be made.
The following co",po,i Lions and conditions were tested.
ExamPle 1 A coextruded three-layer film having a l/ll/l layer structure was manufactured according to the above General Procedure. Charge I i ncl uded Resi n A, Additive B and Resin CGIIIPO~; ~ion C.
Resin A was 7 weight percent of a styrene-isoprene-styrene copoly. "er (SIS) having a melt index (Ml) of 9.0 grams per 10 minutes (9/10 min) (200 degrees centigrade (0)/5 35 kilograms (kg)) and containing 85 weight percent of polymerized isoprene.
Additive B was 5 weight percent of a 15 weight percent silicon dioxide masterbatch in a low density polyethylene (LDPE).
WO 95/01397 2i42353 PCT/USg4l0727g Resin Composition C was 10 weight percent of a high density polyethylene (HDPE) having a density of 0.955 gram per cubic centime~er (g/cm3) and a Ml of 4.0 g/10 min (190C/2.16kg).
The balance to 100 percent for Charge i was a LDPE having a density of 0.921 g/cm3 and a Ml of 3.5 9/l O min (190C/2.16 kg).
Charge ll of the film structure compnsed 80 weight percent of a HDPE having a densityofO.955g/cm3andaMlof4.0g/lOmin(190C/2.16kg);and20weightpercentofa LDPE having a density of 0.923 g/cm3 and a Ml of 1.75 9/l o min (190C/2.16 kg).A film having a of thickness of 90 micrometers of a l/ll/l layer structure was 1O produced by a cast coextrusion process using Charges I and ll described above. The thicknesses (Tl) of the external layers (Charge 1) was 10 micrometers each.
One surface of the film was treated by a "corona" discharge treatment to bring its surface tension above 50 mN/m.
The optical properties of the film is shown in Table 1. The percent gloss measurement of the film was measured in accordance with ASTM D-2457 and the percent haze measurement was measured in accordance with ASTM D- 1003.
The film produced in this Example 1 was printed on the corona treated side usingUV curable inks on flat bed silk screen printing equipment.
The adhesion of the ink on the film was tested using the following four ink 20 adhesion tests:
(1) adhesive tape test, (2) scratch . esislance on the dry film, (3) scratch resistance after immersion of the film for 4 hours in a 50/SO volumepercent solution of water plus shampoo at room te."pe(alure (22C), and (4) scratch rësi,ldnce after immersion of the films for 22 hours in a SO/50 volume percent solution of water plus shampoo at room temperdlure (22C).
The afo, el l ,e"lioned adhesive tape test is descri bed as follows: A 15 mm wide piece of self adhesive tape is pressed onto the surface of the printed area of a film sample. This 30 is then rapidly pulled away from the film. The percer,lage of ink rc,..o/ed from the sample by the tape is cc,..,paræd. The amount of ink is visually compared and a numerical rating of " 1 to 4" is given to the fil m samples wherein " 1 is the lowest amount of ink remaining on the tape and .,4u being the grealesl amount of ink remaining on the tape.
The afc, e",enlioned scratch resi~lance test is described as follows: A film label 35 sample is adhered onto a stiff surface. The printed surface of the film is manually rubbed with a metal spatula. The difficulty or ease of scratching the ink is rated as follows: 1 " not scratchable, 2" sc(at-hable with difficulty, "3 scratchable, "4" easily scratchable, 5"
WO 5SI~ 7 Z14Z353 PCT/US94/07279 scratchable by touching. This test is ~erformed on the dry film or on the wet film after immersion in the solutions described above.
The results of the above ink adhesion tests are listed in Table 11.
Example 2 A three-layer coextruded film having a 1/11/1 layer structure was manufac~ured .nd tested following the procedure of Example 1. The Charges I and 11 were the same as in Example 1 except that Resin A was 14 weight percent SIS having a of 9.0 9/l O min (200C/S kg) and containing 85 weight percent of polymerized isoprene. The optical properties of the resultant film are shown in Table I and the results of the adhesion tests are listed in Table 11.
Example 3 A three-layer coextruded film having a 1/11/1 layer structure was manufaured and tested following the procedure of Example 1. The Charges I and 11 were the same as in Example 1 except that Resin A was 25 weight percent Admer~ L 2000 resin, a polymeric resin containing around 0.6 weight percent of grafted maleic anhydride and commercially available from Mitsui Petrochemicals. The optical properties of the resultant film are shown in Table I and the results of the adhesion tests are listed in Table 11.
Comparative Example A
A three-layer coextruded fil m having a 1111/1 layer structure was manufactured and tested following the procedure of Example 1. The Charges I and 11 were the same as in Example 20 1 except that no Resin A was used in this Example. This comparative example was used as the Control. The optical p~o~e, lies of the Control is shown in Table I and the results of the adhesion tests are listed in Table 11.
Co",~a,d~ Examnle B
The adhesion tests described in Example 1 were carried out on a pure 25 polyethylene film coated with an acrylic coating (Comparative Example B). The results are listed in Table 11.
TABLE I
60 Degree Gloss Haze Film (%) (Z) 30 Co~trol 80 18 (Comparative Example A) Example 1 85 19 Example 2 85 17.5 Example 3 81 18 . ., ~ ~
. ~ " ~ ~ ,.....
C ;l o ~, X
_, E
X
~ ~ C~l C~
X
E
' G 0 C ~
o y U C
c~ F X
o _~ o ~! D
o J~
,~ - . C O C-0'3 U ~ ~I S~;
a~
O ~ ~ o ~ U ~ ~
U ~ C a~ u~ a a~
~¢ ~ U
o -- _ E~ ~ 3 3 E~
WO 95/OL397 . i ` ~ PCT/US94/07279 ` 2~42353 Tabie I shows that the oDtical properties of Examples 1 2 and 3 are simiiar to that of the Controi film.
From the results shown in Table ll films from Exam~les 1 2 and 3 pe, ior", as well as the film of Comparative Example B and far better than the Control film.
5 ExamDle 4 A three-layer coextruded film having a l/ll/l layer structure was manufactured according to the above General Procedure. Charge I included components Resin A Additive B
and Resin Composition C.
ResinAwas12weightpercentofSlShavingaMlof9.0g/10min(200C/5kg)and 10 containing 85 weight percent of polymerized isoprene.
Additive B was S weight percent of a 15 weight percent silicon dioxide masterbatch in a LDPE.
Resi n Co" ,posi lion C was 10 wei ght percent of a HDPE having a density of 0.965 g/cm3and a Ml of 8.09/10 min (190C12.16kg).
The balance to 100 percent for Charge I was a LDPE having density of 0.923 g/cm3and a Ml of 1.75 9/10 min (190C/2.16 kg).
Charge ll of the film structure co",p-ised 70 weight percent of a HDPE having a densityO.965g/cm3andaMlof8.0g/10min(190C/2.16kg); and20weightpercentofa LDPE
having a density of 0.922 g/cm3 and a Ml of 1.2 g/10 min (190C12.16 kg).
A fiim having a thickness of 90 micrometers of a l/ll/l layer structure was produced by a cast coextrusion process using Charges I and ll described above. The thicknesses (T1) of the external layers (Charge 1) was 10 micrometers each.
One surface of the film was treated by a 'corona discharge treatment to bring its surface tension above 50 mN/m.
The optical prope, lies of the film are shown on the following Table lll. The percent gloss measurement of the film was measured in accordance with ASTM D-2457 and the percent haze measurement was measured in accordance with ASTM D-1003.
ExamPle S
A three-layer coextruded film having a l/ll/l layer structure was manufactured and 30 tested following the procedure of Example 4. The Charges I and ll were the same as in Example 4 except that there was no Additive B in Charge 1. The optical properties of the resultant film are shown in Table lll.
Examole 6 A three-layer coextruded film having a l/ll/l layer strunure was manufactured and 35 tested following the procedure of Example 4. The Charges I and ll were the same as in Example 4 except that Resi n A was 12 weight percent of a styrene-isoprene-styrene/styrene-isoprene copolymers blend (SIS/SI) having a Ml of 10.0 9/10 min (200C15 kg) and containing 85 weight WO 95/01397 Z1423S3 PCT/uS94l0727g .
percent of polymerized isoprene. The SIS/SI ratio of the blena was 82/18 percent. The optical properties of the resultant film are shown in Table ill.
ExamDle 7 A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 4. The Charges 1 ana ll were the same as in ExaQ ple 4 except that Resin A was 12 weignt percem of SIS having a Ml of 12.0 9/lO min (200C15 kg) and containing 82 weight percenl of polymerized isoprene. The optical properties of the resultant film are snown in Table lll.
Exam~le 8 1 O A three-layer coextruded fi l m having a l/ll/l layer structure was manufactured and tested following the procedure of Example 4. The Charges I and ll were the same as in Example 4exceptthatResinAwas 12weightpercentofSlShavingaMlof 13.0g/10min(200C/Skg) and containi ng 70 weight percent of polymerized isoprene. The optical properties of the resultant film are shown in Table lll.
Exam~ole 9 A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested fol lowi ng the procedure of Example 4. The Charges I and l l were the same as i n Example 4 except that Resin A was 12 weight percent of SiS having a Ml of 40.0 9/10 min (200C/5 kg) and containing 55 weight percent of polymerized isoprene. The optical properties of the 20 resultant film are shown in Table lll.
WO 95/OL397 ~ PCTtUS94/07279 23~53 Com~arative ExamDle C
A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the Drocedure of Example 4. The Charges I and ll were the same as in Example 4 except that no Resin A was used in Charge 1. This comparative examDie was used as the 5 Control. The opticai pro,oertles of the Control are shown in Table lll.
TABLE III
60 Degree Gloss Haze Film (%) (%) Control 79 25 (Comparative Example C) Example 4 83 22 Example 5 91 18 Example 6 85 20 Example 7 85 20 5 Example 8 85 21 Example 9 95 22 2û Table lll shows that the optical prope- lies of Examples 4-9 are similar to the Control.
Comparative Examole D
A three-layer coextruded film having a l/ll/l layer structure was manufactured according to the above General Procedure. Charge I included co",poner,l~ Resin A Additive B
25 and Resin CG,-,posilion C.
Resin A was 8 weight percent of a sytrene-butadiene-styrene copolymer (SBS) having a Ml of 6.0 9/10 min (200C/5 kg) and containing 60 weight percent of polymerized butadiene.
Additive B was 5 weight percent of a l S weight percent silicon dioxide 30 masterbatch in a LDPE.
Resin Composition C was 10 weight percent of a HDPE having a density of 0.955 g/cm3andaMlof4.0g/10min(190C/2.16kg).
The balance to 100 percent for Charge I was a LDPE having density of 0.921 g/cm3- andaMlof3.5g/10min(190C/2.16kg).
Charge ll of the film structure comprised 80 weight percent of a HDPE having a density 0.955 g/cm3 and a Ml of 4.0 9/10 min (190C/2.16 kg); and 20 weight percent of a LDPE
having a density of 0.923 g/cm; and a Ml of 1.75 9/10 min (190C/2.16 kg).
WO gs/0l3g7 z~4z353 PCT/US94107279 A film having a thickrlès~ 5~ micrometers of a l/ll/l layer structure was produceci by a cast coextrusion process using Charges I and ll descriDed above. The thicknesses (T1) of the external layers (Charge 1) was 10 micrometers each.
One surface of the fi I m was treated by a "corona " discharge treatment to bri ng 5 its surface tension above 50 mN/m.
The opticai properties of the film is shown on the foilowing table IV. The percent gloss measurement of the film was measured in accordance with ASTM D-2457 and the percent haze measurement was measured in accordance with ASTM D- 1003 Comparative Example E
A three-layer coextruded film having a l/ll/l iayer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 excep~that Resin A was 25 weight percent of a ethylene-acrylic acid copolymer (EAA)havingaMlof 10.0g/10min(190C/2.16kg)andcontaining9weightpercentof polymerized acrylic acid. The optical properties of the resultant film are shown in Table IV.
ComDarative ExamDle F
A three-l ayer coextruded film havi ng a l/l l/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that Resin A was Z5 weight percent of a ethylene-methyl acrylate copolymer (EMA)havingaMlof3.0g/10min(190C/2.16kg)andcontaining 15weightpercentof 20 polymerized methyl acrylate. The optical prope, lies of the resultant film are shown in Table IV.
Comparative ExamDle G
A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that Resin A was 25 weight percent of a ethylene-butyl acrylate copolymer 25 (EBA)havingaMlof4.0g/10min(190C/2.16kg)andcontaining 17weightpercentof polymerized methyl acrylate. The optical prope. Lies of the resultant film are shown in Table IV.
WO 95/OL397 ;~1~2353 PCT/US94/07279 ComDarative ExamDle H
A three-iayer coextruded film having a l/ll/l lay~r structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that Resin A was 25 weight percent of a sodium salt of an ethylene-methacryllcacidcopoiymerhavingaMlof2.89/lOmin(190~C/2.16kg)andhavingadensitjof 0.94g/cm n Theoptical~ropertiesoftheresultantfilmareshownin T ableIV.
ComDarative Exam~le I
A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in 10 Example 10exceptthatResinAwas 15weightpercentofahutyl rubber. Theoptical properties of the resultant film are shown in Table IV.
ComDarative ExamPle J
A three-layer coextrùded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that no Resin A was used in Charge 1. This comparative example was used as the Control. The optical properties of the Control are shown in Table IV.
TABLE IV
Film 60 Degree Gloss Haze Control 80 18 (Comparative Example J) Example D 33 42 Example E 72 24 25 Example F 62 24 Example G 70 20 Example H 65 29 Example I 17 66 WO 95/01397 2142353 PCT~JS94/07279 Table IV shows that the optical properties of Comparative Examples D-l are worse(have lower gloss and higher haze~ than the Control film J.
One of the advantages of using the composition of the present invention as one of the layers in a film structure (layer 11 in Figure 1), is the recyclability of the layer. Any regrind, scrap or unused excess material can be reprocessed by reintroducing the material, as recycle, back into the layer made of the present composition or back into another layer of the 10 film without significantly affecting the properties of the film. When recycle material is used, generally from one percent by weight to 50 percent by weight of the recycle material can be added back into the layer.
With, efe-ence to Figure 2, there is shown one p. erer, ed embodiment of a multilayer film structure 2û of the present invention, in this case a three-layer structure, 15 including two outer layers or skin layers 21 with a core layer 22 sandwiched between the t~,vo skin layers 21.
The skin layers 21 are made of the aforementioned composition of the present invention. The core layer 22 can be made of any of the same resins for layer 1 1 and p, ~ te, ably a polyolefin material such as LDPE, MDPE, HDPE, LLDPE, PP or blends thereof.
Also, any of the aforementioned optional additives used for the composition of layer 1 1 can be used in any of the other layers 12 or 21 of the film.
The overall thickness of the film of the present invention can be from 5 microns to 200 microns, prere,ably from 50 to 150 microns. P(ererably~ the skin layer is from 2 percent to 25 percent of the total thickness of the film, preferably from S percent to 20 percent of the 25 total thickness of the film Optionally, at least one of the surfaces of the film, intended to be printed, istreated by a corona discharge treatment to bring the film's surface tension above 40 milli newton per meter (mN/m), p- eferably above 50 mN/m as measured according to ASTM D-2578 The corona discharge treatment is applied to at least one surface of the film. The corona 30 discharge treatment is well known in the art and described for example in surface prope, ~ies andtesting,Plastics&~oly."~.s,April 1969,pages138-142. Whilecoronatreatment,alone, increasesthesurfacetensionofthefilmlayertreatedtoimprovethespreadingoftheinkon the film surface, it is believed thatthe composition of the present invention, in conjunction with corona l,edlment or any other surface treatment of the film, further advantageously 35 enhancff the adhesion of the ink on the film without significant loss of optical prope, lies of the film.
In accordance with another embodiment of the present invention, the monolayer or multilayer films can be used as stock material for manufacturing labels, signs, displays, tags, _5_ wo gS/0~ 14~53 PCT/US94/07279 posters, stickers. For ex3m`plë, the film label stock can be used for making in-mold labels, pressure-sensitive labels and wrap around labels, sleeves and shrink sleeves.
One embodiment of this invention of particular interest relates to polyolefinic films useful for making glossy, or glossy and transparent, and ink-printable pressure-sensitive 5 labels. The clear polyolefinic films made of medium to high density polyethylene fiim and pressure-sensitive labels made from polyethylene film are typically used in labeling bottles.
While it is known to produce labels of polyolefins films, as aforementioned, thepoor printability of the polyolefin fil m usually requi res the application of an ink-pri ntable layer on top of the polyolefin film to impart improved printability to the polyolefin film.
Multilayered label films are commonly produced by coating a poiyolefin film with an ink-printable acrylic polymer, or coextruding or laminating the polyolefin film with a layer of ink-printable polymer. The composition of the present invention can be used to produce in one step polymeric films based on olefinic polymerswithout use of a top coat or ink printable layer. A monolayer film made from the present composition provides excellent printability without a significant loss of other fi l m prope~ lies such as optical properties such as low haze and high gloss.
While a monolayer film can be produced from the cc.-,-posilion of the present invention, for economical reasons, a pref~- ed embodiment of the present invention is to make a multilayer film wherein one of the outer layers or skin layers of the film is made of the 20 CG---pG~i lion of the present invention.
A pressure-sensitive film stock 30 is illustrated i n Figure 3 which i ncludes a single skin layer 11 on the outer side of a core layer 12 and a pressure-sensitive adhesive layer 31 directlyadjacenttheinnersideofthecorelayer 12. Thepressure-sensitiveadhesiveusedfor layer 31 may be any conventional pressure-sensitive adhesive such as acylic and styrene 25 butadiene. The film stock 30 is preferably used for the manufacture of pressure-sensitive labels.
Figure 4 shows another embodiment of a multilayer pressure-sensitive film stock 40includingtwoskinlayers21withacorelayer22andanadhesivelayer31 attachedtoatleastone of the skin layers 21.
In carrying out the process for making the film of the present invention, generally,firstafilmcGI~posilionisformedwhereinthecc"~posi~ioncc."~p~isesatleastone polyolefinmaterialandatleastonepolymericadditivewhichenhancestheinkprintability property of the composition while not adverseiy affecting the optical properties of the cc",.posilion. Then, a film from the composition is formed, for example, by coextrusion 35 techniques. An electrical discharge treatment may be applied to at least one surface of the resultant film to raise the surface tension of the resultant film.
Asafo(elllelllioned~ with the use of a skin layer utilizing the composition of the present invention, the ink printability of a multilayer film is enhanced. The skin layer of the 7 ' ~ PCTIUS94/07279 -- ;~14235~3 multiiayer film can be printed with various printi ng systems. For example, print techniques useful herein, include silk screen printing, rotogravure, letter press, offset, flexographic printing, stipple printing, cold fixing laser printing, copperplate printing.
Various types of inks can also be selected for use in the present invention 5 including, for example, one and two component inks, oxidatively or UV-drying inks, dissolve .
ordispersedor lOO% inksystems. Manycombinationsoffilm/printing,ink/printingtechniques are possible.
General Procedure In the Examples which follow, the general procedure used to manufacture the 10 film of the present invention is as follows:
Charge"l"ofafilmformingresinispreparedcomprisingXweightpercentofa polymeric resin re ~e~ ,ed to below as Resin A", Y percent of a polymeric additive referred to below as Additive B" and Z percent of one or more polyolefin resins refe. ed to below as .
Resin Co",po,iLion C".
Then Charge "Il" of a film forming resin composition comprising one or more polyolefin resins is prepared.
Both the "I" and ll" Charges are fed into extruders and coextruded to form a three-layered film with a l/ll/l layer structure. The total thickness of the film structure is T and the thickness of each layer of Charge I is T1.
An elerical "coronan discharge treatment is applied on one or both surfaces of the film to raise its surface tension.
The resulting film has excellent optical properties (similar haze and gloss as films consisting essentiallyof polyolefin), and hasexcellent ink-printabilitywithoutthe need to add any substrate onto the film's surface.
For econo",ical or practical reasons, it is prefe,c.ble to produce a multilayer film with the Charge I being at least one of the skin layers, but monolayer films comprising only the Charge I can also be made.
The following co",po,i Lions and conditions were tested.
ExamPle 1 A coextruded three-layer film having a l/ll/l layer structure was manufactured according to the above General Procedure. Charge I i ncl uded Resi n A, Additive B and Resin CGIIIPO~; ~ion C.
Resin A was 7 weight percent of a styrene-isoprene-styrene copoly. "er (SIS) having a melt index (Ml) of 9.0 grams per 10 minutes (9/10 min) (200 degrees centigrade (0)/5 35 kilograms (kg)) and containing 85 weight percent of polymerized isoprene.
Additive B was 5 weight percent of a 15 weight percent silicon dioxide masterbatch in a low density polyethylene (LDPE).
WO 95/01397 2i42353 PCT/USg4l0727g Resin Composition C was 10 weight percent of a high density polyethylene (HDPE) having a density of 0.955 gram per cubic centime~er (g/cm3) and a Ml of 4.0 g/10 min (190C/2.16kg).
The balance to 100 percent for Charge i was a LDPE having a density of 0.921 g/cm3 and a Ml of 3.5 9/l O min (190C/2.16 kg).
Charge ll of the film structure compnsed 80 weight percent of a HDPE having a densityofO.955g/cm3andaMlof4.0g/lOmin(190C/2.16kg);and20weightpercentofa LDPE having a density of 0.923 g/cm3 and a Ml of 1.75 9/l o min (190C/2.16 kg).A film having a of thickness of 90 micrometers of a l/ll/l layer structure was 1O produced by a cast coextrusion process using Charges I and ll described above. The thicknesses (Tl) of the external layers (Charge 1) was 10 micrometers each.
One surface of the film was treated by a "corona" discharge treatment to bring its surface tension above 50 mN/m.
The optical properties of the film is shown in Table 1. The percent gloss measurement of the film was measured in accordance with ASTM D-2457 and the percent haze measurement was measured in accordance with ASTM D- 1003.
The film produced in this Example 1 was printed on the corona treated side usingUV curable inks on flat bed silk screen printing equipment.
The adhesion of the ink on the film was tested using the following four ink 20 adhesion tests:
(1) adhesive tape test, (2) scratch . esislance on the dry film, (3) scratch resistance after immersion of the film for 4 hours in a 50/SO volumepercent solution of water plus shampoo at room te."pe(alure (22C), and (4) scratch rësi,ldnce after immersion of the films for 22 hours in a SO/50 volume percent solution of water plus shampoo at room temperdlure (22C).
The afo, el l ,e"lioned adhesive tape test is descri bed as follows: A 15 mm wide piece of self adhesive tape is pressed onto the surface of the printed area of a film sample. This 30 is then rapidly pulled away from the film. The percer,lage of ink rc,..o/ed from the sample by the tape is cc,..,paræd. The amount of ink is visually compared and a numerical rating of " 1 to 4" is given to the fil m samples wherein " 1 is the lowest amount of ink remaining on the tape and .,4u being the grealesl amount of ink remaining on the tape.
The afc, e",enlioned scratch resi~lance test is described as follows: A film label 35 sample is adhered onto a stiff surface. The printed surface of the film is manually rubbed with a metal spatula. The difficulty or ease of scratching the ink is rated as follows: 1 " not scratchable, 2" sc(at-hable with difficulty, "3 scratchable, "4" easily scratchable, 5"
WO 5SI~ 7 Z14Z353 PCT/US94/07279 scratchable by touching. This test is ~erformed on the dry film or on the wet film after immersion in the solutions described above.
The results of the above ink adhesion tests are listed in Table 11.
Example 2 A three-layer coextruded film having a 1/11/1 layer structure was manufac~ured .nd tested following the procedure of Example 1. The Charges I and 11 were the same as in Example 1 except that Resin A was 14 weight percent SIS having a of 9.0 9/l O min (200C/S kg) and containing 85 weight percent of polymerized isoprene. The optical properties of the resultant film are shown in Table I and the results of the adhesion tests are listed in Table 11.
Example 3 A three-layer coextruded film having a 1/11/1 layer structure was manufaured and tested following the procedure of Example 1. The Charges I and 11 were the same as in Example 1 except that Resin A was 25 weight percent Admer~ L 2000 resin, a polymeric resin containing around 0.6 weight percent of grafted maleic anhydride and commercially available from Mitsui Petrochemicals. The optical properties of the resultant film are shown in Table I and the results of the adhesion tests are listed in Table 11.
Comparative Example A
A three-layer coextruded fil m having a 1111/1 layer structure was manufactured and tested following the procedure of Example 1. The Charges I and 11 were the same as in Example 20 1 except that no Resin A was used in this Example. This comparative example was used as the Control. The optical p~o~e, lies of the Control is shown in Table I and the results of the adhesion tests are listed in Table 11.
Co",~a,d~ Examnle B
The adhesion tests described in Example 1 were carried out on a pure 25 polyethylene film coated with an acrylic coating (Comparative Example B). The results are listed in Table 11.
TABLE I
60 Degree Gloss Haze Film (%) (Z) 30 Co~trol 80 18 (Comparative Example A) Example 1 85 19 Example 2 85 17.5 Example 3 81 18 . ., ~ ~
. ~ " ~ ~ ,.....
C ;l o ~, X
_, E
X
~ ~ C~l C~
X
E
' G 0 C ~
o y U C
c~ F X
o _~ o ~! D
o J~
,~ - . C O C-0'3 U ~ ~I S~;
a~
O ~ ~ o ~ U ~ ~
U ~ C a~ u~ a a~
~¢ ~ U
o -- _ E~ ~ 3 3 E~
WO 95/OL397 . i ` ~ PCT/US94/07279 ` 2~42353 Tabie I shows that the oDtical properties of Examples 1 2 and 3 are simiiar to that of the Controi film.
From the results shown in Table ll films from Exam~les 1 2 and 3 pe, ior", as well as the film of Comparative Example B and far better than the Control film.
5 ExamDle 4 A three-layer coextruded film having a l/ll/l layer structure was manufactured according to the above General Procedure. Charge I included components Resin A Additive B
and Resin Composition C.
ResinAwas12weightpercentofSlShavingaMlof9.0g/10min(200C/5kg)and 10 containing 85 weight percent of polymerized isoprene.
Additive B was S weight percent of a 15 weight percent silicon dioxide masterbatch in a LDPE.
Resi n Co" ,posi lion C was 10 wei ght percent of a HDPE having a density of 0.965 g/cm3and a Ml of 8.09/10 min (190C12.16kg).
The balance to 100 percent for Charge I was a LDPE having density of 0.923 g/cm3and a Ml of 1.75 9/10 min (190C/2.16 kg).
Charge ll of the film structure co",p-ised 70 weight percent of a HDPE having a densityO.965g/cm3andaMlof8.0g/10min(190C/2.16kg); and20weightpercentofa LDPE
having a density of 0.922 g/cm3 and a Ml of 1.2 g/10 min (190C12.16 kg).
A fiim having a thickness of 90 micrometers of a l/ll/l layer structure was produced by a cast coextrusion process using Charges I and ll described above. The thicknesses (T1) of the external layers (Charge 1) was 10 micrometers each.
One surface of the film was treated by a 'corona discharge treatment to bring its surface tension above 50 mN/m.
The optical prope, lies of the film are shown on the following Table lll. The percent gloss measurement of the film was measured in accordance with ASTM D-2457 and the percent haze measurement was measured in accordance with ASTM D-1003.
ExamPle S
A three-layer coextruded film having a l/ll/l layer structure was manufactured and 30 tested following the procedure of Example 4. The Charges I and ll were the same as in Example 4 except that there was no Additive B in Charge 1. The optical properties of the resultant film are shown in Table lll.
Examole 6 A three-layer coextruded film having a l/ll/l layer strunure was manufactured and 35 tested following the procedure of Example 4. The Charges I and ll were the same as in Example 4 except that Resi n A was 12 weight percent of a styrene-isoprene-styrene/styrene-isoprene copolymers blend (SIS/SI) having a Ml of 10.0 9/10 min (200C15 kg) and containing 85 weight WO 95/01397 Z1423S3 PCT/uS94l0727g .
percent of polymerized isoprene. The SIS/SI ratio of the blena was 82/18 percent. The optical properties of the resultant film are shown in Table ill.
ExamDle 7 A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 4. The Charges 1 ana ll were the same as in ExaQ ple 4 except that Resin A was 12 weignt percem of SIS having a Ml of 12.0 9/lO min (200C15 kg) and containing 82 weight percenl of polymerized isoprene. The optical properties of the resultant film are snown in Table lll.
Exam~le 8 1 O A three-layer coextruded fi l m having a l/ll/l layer structure was manufactured and tested following the procedure of Example 4. The Charges I and ll were the same as in Example 4exceptthatResinAwas 12weightpercentofSlShavingaMlof 13.0g/10min(200C/Skg) and containi ng 70 weight percent of polymerized isoprene. The optical properties of the resultant film are shown in Table lll.
Exam~ole 9 A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested fol lowi ng the procedure of Example 4. The Charges I and l l were the same as i n Example 4 except that Resin A was 12 weight percent of SiS having a Ml of 40.0 9/10 min (200C/5 kg) and containing 55 weight percent of polymerized isoprene. The optical properties of the 20 resultant film are shown in Table lll.
WO 95/OL397 ~ PCTtUS94/07279 23~53 Com~arative ExamDle C
A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the Drocedure of Example 4. The Charges I and ll were the same as in Example 4 except that no Resin A was used in Charge 1. This comparative examDie was used as the 5 Control. The opticai pro,oertles of the Control are shown in Table lll.
TABLE III
60 Degree Gloss Haze Film (%) (%) Control 79 25 (Comparative Example C) Example 4 83 22 Example 5 91 18 Example 6 85 20 Example 7 85 20 5 Example 8 85 21 Example 9 95 22 2û Table lll shows that the optical prope- lies of Examples 4-9 are similar to the Control.
Comparative Examole D
A three-layer coextruded film having a l/ll/l layer structure was manufactured according to the above General Procedure. Charge I included co",poner,l~ Resin A Additive B
25 and Resin CG,-,posilion C.
Resin A was 8 weight percent of a sytrene-butadiene-styrene copolymer (SBS) having a Ml of 6.0 9/10 min (200C/5 kg) and containing 60 weight percent of polymerized butadiene.
Additive B was 5 weight percent of a l S weight percent silicon dioxide 30 masterbatch in a LDPE.
Resin Composition C was 10 weight percent of a HDPE having a density of 0.955 g/cm3andaMlof4.0g/10min(190C/2.16kg).
The balance to 100 percent for Charge I was a LDPE having density of 0.921 g/cm3- andaMlof3.5g/10min(190C/2.16kg).
Charge ll of the film structure comprised 80 weight percent of a HDPE having a density 0.955 g/cm3 and a Ml of 4.0 9/10 min (190C/2.16 kg); and 20 weight percent of a LDPE
having a density of 0.923 g/cm; and a Ml of 1.75 9/10 min (190C/2.16 kg).
WO gs/0l3g7 z~4z353 PCT/US94107279 A film having a thickrlès~ 5~ micrometers of a l/ll/l layer structure was produceci by a cast coextrusion process using Charges I and ll descriDed above. The thicknesses (T1) of the external layers (Charge 1) was 10 micrometers each.
One surface of the fi I m was treated by a "corona " discharge treatment to bri ng 5 its surface tension above 50 mN/m.
The opticai properties of the film is shown on the foilowing table IV. The percent gloss measurement of the film was measured in accordance with ASTM D-2457 and the percent haze measurement was measured in accordance with ASTM D- 1003 Comparative Example E
A three-layer coextruded film having a l/ll/l iayer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 excep~that Resin A was 25 weight percent of a ethylene-acrylic acid copolymer (EAA)havingaMlof 10.0g/10min(190C/2.16kg)andcontaining9weightpercentof polymerized acrylic acid. The optical properties of the resultant film are shown in Table IV.
ComDarative ExamDle F
A three-l ayer coextruded film havi ng a l/l l/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that Resin A was Z5 weight percent of a ethylene-methyl acrylate copolymer (EMA)havingaMlof3.0g/10min(190C/2.16kg)andcontaining 15weightpercentof 20 polymerized methyl acrylate. The optical prope, lies of the resultant film are shown in Table IV.
Comparative ExamDle G
A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that Resin A was 25 weight percent of a ethylene-butyl acrylate copolymer 25 (EBA)havingaMlof4.0g/10min(190C/2.16kg)andcontaining 17weightpercentof polymerized methyl acrylate. The optical prope. Lies of the resultant film are shown in Table IV.
WO 95/OL397 ;~1~2353 PCT/US94/07279 ComDarative ExamDle H
A three-iayer coextruded film having a l/ll/l lay~r structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that Resin A was 25 weight percent of a sodium salt of an ethylene-methacryllcacidcopoiymerhavingaMlof2.89/lOmin(190~C/2.16kg)andhavingadensitjof 0.94g/cm n Theoptical~ropertiesoftheresultantfilmareshownin T ableIV.
ComDarative Exam~le I
A three-layer coextruded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in 10 Example 10exceptthatResinAwas 15weightpercentofahutyl rubber. Theoptical properties of the resultant film are shown in Table IV.
ComDarative ExamPle J
A three-layer coextrùded film having a l/ll/l layer structure was manufactured and tested following the procedure of Example 10. The Charges I and ll were the same as in Example 10 except that no Resin A was used in Charge 1. This comparative example was used as the Control. The optical properties of the Control are shown in Table IV.
TABLE IV
Film 60 Degree Gloss Haze Control 80 18 (Comparative Example J) Example D 33 42 Example E 72 24 25 Example F 62 24 Example G 70 20 Example H 65 29 Example I 17 66 WO 95/01397 2142353 PCT~JS94/07279 Table IV shows that the optical properties of Comparative Examples D-l are worse(have lower gloss and higher haze~ than the Control film J.
Claims (13)
1. A film comprising at least one outer ink-printable layer, said layer consisting essentially of at least one polyolefin material and at least one polymeric additive which enhances the ink-printability property of said layer while not adversely affecting the optical properties of the film
2. A film of Claim 1 further comprising a pressure-sensitive adhesive layer
3. A label made from the film of Claim 1
4. A pressure sensitive label made from the film of Claim 2
5. The film of Claim 1, wherein the polymeric additive is an olefinic polymer or copolymer having double bonds or double bonds and polystyrene in its chemicai structure
6. The film of Claim 1, wherein the polymeric additive comprises a material selected from the group consisting of styrenic block copolymers, modified polyolefins and polyolefin polymers containing some degree of unsaturation.
7. The film of Claim 1, wherein the polymeric additive is a styrenic block copolymer.
8. The film of Claim 7, wherein the styrenic block copolymer is styrene-isoprene-styrene or styrene-isoprene.
9. The film of Claim 1, wherein the polyolefin material is an ethylene polymer.
10. The film of Claim 1, wherein the polyolefin material is selected from group consisting of LDPE, MDPE, LLDPE, HDPE, PP, propylene-ethylene copolymers, and mixtures thereof.
11. The film of Claim 1, wherein polymeric additive is present in an amount of from 3 weight percent to 50 weight percent.
12. The film of Claim 1, wherein polymeric additive is present in an amount of from 5 weight percent to 30 weight percent.
13. A method of making a label comprising the steps of:
i) providing a film comprising at least one outer ink-printable layer, said layer consisting essentially of at least one polyolefin material and at least one polymeric additive which enhances the ink-printability property of said layer while not adversely affecting the optical properties of the film; and ii) printing on said outer ink-printable layer.
i) providing a film comprising at least one outer ink-printable layer, said layer consisting essentially of at least one polyolefin material and at least one polymeric additive which enhances the ink-printability property of said layer while not adversely affecting the optical properties of the film; and ii) printing on said outer ink-printable layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8800293A | 1993-07-02 | 1993-07-02 | |
| US08/088,002 | 1993-07-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2142353A1 true CA2142353A1 (en) | 1995-01-12 |
Family
ID=22208522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002142353A Abandoned CA2142353A1 (en) | 1993-07-02 | 1994-06-28 | Glossy and transparent ink-printable polyolefinic film composition |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0658177A4 (en) |
| JP (1) | JPH08501125A (en) |
| KR (1) | KR950703027A (en) |
| AU (1) | AU685142B2 (en) |
| CA (1) | CA2142353A1 (en) |
| FI (1) | FI950944A0 (en) |
| NZ (1) | NZ269062A (en) |
| WO (1) | WO1995001397A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6884480B2 (en) | 1995-05-19 | 2005-04-26 | Cryovac, Inc. | Film containing alpha-olefin/vinyl aromatic copolymer |
| ES2305371T3 (en) | 2002-06-26 | 2008-11-01 | Avery Dennison Corporation | POLYMERIC FILMS ORIENTED IN THE DIRECTION OF MACHINING. |
| EP2049333B1 (en) | 2006-06-14 | 2012-12-05 | Avery Dennison Corporation | Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing |
| WO2007149900A2 (en) | 2006-06-20 | 2007-12-27 | Avery Dennison Corporation | Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof |
| EP2350185B1 (en) * | 2008-11-26 | 2013-05-08 | E. I. du Pont de Nemours and Company | Recyclable coated banner substrate |
| JP5540315B2 (en) * | 2010-03-30 | 2014-07-02 | 株式会社フジシール | Plastic label |
| US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
| BR112016028445B1 (en) | 2014-06-02 | 2022-05-31 | Avery Dennison Corporation | Oriented film with abrasion resistance, clarity and conformability, label assembly comprising the film and method for producing a labeled article |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3493480A (en) * | 1965-09-10 | 1970-02-03 | Mitsubishi Petrochemical Co | Composition containing polypropylenevinylpyridine-acrylate ester graft copolymer |
| NL7002442A (en) * | 1969-02-26 | 1970-08-28 | ||
| JPS5119460B2 (en) * | 1972-01-14 | 1976-06-17 | ||
| US4479989A (en) * | 1982-12-02 | 1984-10-30 | Cutter Laboratories, Inc. | Flexible container material |
| JPS59105039A (en) * | 1982-12-08 | 1984-06-18 | Mitsui Toatsu Chem Inc | Polyethylene resin composition for oriented film |
| CA1240808A (en) * | 1985-06-27 | 1988-08-23 | Vaclav G. Zboril | Process for the dyeing of polymers of ethylene |
| EP0358445A3 (en) * | 1988-09-07 | 1990-11-14 | Tonen Sekiyukagaku K.K. | Polyethylene composite film and label |
| DE3838027A1 (en) * | 1988-11-09 | 1990-05-10 | Zweckform Etikettiertechnik | ADHESIVE LABEL FOR STICKING ON A PACKAGE OF PP |
-
1994
- 1994-06-28 JP JP7503599A patent/JPH08501125A/en active Pending
- 1994-06-28 EP EP94922038A patent/EP0658177A4/en not_active Withdrawn
- 1994-06-28 KR KR1019950700787A patent/KR950703027A/en not_active Application Discontinuation
- 1994-06-28 AU AU72520/94A patent/AU685142B2/en not_active Ceased
- 1994-06-28 WO PCT/US1994/007279 patent/WO1995001397A1/en not_active Application Discontinuation
- 1994-06-28 CA CA002142353A patent/CA2142353A1/en not_active Abandoned
- 1994-06-28 NZ NZ269062A patent/NZ269062A/en unknown
-
1995
- 1995-03-01 FI FI950944A patent/FI950944A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU7252094A (en) | 1995-01-24 |
| EP0658177A1 (en) | 1995-06-21 |
| WO1995001397A1 (en) | 1995-01-12 |
| NZ269062A (en) | 1997-05-26 |
| JPH08501125A (en) | 1996-02-06 |
| KR950703027A (en) | 1995-08-23 |
| FI950944A (en) | 1995-03-01 |
| FI950944A0 (en) | 1995-03-01 |
| AU685142B2 (en) | 1998-01-15 |
| EP0658177A4 (en) | 1996-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60017797T2 (en) | FILMS AND LABELS OF COMPOSITIONS BASED ON POLYPROPYLENE | |
| EP1351823B1 (en) | Label film with improved adhesion | |
| US6770360B2 (en) | Multilayered thermoplastic film and sign cutting method using the same | |
| US8187692B2 (en) | In-mold label and molded article using the same | |
| US5849419A (en) | Uniaxially oriented label film with compatibilizer | |
| US9149976B2 (en) | Label for in-mold forming and resin container with the label | |
| US6025058A (en) | Composite plastics film or sheet | |
| EP1528978B1 (en) | Label film for in-mould methods | |
| US6040042A (en) | Composite plastics film or sheet | |
| US20040146699A1 (en) | Synthetic paper | |
| US8097338B2 (en) | In-mold label, and labeled resin-labeled article | |
| AU685142B2 (en) | Glossy and transparent ink-printable polyolefinic film composition | |
| WO2005100019A2 (en) | Biaxially oriented polypropylene film for labels | |
| EP1486528B1 (en) | Recording paper and label paper using same | |
| EP2094482B1 (en) | Labels | |
| EP0607783B1 (en) | Molding materials for calendering sheets of thermoplastic plastics, thermoplastic laminated sheets and process for the manufacture of sheets | |
| EP4282771A1 (en) | Container with label | |
| JP2000167994A (en) | Polypropylene synthetic paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |