Patent Grant
9662867
This invention relates to labelstocks that are conformable, printable and die-cuttable, and to a process for preparing such labelstocks and die-cut labels. More particularly, the invention relates to die-cuttable and printable adhesive containing labelstocks useful in preparing labels, and to the die-cut labels obtained therefrom.
It has long been known to manufacture and distribute pressure-sensitive adhesive labelstock for labels by providing a layer of a face or facestock material for the label or sign backed by a layer of pressure sensitive adhesive and PSA which in turn, generally is covered by a release liner or carrier. The liner or carrier protects the adhesive during shipment and storage and allows for efficient handling of an array of individual labels after the labels are die-cut and the matrix is stripped from the layer of facestock material and up to the point where the individual labels are dispensed in sequence on a labeling line. During the time from die-cutting to dispensing, the liner or carrier remains uncut and may be rolled and unrolled for storage, transit and deployment of the array of individual labels carried thereon.
Failure to reliably dispense is typically characterized by the label following the carrier around a peel plate without dispensing or “standing-off” from the carrier for application to the substrate. Such failure to dispense is believed to be associated with excessive release values between the label facestock material and the liner. Dispensability also is dependent upon the stiffness of the facestock. Failure to dispense may also be characterized by the wrinkling of the label due to lack of label stiffness at the dispensing speed as it is transferred from the carrier to the substrate. Another particular need in labeling applications is the ability to apply polymeric-film labels at high line speeds, since an increase in line speed has obvious cost saving advantages.
There is also a growing need for down-gauging of label films in order to improve the cost performance ratio of labelstock. A disadvantage of down-gauging of films is that the stiffness in the machine direction will become too low to guarantee good dispensing of the labels. This problem has been overcome in the past by utilizing materials having a higher modulus of elasticity and, hence, higher stiffness.
Polypropylenes, and in particular biaxially oriented polypropylene (BOPP), have been utilized successfully in down-gauging applications since polypropylene is relatively inexpensive and exhibits sufficient stiffness to dispense well. However, polypropylenes in general exhibit relatively high tensile modulus values in both machine-direction and cross-direction which results in labels that are not very conformable, and polypropylenes are not easily printable with UV based inks that are most commonly used to print on pressure sensitive labels. Accordingly, it is common practice to improve the printability of polypropylene by adding a print skin (by coextrusion) or a print receptive coating. These solutions, however, add complexity and costs to the production process.
In one embodiment, this invention relates to a die-cuttable and printable adhesive containing labelstock for use in adhesive labels that comprises
(A) an extruded machine direction oriented monolayer film facestock having an upper surface and a lower surface and comprising a mixture of
wherein the machine direction oriented film is obtained by stretching the extruded film in the machine direction at a stretching temperature of from about the melting temperature of the polyethylene up to the melting temperature of the propylene polymer or copolymer, and
(B) an adhesive layer having an upper surface and a lower surface wherein the upper surface of the adhesive layer is adhesively joined to the lower surface of the facestock.
In another embodiment, the invention relates to a die cuttable and printable adhesive containing labelstock for use in adhesive labels that comprises
(A) an extruded machine direction oriented multilayer film facestock that comprises
wherein the propylene content of the base layer is greater than the propylene content of the skin layer and the machine direction oriented film is obtained by stretching the extruded film at a stretching temperature of from about the melting temperature of the polyethylene up to the melting temperature of the propylene polymer or copolymer, and
(B) an adhesive layer having an upper surface and a lower surface wherein the upper surface of the adhesive layer is adhesively joined to the lower surface of the facestock.
In another embodiment, the invention relates to die-cut labels which are obtained from the adhesive labelstock of the invention.
In yet another embodiment, the invention relates to a process for preparing die-cuttable and printable adhesive containing labelstocks that comprises
(A) extruding a monolayer film having an upper surface and a lower surface and comprising a mixture of
(B) stretch orienting the extruded film in the machine direction at a stretching temperature of from about the melting temperature of the polyethylene up to the melting temperature of the propylene homopolymer or copolymer, and
(C) applying an adhesive layer having an upper surface and a lower surface to the lower surface of the film wherein the upper surface of the adhesive layer is joined to the lower surface of the film to form an adhesive labelstock.
In yet another embodiment, die-cut labels are prepared from the above prepared adhesive labelstock by
(D) applying a release liner to the lower surface of the adhesive layer, and
(E) die-cutting labels in the adhesive labelstock but not the liner.
In another embodiment the invention relates to a process for preparing machine direction oriented multilayer films that comprises
In yet another embodiment, the invention relates to a process for preparing die cut machine direction oriented multilayer film labels that comprises
In one embodiment, the polyethylene of the monolayer or multilayer film facestock comprises a low density polyethylene. The labelstock and labels obtained in accordance with the present invention exhibit desirable stiffness, conformability, dispensability and printability characteristics.
The present invention, in one embodiment, relates to the discovery that machine-direction oriented monolayer and multilayer films can be prepared that are characterized as having improved conformability, die-cuttability, printability and/or dispensability. As will be described in more detail hereinafter, the adhesive containing labelstocks of the invention, in one embodiment, comprise
(A) an extruded machine direction oriented monolayer film facestock having an upper surface and a lower surface and comprising a mixture of
(B) an adhesive layer having an upper surface and a lower surface wherein the upper surface of the adhesive layer is adhesively joined to the lower surface of the facestock.
The propylene homopolymers that may be utilized as component (A-1) in the monolayer film either alone or in combination with a propylene copolymer as described herein include a variety of propylene homopolymers such as those having melt flow rates (MFR) of from about 1 to about 20 g/10 min. as determined by ISO 1133 (230° C. and 2.16 kg). In another embodiment, melt flow rate of the propylene homopolymers that can be utilized in the present invention may range from about 1 to about 15 g/10 min.
A number of useful propylene homopolymers are available commercially from a variety of sources. SABIC® PP 500P is a propylene homopolymer having a melt flow rate of 3.1 g/10 min., a density of 0.905 g/cm3 and a DSC melting point of 160° C. SABIC® PP 520P is a propylene homopolymer having a melt flow rate of 10.5 g/10 min. and a density of 0.905 g/cm3. Another useful propylene homopolymer is SABIC® PP 575P which has a melt flow rate of 10.5 g/10 min., a density of 0.905 g/cm3 and a DSC melting point of 167° C. Other commercially available propylene homopolymers that can be utilized in the films of the present invention include those listed in the following Table I.
The propylene copolymers that can be utilized as a component in the monolayer film facestock in accordance with the present invention generally comprise copolymers of propylene and up to about 40% by weight of at least one alpha olefin selected from ethylene and alpha olefins containing from 4 to about 8 carbon atoms. Examples of useful alpha olefins include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. More often, the copolymers of propylene that may be utilized in the present invention comprise copolymers of propylene with ethylene, 1-butene or 1-octene. The propylene-alpha-olefin copolymers useful in the present invention include random copolymers as well as block copolymers. Blends of the copolymers as well as blends of the copolymers with propylene homopolymers can be utilized in the film compositions of the invention.
In one embodiment, the propylene copolymers are propylene-ethylene copolymers with ethylene contents of from 0.2% to about 10% by weight or from about 3 to about 6% by weight. With regard to the propylene-1-butene copolymers, 1-butene contents of up to about 15% by weight are useful. Propylene-1-octene copolymers that are useful in the present invention may contain up to about 40% by weight of 1-octene.
A number of useful propylene copolymers are available commercially and some of these are listed in the following Table II.
In one embodiment, the amount of propylene homopolymer or copolymer, or blend thereof (A-1) contained in the mixture used to form the monolayer films may range from about 25% to about 80% by weight. In other embodiments, the amount may range from about 30% to about 80%, or from about 40% to about 80% by weight of propylene homopolymer or copolymer of blends thereof. In yet other embodiments, the amount of propylene homopolymer or copolymer or blends thereof may range from about 50% to about 80% by weight. In another embodiment, the amount may range from about 55% to about 75% by weight.
A second component of the monolayer film facestocks utilized in the present invention comprises at least one polyethylene. In one embodiment, the polyethylene is a low density polyethylene. The term “low density” as utilized in this application, includes polyethylenes having a density of about 0.935 g/cm3 or less. Polyethylenes having densities of from about 0.850 to about 0.935 g/cm3 generally are referred to as low density polyethylenes. The polyethylenes that are useful in the present invention can be characterized as having a melt flow rate in the range of from about 0.1 to about 20 g/10 min. In another embodiment, the polyethylenes useful in the invention are characterized as having a melt flow rate of from about 1 to about 5 or 10 g/10 min.
The amount of polyethylene included in the monolayer films may range from about 20% to about 75% by weight. In other embodiments, the films contain from about 20% to about 70%, or from about 20% to about 60% by weight of the polyethylene. In yet other embodiments, the films contain from about 25% to about 50% or from about 25% to about 45% by weight of at least one polyethylene (A-2).
The low density polyethylenes useful in this invention are exemplified by the low density polyethylenes (LDPE), the linear low density polyethylenes (LLDPE), the very low density polyethylenes (VLDPE), the ultra low density polyethylenes (ULDPE) and the plastomers which are VLDPEs prepared by single site catalysts.
The low density polyethylenes (LDPE) may comprise homopolymers of ethylene or copolymers of ethylene with alpha olefins such as 1-butene, 1-hexene and 1-octene, or polar monomers such as vinyl acetate, methyl acrylate, or ethyl acrylate. LDPE homopolymers may have a density in the range of from about 0.920 to about 0.935. The amount of comonomers polymerized with the ethylene generally does not exceed 3.5 or 4% by weight.
Linear low density polyethylenes (LLDPE) are copolymers of ethylene and alpha-olefins. Although any alpha olefin containing from 3 to 20 carbon atoms can be used as a comonomer for LLDPE, the four most commonly used are 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In one embodiment, the LLDPE is characterized as having a density in the range of from about 0.915 to about 0.925 g/cm3.
The very low density (VLDPE) and ultra low density (ULDPE) polymers generally contain less than 4% of a comonomer and are characterized as having a density of less than 0.915 g/cm3.
Very low density polymers prepared using single-site catalysts and referred to in the art as plastomers generally contain higher amounts of comonomer (i.e., up to about 25% by weight), and plastomers are generally characterized as having a density of about 0.912 or less.
Linear low density polyethylenes are available commercially. A number of LLDPEs are available from Dex Plastomers under the general trade designation “STAMYLEX”. For example, STAMYLEX® 1016LF is a 1-octene linear low density polyethylene having a melt flow rate of 1.1 g/10 min., a density of about 0.919 g/cm3 and a DSC melting point of 123° C., STAMYLEX® 1026F is a 1-octene liner low density polyethylene having a melt flow rate of 2.2, a density of 0.919 g/cm3, and a DSC melting point of 123° C.; STAMYLEX® 1046F is a 1-octene linear low density polyethylene having a melt flow rate of 4.4 g/10 min., a density of 0.919 g/cm3 and a DSC melting point of 122° C.; STAMYLEX® 1066F is another 1-octene linear low density polyethylene that has a melt flow rate of 6.6 g/10 min., a density of 0.919 g/cm3 and a DSC melting point of 124° C.
Useful LLDPE are also available from Borealis A/S (Denmark) under the trade designation BORSTAR®. For example, BORSTAR® FB 4230 is a bimodal linear low density polyethylene film grade having a density of 0.923 g/cm3, a melting temperature (ISO 11357/03) of 124° C. and a melt flow rate (190° C./2.16 kg) of 0.4 g/10 min (ISO 1133); and BORSTAR® FB 2310 is a high molecular weight polyethylene film grade having a density of 0.931 g/cm3, a melt flow rate (190° C./2.16 kg) of 0.2 g/10 min, and a melting temperature of 127° C. Useful LLDPE available from Dow Chemical Co. include DOWLEX® 2042E which is an ethylene/octene-1 copolymer having a density of 0.930 g/cm3 and a melt index (ASTM D1238) of 1 g/10 min; DOWLEX® 2035G having a density of 0.919 g/cm3 and a melt index of 6 g/10 min., and DOWLEX® SC2107, another ethylene/octene-1 copolymer.
An example of a useful LDPE is HIMOD™ FT 5270 from Borealis NS. This material has a density of 0.927 g/cm3, a melt flow rate (190° C./2.16 kg) of 0.75 g/10 min, and a melting temperature of 115° C.
In one embodiment, a second component of the monolayer film facestocks utilized in the present invention comprises at least one medium or high density polyethylene. Medium density polyethyenes (MDPE) generally have a density between about 0.935 and 0.940 g/cm3. The term “high density polyethylene” or “HDPE” refers to a polyethylene having a density of about 0.940 to about 0.965 g/cm3.
The plastomers that may be utilized in the films of the present invention are very low density copolymers and terpolymers of ethylene with an alpha olefin, and these plastomers are characterized as having a density of about 0.912 g/cm3 or less. These copolymers typically comprise from about 2 to about 30% or from about 5 to about 25% of the alpha olefin. The alpha olefins, which have been described above, include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and 1 dodecene. Particularly useful alpha olefins include 1-butene and 1-hexene. An example of an ethylene terpolymer is ethylene-1-hexene-1-butene. These low density ethylene copolymers are obtained by copolymerization of ethylene with an alpha olefin using single-site metallocene catalysts. Such copolymers are available commercially from Exxon Mobil Chemical Company, Basell, and Dow Chemical Company.
Examples of useful ethylene plastomers include the EXACT series plastomers that are available from Exxon-Mobil Chemical Co. which include linear ethylene-butene copolymers such as EXACT® 3024 having a density of about 0.905 gms/cc and a melt index of about 4.5 g/10 min.; EXACT® 3027 having a density of about 0.900 gms/cc and a melt index of about 3.5 g/10 min.; EXACT® 4011 having a density of about 0.888 gms/cc and a melt index of about 2.2 g/10 min.; EXACT® 4049 having a density of about 0.873 gms/cc and a melt index of about 4.5 g/10 min; and ethylene-hexene copolymers such as EXACT® 4150 having a density of about 0.895 gms/cc and a melt index of about 3.5 g/10 min.
Ethylene plastomers such as those sold by Dow Chemical Co. under the tradename AFFINITY® also may be employed in the invention. These plastomers are believed to be produced in accordance with U.S. Pat. No. 5,272,236, the teachings of which are incorporated herein in their entirety by reference. The ethylene plastomers include interpolymers of ethylene with at least one C3-C20 alpha-olefin and/or C2-C20 acetylenically unsaturated monomer and/or C4-C18 alpha-olefins.
Examples of these ethylene plastomers include AFFINITY® PF 1140 having a density of about 0.897 gms/cc, and a melt flow index of about 0.5 g/10 mins; AFFINITY® PF 1146 having a density of about 0.90 gms/cc, and a melt index of about 1 gms/10 min; AFFINITY® PL 1880 having a density of about 0.902 gms/cc, and melt index of about 1.0 gms/10 min; AFFINITY® EG 8100 having a density of about 0.87 gms/cc, and a melt index of about 1 gms/10 min.; AFFINITY® EG 8150 having a density of about 0.868 gms/cc, and a melt index of about 0.5 gms/10 min.; AFFINITY® EG 8200 having a density of about 0.87 gms/cc, and a melt index of about 5 g/10 min.; and AFFINITY® KC 8552 having a density of about 0.87 gms/cc, and a melt index of about 5 g/10 min.
Examples of terpolymers are Exxon's EXACT® 3006 (an ethylene-butene-hexene terpolymer with a density of 0.910 g/cm3 and M.F.I. of 1.2 g/10 min; EXACT® 3016 (an ethylene-butene-hexene terpolymer having a density of 0.910 g/cm3 and a M.F.I. of 4.5 g/10 min; EXACT® 3033 (an ethylene-butene-hexene terpolymer having a density of 0.900 g/cm3 (g/cc) and a M.F.I. of 1.2 g/10 min (g/10′)); EXACT® 3034 (an ethylene-butene-hexene terpolymer having a density of 0.900 g/cm3 (g/cc) and a M.F.I. of 3.5 g/10 min (g/10′)); Dow AFFINITY® PL 1840 (an ethylene-propylene-butylene terpolymer); Dow AFFINITY PL 1845 (an ethylene-propylene-butylene terpolymer); Dow AFFINITY® PL 1850 (an ethylene-propylene-butylene terpolymer); and Exxon Mobil ZCE 2005 (an ethylene-propylene-butylene terpolymer).
In one embodiment, the polyethylenes useful in the films used in the present invention include polyethylenes having a melt flow rate (MFR) as determined by ISO 1133 in the range of about 0.1 to about 20, and more often, in the range of about 1 to about 10. In another embodiment, it is desirable for the polyethylene and the propylene homopolymer or copolymer to have about the same viscosity at the extrusion conditions of temperature (200°-240° C.) and shear rate in the extruder.
In one embodiment, the facestock films may be nucleated. Various nucleating agents can be incorporated into the film formulations used in the present invention, and the amount of nucleating agent added should be an amount sufficient to provide the desired modification of the crystal structure while not having an adverse effect on the desired properties of the film. It is generally desired to utilize a nucleating agent to modify the crystal structure and provide a large number of considerably smaller crystals or spherulites to improve the transparency (clarity) of the film. The amount of nucleating agent added to the film formulation should not have a deleterious affect on the clarity of the film. The amounts of nucleating agent incorporated into the film formulations of the present invention are generally quite small and range from about 500, or from about 750 or from about 850 ppm. The nucleating agents may be present in an amount up to 5000, or up to about 3000, or up to about 1000.
Nucleating agents that have been used heretofore for polymer films include mineral nucleating agents and organic nucleating agents. Examples of mineral nucleating agents include carbon black, silica, kaolin and talc. Among the organic nucleating agents that have been suggested as useful in polyolefin films include salts of aliphatic mono-basic or di-basic acids or arylalkyl acids such as sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, aluminum phenyl acetate, and sodium cinnamate. Alkali metal and aluminum salts of aromatic and alicyclic carboxylic acids such as aluminum benzoate, sodium or potassium benzoate, sodium beta-naphtholate, lithium benzoate and aluminum tertiary-butyl benzoate also are useful organic nucleating agents. Wijga in U.S. Pat. Nos. 3,207,735, 3,207,736, and 3,207,738, and Wales in U.S. Pat. Nos. 3,207,737 and 3,207,739, all patented Sep. 21, 1966, suggest that aliphatic, cycloaliphatic, and aromatic carboxylic, dicarboxylic or higher polycarboxylic acids, corresponding anhydrides and metal salts are effective nucleating agents for polyolefin. They further state that benzoic acid type compounds, in particular sodium benzoate, are the best embodiment of the nucleating agents.
In one embodiment, the nucleating agents are sorbitol derivatives or organic phosphates. Substituted sorbitol derivatives such as bis (benzylidene) and bis (alkylbenzilidine) sorbitols wherein the alkyl groups contain from about 2 to about 18 carbon atoms are useful nucleating agents. More particularly, sorbitol derivatives such as 1,3,2,4-dibenzylidene sorbitol, and 1,3,2,4-di-para-methylbenzylidene sorbitol are effective nucleating agents for polypropylenes. Useful nucleating agents are commercially available from a number of sources. MILLAD® 8C-41-10, MILLAD® 3988 and MILLAD® 3905 are sorbitol nucleating agents available from Milliken Chemical Co.
Other acetals of sorbitol and xylitol are typical nucleators for polyolefins and other thermoplastics as well. Dibenzylidene sorbitol (DBS) was first disclosed in U.S. Pat. No. 4,016,118 by Hamada, et al. as an effective nucleating and clarifying agents for polyolefin. Since then, large number of acetals of sorbitol and xylitol have been disclosed. Representative US patents include: Kawai, et al., U.S. Pat. No. 4,314,039 on di(alkylbenzylidene) sorbitols; Mahaffey, Jr., U.S. Pat. No. 4,371,645 on di-acetals of sorbitol having at least one chlorine or bromine substituent; Kobayashi, et al., U.S. Pat. No. 4,532,280 on di(methyl or ethyl substituted benzylidene) sorbitol; Rekers, U.S. Pat. No. 5,049,605 on bis(3,4-dialkylbenzylidene) sorbitols including substituents forming a carbocyclic ring. These patents are hereby incorporated by reference. These patents are hereby incorporated by reference.
The machine direction oriented monolayer films used in the present invention may also contain antiblocking agents. The addition of antiblocking agents to the film formulations reduces the tendency of the films to block during windup, regulates the slip and anti-static properties of the films and allows a smooth unwinding from the reels. Any of the antiblocking agents described in the prior art as useful additives modifying the properties of polymer films, and in particular, olefin polymer films, can be included in the film formulations of the present invention. Silicas with average particle sizes of about 2 microns or less can be utilized for this purpose, and only small amounts (for example, 1000 to 5000 ppm) of the fine silica are needed. Several antiblocking agents based on synthetic silica are available from A. Schulman, Inc., Akron, Ohio, under the general trade designation POLYBATCH®. These materials are antiblocking masterbatches and comprise free-flowing pellets comprising propylene homopolymers or copolymers and the synthetic silica. For example, POLYBATCH® ABPP-05 comprises 5% synthetic silica in a propylene homopolymer; ABPP-10 comprises 10% synthetic silica in a propylene homopolymer; and ABPP-05SC comprises 5% synthetic silica and a random propylene copolymer. When the antiblocking agents are to be utilized in the preparation of the multilayer films of the present invention, the antiblocking agent generally is added to the skin layer formulations only. Useful antiblocking agents are Ampacet's Seablock 1 and Seablock 4.
In another embodiment, the film compositions may contain at least one processing aid. The processing aid acts to facilitate extrusion. These processing aids include hexafluorocarbon polymers. An example of a commercially available processing aid that can be used is AMPACET® 10919 which is a product of Ampacet Corporation identified as a hexafluoro carbon polymer. Another example of a useful processing aid is AMPACET® 401198. The processing aids are typically used at concentrations of up to about 1.5% or form about 0.5% to about 1.2% by weight. In another embodiment, the processing aid is present in an amount up to about 0.25% by weight, and in one embodiment about 0.03% to about 0.15% by weight.
The film compositions used in the present invention also may contain other additives and particulate fillers to modify the properties of the film. For example, colorants may be included in the film such as TiO2, CaCO3, etc. The presence of small amounts of TiO2, for example, results in a white facestock. Antiblock agents also can be included in the formulations. AB-5 is an antiblock concentrate available from A. Schulman Inc., Akron, Ohio which comprises 5% solid synthetic amorphous silica in 95% low density polyethylene. ABPP05SC is an antiblock concentrate from Schulman containing 5% of a synthetic amorphous silica antipropylene copolymer. The amount of antiblock agent (silica) present in the formulations may range from about 500 to 5000 ppm.
In some embodiments, particularly where it is desired that the film is clear, the film is free of inert particulate filler material although very small amounts of particulate filler material may be present in the film due to impurities, etc. The term “free of” as used herein, is intended to mean that the film contains less than about 0.1% by weight of the particulate filler material. Films that are free of particulate filler are particularly useful when it is desired to prepare a film that is clear and that may be characterized as having low haze, for example, less than 10% or even less than 6% haze. Haze or clarity is determined using a BYK-Gardner haze-gloss meter as known in the art.
The following examples in Table III illustrate some of the compositions that are useful in the preparation of the machine direction oriented monolayer films used in the present invention. Unless otherwise indicated in the following examples, in the claims, and elsewhere in the written description, all parts and percentages are by weight, temperatures are in degrees centigrade, and pressures are at or near atmospheric pressure.
The monolayer films useful in the present invention are prepared by extrusion techniques well known to those skilled in the art, and the films may range in thickness of from about 0.5 mils (12.5 microns) to about 3, 4 or 5 mils. More often, the films have a thickness of from about 2 to about 3 mils. It has been discovered that such down gauged films exhibit desirable stiffness and modulus values to provide films that are die-cuttable/dispensable in high speed dispensing, and conformable. In one embodiment, the films are stretch oriented in the machine direction only.
As noted above, the monolayer films utilized in the present invention are films that have been oriented in the machine direction. In one embodiment, the machine direction oriented films are obtained by hot-stretching films in the machine direction at a stretch ratio of at least 2:1. In other embodiments of the invention, the films are hot stretched at ratios of at least about 3:1, or at least 5:1 or at least about 6:1 or at least about 7:1 up to about 9:1 or 10:1. In one embodiment, the films are hot stretched at a ratio of 6:1 to about 9:1.
One feature of the present invention is that the hot stretching is carried out at a temperature within the range of from about the melting temperature of the polyethylene up to the melting temperature of the propylene polymer or copolymer used in the mixture to form the film. The term “melting temperature” as used herein refers to the DSC melting point of the polymers (DIN 53765). It has been discovered that when the hot stretching is conducted at about or above the melting temperature of the polyethylene and below the melting temperature of the polypropylene, improved die-cuttability and printability are obtained. Accordingly, typical stretching temperatures, depending upon the particular polyethylene used, may range from about 115° to 145° C. In other embodiments, stretching temperatures at or above about 125° C. are utilized. Stretching at such higher temperatures generally results also in a low shrinkage film (for example e.g., less than 2% shrinkage at 70° C.)
In one embodiment, the monolayer films (or the multilayer films of the invention described below) that have been stretch oriented in the machine direction while in a heated condition are then passed over heated annealing rolls where the stretched films are annealed or heat-set. After the heat setting or annealing operation, the film is then passed over chill rolls to complete the stretch and heat-set operations. The temperature used in the heat setting step (as with the stretching step) depends on the particular polymers used in the blends, and these temperatures may range from about 100° C. to about 150° C. The temperature used for the hot stretching and heat setting steps may be about the same, although in some instances, the temperature of heat setting is lower than the temperature used for heat stretching. In one embodiment, the temperature of the annealing rolls may be from about 100° C. to about 140° C., and in another embodiment, the annealing temperature may range from about 110° C. to about 135° C.
In one embodiment, the extruded monolayer films, which are machine-direction oriented, may be prepared by the general procedure described and illustrated in
As mentioned above, the stiffness of the film is important to the proper dispensing of the labels at higher line speeds.
After passing the flatstock M around pre-heat rolls 201 and 202 which soften the stock, the softened flatstock is then stretched between the heated orientation roll pair 205 and 206, the latter rotating at a multiple of the speed of the pre-heat rolls 201 and 202, corresponding to the desired stretch ratio of, for example, 7:1. After stretching, the stock then passes over the annealing rolls 209 and 210 at which the stock is annealed or heat set, and finally, the stock passes over the chill roll 212 to complete the hot stretch operation. The stock may then be taken up in roll form as shown in
The following Examples A-V in Table IV illustrate the preparation of the machine direction oriented monolayer films utilized in the present invention. The films are prepared utilizing the general procedure described above utilizing the casting, pre-heat, stretching and annealing temperatures, and the stretch ratios specified in Table IV. Control films, identified as Examples C-A through C-F also are prepared utilizing the same apparatus, but utilizing lower stretching temperatures.
Machine-direction oriented multilayer films also may be utilized in the present invention. The multilayer films generally will comprise
(A) a base layer having an upper surface and a lower surface and comprising a mixture of at least one propylene polymer or copolymer and at least one polyethylene, and
(B) at least one skin layer on the upper surface of the base layer or on both the upper and lower surfaces of the base layer wherein the skin layer comprises
In one embodiment, the propylene homopolymer or copolymer content in the base layer is greater than the propylene homopolymer or copolymer content in the skin layers. Thus, the mixture utilized in the base layer may comprise from about 30% or about 50% or about 60% or even 70% up to about 95% or even 99% by weight of polypropylene, and from about 1 or 5% up to about 70% of the polyethylene. For example, in one embodiment of the invention, the base layer comprises about 60% by weight of a propylene homopolymer and about 40% by weight of an LLDPE, and the skin layer comprises about 40% of a propylene homopolymer or a random propylene copolymer and about 60% of an LLDPE.
Generally, the base layer is relatively thick compared to the skin layer or layers. Thus, in one embodiment, the thickness of the base layer is about 5 to 10 or more times the thickness of the skin layer. For example, thickness ratios for two layered films (base:first skin) include 50:5, 45:10, and 45:5, and for three layered films (first skin:base:second skin) 5:50:5, etc.
In one embodiment the multilayer films comprising a base layer and at least one skin layer may be prepared by coextrusion of the layers or by laminating preformed layers together as known in the art. The layers of the coextrudate may be formed by simultaneous extrusion from a suitable known type of coextrusion die, and the layers are adhered to each other in a permanently combined state. In some embodiments, the base layer may be relatively thick compared to the skin layer or layers.
In one embodiment, the propylene homopolymers or copolymers utilized in the base layer are the same as the propylene homopolymers or copolymers utilized in the skin layer(s), and in another embodiment, the propylene homopolymers or copolymers are different. Similarly, in one embodiment, the polyethylene utilized in the base layer is the same as the polyethylene utilized in the skin layer(s), or the polyethylene utilized in the base layer may be different from the polyethylene utilized in the core layer. Where different polyethylenes are utilized in the mixtures of the base layer and the mixtures of the skin layer(s), the stretching temperature utilized in the orientation of the film is at least the melting temperature of the lower melting polyethylene.
Any of the propylene homopolymers and copolymers and the polyethylenes described above as being useful in the monolayer films may be used in the base layer and the skin layer or skin layers of the multilayer films.
The multilayer films may be prepared by means known to those skilled in the art. Typically, the films are coextruded at temperatures between 120° to about 290° C. or from about 150° to about 260° C. A useful procedure for preparing the multilayer films is coextrusion at 230° C. The coextruded multilayer films are oriented in the machine direction in the same manner and under the same conditions as described above for the monolayer films. That is, the stretch orientation of the multilayer film is carried out at a temperature at about or above the melting temperature of the polyethylene(s) in the base and skin layer(s). If more than one type of polyethylene is included in the multilayer film, the film is stretch oriented at a temperature at or above the highest melting polyethylene. The stretch oriented multilayer films may then be annealed or heat set as described above with regard to the monolayer films. Thus, the procedure described above with respect to
In the coextruded machine direction oriented multilayer films as described above wherein the base layer contains an increased amount of propylene homopolymer or copolymer, such base layers are characterized as having higher stiffness than would be obtained if a lower amount of polypropylene were used in the base layer. Also, in one embodiment, satisfactory adhesion of the skin layer or layers to the base layer is adhered without the need for an adhesive tie layer between the base layer and the skin layer or layers.
The following Example AA illustrates the preparation of a machine direction oriented multilayer film in accordance with the present invention.
The film formulation of Example 19 and the film formulation of Example 8 are coextruded by simultaneous extrusion through a coextrusion die, and the two layers are adhered to each other in a permanently combined state. A thickness of each of the layers is adjusted to provide a two layer film, after stretching having a total thickness of about 60 microns with a thickness of the base layer being 10 times the thickness of the skin layer. The two layer film is then preheated, stretched and annealed with the procedures described above for the monolayer films utilizing a casting temperature of 65° C., a preheat temperature of 110° C., a stretching temperature of 125° C. and an annealing temperature of 105° C. The stretch ratio is 8:1. The oriented two layer film obtained in this manner is characterized as having a caliper of 61 microns.
In another embodiment the invention relates to a process for preparing machine direction oriented multilayer film labelstock that comprises
In one embodiment, the stretch oriented multilayer film obtained in (B) is annealed or heat set before applying the adhesive layer in (C).
One of the features of the relatively thin films used in the invention, prepared as described above, is that the stiffness of the thin films in the machine direction is sufficiently high to provide for improved properties such as high speed dispensability, and the stiffness in the cross direction is sufficiently low as to provide a die cut label that is conformable. In one embodiment, the MD stiffness of the films is at least 20 mN, and in other embodiments, the MD stiffness is at least 25, or at least 28 or at least 30 or even 35 mN. The stiffness of the films described above in the cross direction (CD) is much less than the MD. Thus, for example, in one embodiment, the MD stiffness is at least 2 to 3 times the CD stiffness. In other embodiments, the MD stiffness is from about 3 to about 5 times the CD stiffness.
The stiffness of the machine-direction oriented monolayer and multilayer films utilized in the present invention is determined using an L&W Bending Resistance Tester (Test Method: ISO 2493). In general, the relationship between the L&W stiffness in mN to the Gurley stiffness as measured by TAPPI T543PM-84 is as follows: L+W=1.75×Gurley.
The results of the L+W stiffness tests on the films of Examples A-G and AA, and comparative films CA-CF, as determined by Test Method ISO 2493, are summarized in Table IV. In the tests, the bending angle is 15°; the distance between the measuring edge and the pivoting ax is 5 mm; the height of the sample is 38 mm; and the length of the sample is sufficient to be clamped and to touch, with an overlap, the measuring edge (typically about 50 mm).
One of the advantages of the labelstock and labels of the present invention is that useful labels can be prepared that are thinner than many of the labels presently utilized in the art. Accordingly, it has been discovered that labelstocks and labels of the invention containing a facestock having a thickness of from 25 to 75 microns (1 to 3 mils) or from about 45 to about 65 microns are useful in high speed dispensing. Accordingly, the L&W stiffness values for the films utilized in the invention (e.g., films A through G and AA) and the control films (films C-A through C-F) are corrected to 55 microns to provide an indication of their relative utility at this thickness. The correction to 55 microns utilizes the following equation where m is the measured thickness of the film tested.
MD55=MDmX(55/m)3
This calculation is based on the assumption that the film is homogenous in the thickness; that is, the modulus of elasticity is the same throughout the thickness.
The films that have been described above and that are useful in the facestocks and labels of the invention also are characterized as having a much higher modulus in the MD than in the CD. In one embodiment, the modulus of the films in the MD may be about 2500 MPa or higher, and the modulus in the CD as low as 400 or 500 MPa. In another embodiment, the MD modulus is at least 3.5 or at least 4 times the CD modulus. Modulus is Young=s modulus measured according to ISO 527-1 using a Zwick Z010.
The facestock films described above and which are utilized in the preparation of the labelstocks and labels of the present invention also are characterized by having a low shrinkage. In one embodiment, the films exhibit a shrinkage of less than 3% or even less than 2% at 70° C. In one embodiment, the films exhibit a shrinkage of less than 1% at 70° C. In this test, after conditioning the film at 23° C. and 50% relative humidity, the length of a film is measured before and after immersion in water at 70° C. for 2 minutes, and the shrinkage is calculated by the formula: (length before−length after/length before).
The results of the shrinkage testing of the films of Examples A to G and Comparative Examples CA to CD are summarized in Table V.
The facestock films described above and which utilized in the labelstocks and labels of the present invention also are characterized as having improved printability, particularly, with UV based inks that are most commonly used to print pressure sensitive labels, without reducing other desirable properties such as die-cuttability, shrinkage, etc. The printability of the labelstocks and labels of the present invention is determined by corona treating the film on a Vetaphone Corona Plus TF-415 at 50 W-min/m2. Subsequently a layer of 2.1 to 2.7 g/m2 of Uvonova Process Magenta UNV30080 from XSYS is applied with an IGT C1 printability tester. The ink is UV cured on a Primarc Minicure at 30 m/min and 80 W/cm, and the ink adhesion is evaluated with the tape test method with SCOTCH® 810 tape according to ASTMD3359 directly and after 24 hours. In this test ink adhesion or anchorage is evaluated by applying a SCOTCH® 810 tape with pressure to the top of the printed image, and the tape is then quickly removed. The amount of ink remaining in the film tape is noted on a scale of 0 to 5, a A0″ representing complete transfer of the ink to the tape, a A1″ representing severe ink transfer to the tape, and a A5″ representing no ink transfer to the tape.
The results of the ink adhesion testing on the film of Examples A to G and Comparative Examples C-A to C-D are summarized in Table V. The results of the ink adhesion testing on the films of Examples H-V, AA and control films CE and CF are summarized in Table VI. As shown therein, the machine direction oriented films of Examples A to G, which were stretch oriented at a temperature above the melting temperature of the polyethylene, exhibited better ink adhesion as compared with the films C-A to C-D, which were stretched at a lower temperature.
In one embodiment, the present invention relates to a die-cuttable and printable adhesive-containing a labelstock for use in adhesive labels. The films that have been described above are utilized as facestock films in the labelstocks and labels of the present invention. Labelstocks generally comprise the machine direction oriented monolayer or multilayer films (facestocks) described above and an adhesive layer. The adhesive layer generally is in contact with and adhesively joined to the surface of the monolayer films. A protective release liner may be attached to the exposed surface of the adhesive layer.
The adhesive layer utilized in the labelstocks of the present invention such as illustrated in
In one embodiment, the present invention relates to the preparation of die-cut machine direction oriented monolayer film labels by a procedure that comprises
(A) extruding a monolayer film facestock having an upper surface and a lower surface and comprising a mixture of
(B) stretch orienting the extruded film in the machine direction at a stretching temperature at about or above the melting temperature of the polyethylene up to the melting temperature of the propylene homopolymer or copolymer,
(C) applying an adhesive layer having an upper surface and a lower surface wherein the upper surface of the adhesive layer is joined to the lower surface of the film.
(D) applying a release liner to the lower surface of the adhesive layer, and
(E) die-cutting labels in the adhesive labelstock.
In another embodiment die cut machine direction oriented film labels are prepared by the procedure that comprises
(A) preparing a multilayer film facestock comprising
(B) stretch orienting the film in the machine direction at a stretching temperature at about or above the melting temperature of the polyethylene up to the melting temperature of the propylene homopolymer or copolymer,
(C) applying an adhesive layer having an upper surface and a lower surface wherein the upper surface of the adhesive layer is joined to the lower surface of the multilayer film,
(D) applying a release liner to the lower surface of the adhesive layer, and
(E) die-cutting labels in the adhesive labelstock.
As indicated above, the stretch oriented films may be annealed or heat set prior to applying the adhesive layer, and the adhesive layer and the release liner may be joined to the monolayer and multilayer film facestock in one step by initially coating the adhesive on a release liner and then applying the exposed adhesive surface to the film facestock.
The manufacture of labelstocks and die-cut labels in accordance with the invention is illustrated in
The release face of the release liner or carrier may be coated with a layer of adhesive for subsequent transfer of the adhesive to the facestock with which the liner or carrier is joined. When the facestock is combined with the liner or carrier, the adhesive is joined to the facestock. Later, the liner or carrier is removed to expose the adhesive, which now remains permanently joined to the facestock.
Thus, as indicated in
In some applications, the adhesive may be a heat-activated adhesive or a hot-melt adhesive such as used in in-mold label applications, as distinguished from a pressure-sensitive adhesive, in which case there may be no need for the provision of a release liner or inherent releasability such as is required when using a pressure-sensitive adhesive.
The label facestock may be printed at a printing station (not shown) prior to being die-cut into individual labels. The printing step may occur before or after the combining of liner and facestock, but will precede the die-cutting of the facestock into individual labels. The film must remain in accurate register between printing steps (for example, between successive impressions in different colors) in order that image or text be of high quality, and between printing and subsequent die-cutting in order that image or text be located properly on the labels. The film is under tension during printing, and may be subjected to some increase in temperature, as for example when UV inks are cured, and must not stretch significantly in the machine-direction. The MD tensile properties of the facestock film are particularly important when a polymeric film liner is used or when no liner is required.
The workpieces 33 may constitute rigid substrates such as glass bottles or other rigid articles tending to have irregularities in the surface and therefore requiring labels that are flexible and closely adhere (conform) to the surface without bridging local surface depressions. Alternatively, the workpieces may be soft, flexible substrates such as plastic containers requiring labels that flex when the container is flexed.
It will be understood that the operations shown in
Facestock that is formed into labels is usually wound and unwound in roll form, and is therefore one form of what is known as “roll stock” or “roll facestock,” and the accompanying liner or carrier is called “roll liner.”
One important advantage of the monolayer machine direction oriented film facestocks described above and which are used in the die-cut labels of the invention is the improved die-cuttability of the labels. It has been observed, for example, that die-cutting of the labels of the present invention provides sharp and distinct cuts with full separation of the label from the matrix along the cut label edge being achieved at a lower die-cutting pressure, and the cutting tool does not have to be as sharp when cutting the facestock label films of the present invention. Failure to achieve a clean die-cut perimeter between the label and surrounding matrix can cause the matrix to break, in either the machine or cross directions, and remain with the label on the release liner. This defect will adversely affect the dispensing operation by applying a double label or label plus matrix strip(s) to the substrate.
The die-cuttability of the films prepared from the compositions of the examples at the elevated stretching temperatures is evaluated by die-cutting shapes in the films and thereafter measuring the frictional energy (DFE) required to separate the matrix from the die-cut shape. As described below, the frictional energy is calculated by measuring the force required to separate the die cut shape from its matrix, during the displacement of the test sample. A low frictional energy value indicates the laminate exhibits good die-cuttability. This test which is conducted as follows is described in more detail in U.S. Pat. No. 5,961,766 which is hereby incorporated by reference.
A test sheet of each film having the dimensions of 7×10″ (17.8×25.4 cm) is advanced through a die-cutter where 10 labels are cut in the facestock. The die-cutter has a cylindrical profile. The die-cutting roll has a diameter of 3 inches (76.2 mm), with one cavity across and 10 cavities around. Each of the cavities are 6 inches (152.4 mm) long (or across), 1 5/16 inch (22.25 mm) wide (or deep) and have rounded corners with diameters of 3/32 inch (2.38 mm). The separation between adjacent cavities is ⅛ inch (3.175 mm). The anvil roll has a diameter of 5 inches (127 mm). The gap between the anvil and the tip of the die is 2.2 mils (0.0559 mm). The die pressure is 300 psi (0.2 Mpa), and the speed of the die is 15 m/min.
The die-cut in each test sheet is deep enough to penetrate the film. The labels that are formed are rectangular in shape and arranged side-by-side on the test sheet, one label across and ten deep. The long dimension of each label is parallel to the long dimension of the next adjacent label. The labels have the dimensions of ⅞×6″ (22.25 mm×152.4 mm) and are equidistant from each other. The gap between each label is ⅛ inch (3.175 mm). A matrix, which consists of the portion of the waste facestock around the labels, is also formed during the die-cutting.
A test sample is formed by cutting the die-cut test sheet along the center line of the long dimension of one label and then along the center line of the long dimension of the next adjacent label. The cuts are parallel to each other. Each test sample consists of one-half of one label, one-half of the next adjacent label sample, and the matrix around the label portions.
The frictional energy (DFE) required to separate the matrix from the die-cut labels of each sample is measured using a modified TA-XT2 Texture Analyzer provided by Stable Micro Systems, Unit 105, Blackdown Rural Industries, Haste Hill, Haslemere, Surrey GU 27 3AY, England. The TA-XT2 Texture Analyzer is a tensile testing device. It is modified as follows: the fixture on the top crosshead is removed and substituted by an upper L-shaped bracket; one arm of the upper L-shaped bracket is attached to the upper frame; the platform mounted on the base is removed and substituted by a lower L-shaped bracket. Each test sample is tested by attaching an edge of the matrix of the test sample to the upper L-shaped bracket, and attaching the edge of each label portion adjacent to the attached matrix edge to the lower L-shaped bracket. The texture analyzer is activated and the matrix is separated from the label portions at a rate of 5 mm/s.
The force used to separate the matrix, and the displacement of this force along the length of the test sample during separating is plotted using software provided with the TA-XT2 Texture Analyzer. The area under the plot is also determined using software provided with the TA-XT2 Texture Analyzer. The area under the plot has the units of gram-seconds. The result is multiplied by the stripping speed (5 mm/sec) and after making appropriate corrections for units (i.e., mm to cm), the friction energy results are provided in terms of gram-centimeters (g-cm). Higher friction energy numbers are associated with poorly cut facestocks or adhesive flowback.
For each film, 10 test samples are tested and the averages for these test samples are reported. A reading of zero (0) indicates a clean cut label completely free from the matrix after die cutting.
The results of the frictional energy tests on the films of Examples A-V, AA, and Control Examples CA to CG are summarized in Tables V and VI. As shown therein the machine direction oriented films of Examples A to G, which were stretch oriented at a temperature above the melting temperature of the polyethylene exhibited good die-cuttability whereas the corresponding films stretched at lower temperature split or were not readily and clearly cuttable.
1corrected to a thickness of 55 μm.
While the invention has been explained in relation to its embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.
This application is a national phase of International Application No. PCT/US2007/071084, filed Jun. 13, 2007, which claims priority to U.S. Provisional Application Ser. No. 60/804,757, filed Jun. 14, 2006 and U.S. Provisional Application Ser. No. 60/823,684 filed Aug. 28, 2006. The entire disclosure of this international application and the entire disclosure of both provisional applications are hereby incorporated by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US2007/071084 | 6/13/2007 | WO | 00 | 12/3/2008 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2007/146986 | 12/21/2007 | WO | A |
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| Number | Date | Country | |
|---|---|---|---|
| 20090130360 A1 | May 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60804757 | Jun 2006 | US | |
| 60823684 | Aug 2006 | US |
