Printing systems and methods including multilayer films

Abstract

To provide printing systems including multilayer films that achieve proper wetting and anchoring of ink compositions without requiring additional primer layer or corona or plasma treatments.SOLUTION: The present invention relates to printing systems and methods that may include an ink composition including electrically charged ink particles dispersed in a hydrocarbon liquid and a multilayer film. The multilayer film may include a polymeric core layer; and one or more printing layers adjacent to the polymeric core layer. The one or more printing layers may include at least 50 wt.% of an ethylene vinyl acetate copolymer having acid and acrylate functional groups. The ethylene vinyl acetate copolymer having acid and acrylate functional groups may include from 0.5 wt.% to 4 wt.% methacrylic or acrylic acid; from 0.5 wt.% to 4 wt.% acrylate, from 7 wt.% to 40 wt.% vinyl acetate; and the balance ethylene, based on the total weight of the ethylene vinyl acetate copolymer having acid and acrylate functional groups.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Cross-reference of related applications This application is a prior art of U.S. Provisional Patent Application No. 62 / 842,012, filed on May 2, 2019. Priority is asserted, and the entire disclosure is incorporated herein by reference.

[0002] The embodiments described herein generally relate to multilayer films, and in particular to digital printing systems. This relates to the multilayer films used in the system. [Background technology]

[0003] In recent years, the printing process of digital printing presses has had an impact on the graphic arts market. In conventional printing methods that use fixed, etched plates, the ink is The ink is attracted to the substrate by the physical movement of the ink from the ink tray to the cylinder. In the printing process of a cylinder printing press, the ink composition is physically transferred from the ink tray to the cylinder. It is not a matter of natural movement, but rather it is attracted to the photographic imaging plate by electric charge. [Overview of the project]

[0004] The process of digital printing presses involves inks containing ethylene and acrylic copolymers. Using these compositions, these ink compositions are heated and applied to a substrate such as a flexible film. It is applied. Similar to conventional printing presses, the printing process of a digital printing press involves applying liquid ink. Use to print images. However, in the digital printing process, the ink is charged The particles contained within are attracted to the electrostatic field formed on the photographic imaging plate. When the ink composition is placed on the photographic imaging plate, the placed ink composition, Direct contact between the heated blanket and the ink composition on the photographic imaging plate. It is then transferred directly to the heated blanket. On the heated blanket, The ink particles in the ink composition melt to form a smooth ink film, which is then transferred onto the substrate. It will be done.

[0005] In the printing process of conventional digital printing presses, overprint varnish (OPV) and The lamination process is used to transfer the printed material onto the final package structure (transfer It protects the ink film (on which the image is captured). Furthermore, in the printing process of conventional digital printing presses Corona-treated film provides proper wetting and fixes the printed illustrations in place. It is often necessary to apply a primer on top of it. , increased process complexity, increased costs associated with the process, and internal / external (ratch (P-seal) has drawbacks, including reduced sealing when a seal is required for the package design. ru.

[0006] Therefore, without requiring an additional primer layer or corona or plasma treatment. Printing systems that utilize multilayer films to achieve proper wetting and fixation of ink compositions. This is required. Embodiments of this disclosure provide an ink composition suitable during the digital printing process. A multilayer film including an ink fixing layer ("printing layer") that can be thoroughly wetted and fixed. These needs are met by providing a film. Multilayer films also have a core layer. This allows the multilayer film to exhibit appropriate rigidity and maintain appropriate dimensions. It can be printed using a digital printer line.

[0007] A printing system is provided according to at least one embodiment of the present disclosure. Embodiments of Tem include an ink composition comprising charged ink particles dispersed in a liquid, and multi It may include a multilayer film. The multilayer film includes a polymer core layer and adjacent to the polymer core layer. It may include one or more printed layers. One or more printed layers may contain at least 50% by weight of acid It may contain ethylene vinyl acetate copolymer having acrylate functional groups. Acid and Ethylene vinyl acetate copolymers having acrylate functional groups are acidic and acrylate functional Based on the total weight of the ethylene vinyl acetate copolymer containing the group, 0.5% to 4% by weight Methacrylic acid or acrylic acid, 0.5% to 4% by weight of acrylate, 7% by weight It may contain 40% by weight of vinyl acetate and the remainder ethylene.

[0008] According to at least one embodiment of the present disclosure, a printing method is provided. The application method may include transferring the ink composition to the printing layer of a multilayer film. The material may contain charged ink particles dispersed in a liquid. The multilayer film is made of polymer. It includes a layer A and one or more printed layers adjacent to the polymer core layer, and the one or more printed layers are At least 50% by weight of ethylene vinyl acetate copolymer having acid and acrylate functional groups. Ethylene vinyl acetate copolymers containing rimers and having acid and acrylate functional groups, Based on the total weight of ethylene vinyl acetate copolymer having acid and acrylate functional groups , 0.5% to 4% by weight of methacrylic acid or acrylic acid, 0.5% to 4% by weight of It contains acrylate, 7% to 40% by weight of vinyl acetate, and the remainder is ethylene.

[0009] Therefore, embodiments of the present disclosure include an additional primer layer or corona or plasma Without requiring pre-treatment, proper wetting and fixing of the ink composition during the digital printing process. We can provide printing systems and methods that can achieve this.

[0010] These and other embodiments are further described in the following “Modes for Carrying Out the Invention” I will describe it in detail. [Modes for carrying out the invention]

[0011] Here, we will describe specific embodiments of this application. These embodiments are described in more detail in this disclosure. It is complete and provided to fully convey the scope of the subject matter to those skilled in the art.

[0012] The term "polymer" refers to monomers, whether of the same or different type. It refers to polymer compounds prepared by polymerizing [a certain substance]. Therefore, in general terms... The term "polymer" encompasses the term "homopolymer," which usually refers to one type of polymer. A "polymer" refers to a polymer prepared from only monomers, while a "copolymer" refers to a polymer prepared from two or more different monomers. This refers to polymers prepared from. As used herein, "interpolymer" is used in this context. The term refers to a polymer prepared by the polymerization of at least two different types of monomers. It refers to more than two polymers, such as terpolymers. Therefore, the general term interpolymer refers to more than two polymers. It contains copolymers or polymers prepared from different types of monomers.

[0013] As used herein, “acid copolymer” refers to a direct copolymer or graft copolymer. It can be a polymer. The term "direct copolymer" means that the monomer is on an existing polymer chain. Unlike graft copolymers polymerized in one way, this process involves polymerizing monomers together at the same time. This can refer to the copolymer produced by this process.

[0014] "Polyethylene" or "ethylene-based polymer" is a unit derived from ethylene monomer. This refers to polymers containing more than 50 mol%. This includes ethylene-based homopolymers. This technique contains a mer or copolymer (meaning a unit derived from two or more comonomers). A common form of ethylene-based polymer known in the field is low-density polyethylene. (LDPE), Linear Low-Density Polyethylene (LLDPE), Ultra-Low-Density Polyethylene (Ul tra Low Density Polyethylene (ULDPE), ultra-low density Polyethylene (Very Low Density Polyethylene: VLD) Syn (PE), including both linear and substantially linear low-density resins (m-LLDPE) Linear low-density polyethylene and medium-density polyethylene (MDPE) produced by glucite catalysts, Examples include, but are not limited to, ethylene and high-density polyethylene (HDPE). Copolymers are produced using polymer technology, either in an autoclave or a tubular reactor. It can be manufactured by well-known processes. Copolymerization is permitted by U.S. Patent No. 3,264,2 Issues 72, 4,351,931, 4,248,990, and 5,028,67 As disclosed in Patent No. 4 and International Patent Application No. 99 / 25742, Autocre It can be executed as a continuous process within the same application.

[0015] Ethylene vinyl acetate (EVA) is a copolymer of ethylene and vinyl acetate. An example of EVA copolymer is DuPont Company, Wilmington, De It is available from multiple sources, including l.

[0016] Ethylene / acid copolymers and methods for preparing them are well known in the art, for example, For example, U.S. Patent Nos. 3,264,272, 3,404,134, and 3,355,31 Disclosed in Patent No. 9 and No. 4,321,337. Use in the present invention as described herein Suitable commercially available acid copolymers include those from DuPont Company, Wilmington, It is available from various sources, including Del.

[0017] The term "LDPE" is short for "high-pressure ethylene polymer" or "highly branched polyethylene." It is sometimes called "ethylene," and the polymer acts as a free radical initiator for peroxides and other free radicals. By using this, you can achieve pressures exceeding 14,500 psi (100 MPa) automatically In a clave or tubular reactor, partial or complete homopolymerization or copolymerization occurs. Defined to mean (for example, the United States incorporated herein by reference) (See publications No. 4,599,392). LDPE resin is typically 0.916~0 It has a density in the range of 0.940 g / cc.

[0018] The term "LLDPE" refers to resin produced using the Ziegler-Natta catalyst system. The resin contains lipids and resins made using a single-site catalyst, and a bismetallocene catalyst. (Sometimes referred to as "m-LLDPE"), phosphine imine, constrained geometric catalyst, and This includes, but is not limited to, resins made using post-metallocene molecular catalysts. Furthermore, bis(biphenylphenoxy) catalysts (also called polyvalent aryloxy ether catalysts) ) are included, but not limited to, LLDPEs are linear, substantially linear, or includes heterogeneous ethylene copolymers or homopolymers. LLDPE is LDP It contains fewer long-chain branches than E, and is registered under U.S. Patent No. 5,272,236 and U.S. Patent No. 5,222,2236. U.S. Patent No. 78,272, U.S. Patent No. 5,582,923, and U.S. Patent No. 5,733,15 A substantially linear ethylene polymer, as further defined in Article 5, U.S. 3,6 Uniform branched linear ethylene polymer compositions, such as those described in Patent No. 45,992, U.S. Patent Heterogeneous branching, such as that prepared according to the process disclosed in Patent No. 4,076,698. Ethylene polymers, their blends (U.S. Patent No. 3,914,342 and U.S. Patent No. 1) Examples include those disclosed in Patent No. 5,854,045. LLDPE resin is said Using any type of reactor or reactor configuration known in the technical field, gas phase, liquid phase It can be produced by slurry polymerization, or any combination thereof.

[0019] A "multilayer structure" refers to any structure that has two or more layers. For example, a multilayer structure (For example, a film) may have two, three, four, five, or more layers. A layered structure can be described as having layers indicated by letters. For example, A / B / C The three-layer structure may have a core layer B, and two outer layers A and C. Similarly, two A structure having core layers B and C, and two outer layers A and D, is clearly defined as A / B / C / D. As will be shown, in some embodiments, the multilayer film of the present disclosure has at least two layers In some embodiments, the multilayer films of this disclosure include up to 15 layers.

[0020] Here, embodiments of the printing system are described in detail. As previously stated herein, Embodiments of the printing system may include an ink composition and a multilayer film.

[0021] Here, embodiments of the ink composition for the printing system are referred to in detail. The ink composition It may contain charged ink particles dispersed in a liquid. However, it is not bound by theory. The particles of the ink composition are on the photographic imaging plate during the digital printing process. It can be charged as if attracted to the electrostatic field that is constructed. By force, the ink composition is precisely positioned on the photographic imaging plate, and then, this specification It can be transferred to a substrate such as the multilayer film embodiment described in the book.

[0022] Charged ink particles may contain one or more pigments and resin materials. The resin material is It may contain a luopolymer resin. The ink composition is approximately based on the total weight of the ink composition. 0.001% to approximately 2% by weight, or approximately 0.001% to approximately 1% by weight of fluoropoly It may contain a resin. One or more pigments of the charged ink particles are known in the field of digital printing. It may contain pigments. The ink composition is approximately 0 based on the total weight of the ink composition. One or more faces ranging from 0.001% to approximately 5% by weight, or from approximately 0.001% to approximately 2.5% by weight. May include charges.

[0023] As mentioned above, charged ink particles can be dispersed in a liquid. This liquid is It is sometimes also called a "carrier liquid." In this embodiment, charged ink particles are in the liquid. It can be completely encapsulated. In some embodiments, the liquid may be a hydrocarbon liquid. In further embodiments, the hydrocarbon liquid may include petroleum hydrocarbons. The ink composition Based on the total weight of the ink composition, less than approximately 90% by weight or less than approximately 80% by weight of liquid It may include.

[0024] Here, we refer in detail to an embodiment of a multilayer film for a printing system. The multilayer film is It may include a polymer core layer and one or more printed layers adjacent to the polymer core layer. (Theory) Although not restricted by this, one or more printed layers of a multilayer film may have an additional primer layer. Alternatively, ink assembly during the digital printing process without requiring corona or plasma treatment. It is thought that this may enable proper wetting and fixation of the material. It is not bound by theory. However, the polymer core layer of the multilayer film can provide appropriate rigidity, and as a result, multilayer film It is believed that the object can be printed on a digital printer line while maintaining appropriate dimensions.

[0025] In one or more embodiments, the multilayer film may include at least two layers. In one embodiment, the multilayer film of the present disclosure comprises up to 15 layers. In further embodiments... Multilayer films are available in 2-15 layer, 2-10 layer, 2-5 layer, 5-15 layer, and 5- It may include 10 layers, or 10 to 15 layers.

[0026] In further embodiments, the multilayer film may have a two-layer structure explicitly labeled A / B, and The printing layer may be explicitly labeled A, and the polymer core layer may be explicitly labeled B. In other embodiments, multiple The layer film may have a three-layer structure clearly labeled A / B / C, and the polymer core layer may be clearly labeled B. The printed layers may be clearly labeled A and C.

[0027] As mentioned above, embodiments of multilayer films may include a polymer core layer. In this embodiment, the polymer core layer is made of polyethylene terephthalate, polyamide, and ethylene Includes one or more of the following polymers: polypolymers, propylene polymers, or a combination thereof. Obtain. In embodiments, the polymer core layer comprises an ethylene-based polymer. Several embodiments In this state, the polymer core layer may contain more than 50 mol% of units derived from ethylene monomer. In further embodiments, the polymer core layer is an ethylene-based homopolymer or copolymer. This may include. Embodiments of the polymer core layer include low-density polyethylene (LDPE), straight Chain-type low-density polyethylene (LLDPE), ultra-low-density polyethylene (Ultra Low Density Polyethylene (ULDPE), Ultra-Low Density Polyethylene (V) Polyethylene (VLDPE), linear A single-site catalyst containing both a substantially linear low-density resin (m-LLDPE) and a single-site catalyst containing both. Linear low-density polyethylene, medium-density polyethylene (MDPE), and high-density polyethylene are produced by this process. Examples include, but are not limited to, ethylene (HDPE).

[0028] In the embodiment, the polymer core layer has a secant modulus of 2% that exceeds approximately 150 MPa. It may contain an ethylene-based polymer. In some embodiments, the polymer core layer is about 15 It may contain an ethylene-based polymer having a secant modulus of 2% in the range of 0 MPa to approximately 1500 MPa. In other embodiments, the polymer core layer is subjected to pressures of approximately 150 MPa to approximately 1000 MPa, and approximately 150 MPa ~ approx. 750 MPa, approx. 150 MPa ~ approx. 500 MPa, approx. 150 MPa ~ approx. 250 MPa, about 250 MPa to about 1500 MPa, about 250 MPa to about 1000 MPa, about 2 50 MPa to about 750 MPa, about 250 MPa to about 500 MPa, about 500 MPa to about 1 500 MPa, about 500 MPa to about 1000 MPa, about 500 to about 750 MPa, about 75 0 MPa to about 1500 MPa, about 750 MPa to about 1000 MPa, or about 1000 M Pa to about 1500 MPa and may include an ethylene polymer having a secant modulus of elasticity of 2%. The reason Although not bound by theory, the rigidity of the polymer core layer is considered to enable dimensional stability during the digital printing process.

[0029] In some embodiments, the polymer core layer, when measured according to ASTM D792, has a density of about 0.865 grams per cubic centimeter (g / cm 3 ) to about 0.965 g / cm 3 . In some embodiments, the polymer core layer is about 0.865 g / cm 3 to about 0.945 g / cm 3 , about 0.865 g / cm 3 to about 0.925 g / cm 3 , about 0.865 g / cm 3 to about 0.905 g / cm 3 , about 0.865 g / cm 3 to about 0 .885 g / cm 3 , about 0.885 g / cm 3 to about 0.965 g / cm 3 , about 0.885 g / cm 3 to about 0.945 g / cm 3 , about 0.885 g / cm 3 to about 0.925 g / cm 3 , about 0.885 g / cm 3 to about 0.905 g / cm 3 , about 0.905 g / cm3 ~about 0 0.965g / cm³ 3 , about 0.905g / cm 3 ~Approx. 0.945g / cm 3 , about 0.905 g / cm 3 ~Approx. 0.925g / cm 3 , about 0.925g / cm 3 ~Approx. 0.965g / cm 3 , about 0.925g / cm 3 ~Approx. 0.945g / cm 3 , or approximately 0.945 g / cm³ 3 ~Approx. 0.965g / cm 3 It may have a density of .

[0030] The polymer core layer was measured at 190°C and 2.16 kg according to ASTM D1238. If set, the amount of merchandise per 10 minutes will be approximately 0.1 grams (g / 10 minutes) to approximately 45.0 grams / 10 minutes. It may have a flow rate. In some embodiments, the polymer core layer is about 0.2 g / 10 minutes ~ approx. 40.0g / 10 minutes, approx. 0.2g / 10 minutes ~ approx. 30.0g / 10 minutes, approx. 0.2 g / 10 minutes ~ approx. 20.0 g / 10 minutes, approx. 0.2 g / 10 minutes ~ approx. 10.0 g / 10 minutes, approx. 0 .2g / 10 minutes ~ approx. 1.0g / 10 minutes, approx. 1.0g / 10 minutes ~ approx. 45.0g / 10 minutes, approx. 1.0g / 10 minutes ~ approx. 30.0g / 10 minutes, approx. 1.0g / 10 minutes ~ approx. 20.0g / 10 minutes , about 1.0g / 10 minutes to about 10.0g / 10 minutes, about 1.0g / 10 minutes to about 5.0g / 10 min, approx. 10g / 10 min ~ approx. 45.0g / 10 min, approx. 10.0g / 10 min ~ approx. 20.0g / 10 minutes, about 10.0g / 10 minutes to about 15.0g / 10 minutes, about 15.0g / 10 minutes to about 40 Meltflore at 0.0g / 10 minutes, or approximately 15.0g / 10 minutes to approximately 20.0g / 10 minutes. It may have a trait.

[0031] Various commercial embodiments are considered suitable for polymer core layers. For example, preferred The polymer core layer is manufactured under the trademark DOWLEX® GM 8070. Linear low-density ethylene polymers commercially available from Chemical Company It may include.

[0032] In some embodiments, the thickness of the polymer core layer is approximately 10 microns to approximately 445 microns. It may be 10 micrometers (m³). In other embodiments, the polymer core layer is about 10 micrometers (m³). (Long) ~ approx. 400 microns, approx. 10 microns ~ approx. 300 microns, approx. 10 microns ~ approx. 2 00 microns, approximately 10 microns to approximately 100 microns, approximately 100 microns to approximately 445 microns n, approximately 100 microns to approximately 400 microns, approximately 100 microns to approximately 300 microns, approximately 1 00 microns to approximately 200 microns, approximately 200 microns to approximately 445 microns, approximately 200 microns Long ~ approximately 400 microns, approximately 200 microns ~ approximately 300 microns, approximately 300 microns ~ approximately 445 microns, approximately 300 microns to approximately 400 microns, or approximately 400 microns to approximately 4 It could be 45 microns.

[0033] Herein, embodiments of one or more printed layers of the multilayer film described herein will be referenced in detail. As mentioned above, although not bound by theory, one or more printing of multilayer films The layer does not require an additional primer layer or corona or plasma treatment, digital This is thought to enable proper wetting and fixation of the ink composition during the printing process.

[0034] In the embodiment, one or more printed layers are ethylene having acid and acrylate functional groups. Contains vinyl acetate copolymer. Ethylene vinyl acetate having acid and acrylate functional groups. Copolymers are copolymers of ethylene with vinyl acetate, acrylate, and acid comonomers. By means of, or by blending two or more copolymers or terpolymers Therefore, by grafting, or by other methods known in the art, directly It can be generated. In some embodiments, the acid and acrylate functional groups are ethyleneacetic acid. It can be grafted onto the vinyl polymer main chain. In other embodiments, acids and acrylate tubes The active group is an ethylene vinyl acetate polymer having an acid group, an acrylate group, or both. This can be achieved by blending with one or more polymers. Further implementation In terms of form, ethylene vinyl acetate copolymer having acid and acrylate functional groups is ethylene A vinyl acetate polymer has acid groups, acrylate groups, or both. It can be produced by melt-blending with a polymer or terpolymer. One implementation In this state, ethylene vinyl acetate polymer is ethylene (C3-C10) alkyl acrylate It can be blended with tocopolymers and ethylene monocarboxylic acid copolymers, monocarbon The acid may include acrylic acid or methacrylic acid. In another embodiment, ethylene vinyl acetate The compound can be blended with ethylene alkyl acrylate monocarboxylic acid polymers. In one embodiment, the ethylene alkyl acrylate monocarboxylic acid terpolymer is ethylene Contains isobutyl acrylate methacrylate polymer. Ethylene vinyl acetate polymer - When measured at 190°C and 2.16 kg according to ASTM D1238, it is approximately 0 .5g / 10 minutes ~ approx. 10g / 10 minutes, approx. 1g / 10 minutes ~ approx. 10g / 10 minutes, approx. 2g / 10 Melt index of approximately 10g / 10 minutes, or approximately 5g / 10 minutes to approximately 10g / 10 minutes. Ethylene alkyl acrylate copolymers or terpolymers may have the following characteristics: When measured at 190°C and 2.16 kg according to D1238, approximately 0.5 g / 10 min ~Approx. 15g / 10 minutes, approx. 1g / 10 minutes ~ approx. 15g / 10 minutes, approx. 5g / 10 minutes ~ approx. 15g / It may have a melt index of 10 minutes, or approximately 10g / 10 minutes to approximately 15g / 10 minutes.

[0035] Although not bound by theory, ethylene vinegar containing acid and acrylate functional groups Vinyl acetate copolymers require an additional primer layer or corona or plasma treatment. This allows for proper wetting and fixing of the ink composition during the digital printing process. This is considered to be the case. In the embodiment, ethylene vinyl acetate having acid and acrylate functional groups. The copolymer is a total ethylene vinyl acetate copolymer having acid and acrylate functional groups. Based on weight, approximately 0.5% to approximately 4% by weight of methacrylic acid or acrylic acid, approximately 0. 5% to approximately 4% by weight of acrylate, approximately 10% to approximately 40% by weight of vinyl acetate, and It may contain residual ethylene.

[0036] Based on the total weight of ethylene vinyl acetate copolymer having acid and acrylate functional groups In some embodiments, ethylene vinyl acetate having acid and acrylate functional groups The rucopolymer contains approximately 0.5% to 4% by weight of methacrylic acid or acrylic acid, Approximately 0.5% to 3% by weight, approximately 0.5% to 2% by weight, approximately 0.5% to 1% by weight Amount%, about 1% to about 4% by weight, about 1% to about 3% by weight, about 1% to about 2% by weight, about 2% to approximately 4% by weight, or approximately 3% to approximately 4% by weight, of methacrylic acid or acrylic acid. It may contain acid.

[0037] In the embodiment, an ethylene vinyl acetate copolymer having acid and acrylate functional groups is used. The acrylate is an alkyl acrylate having 1 to 4 carbon atoms in the alkyl portion. It may include. In further embodiments, the acrylate may be methyl acrylate, ethyl acrylate. Rate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate It may also contain acid and isobutyl acrylate. In other embodiments, it may contain acid and acrylate. Acrylates of ethylene vinyl acetate copolymers having trifunctional groups are methyl methacrylates. T, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n- Hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate Methacrylic acid such as n-decyl methacrylate and dodecyl methacrylate It may contain alkyl esters. Ethylene vinyl acetate having acid and acrylate functional groups. Based on the total weight of the copolymer, in some embodiments, acid and acrylate functional groups Ethylene vinyl acetate copolymer having about 0.5% to about 4% by weight of acrylate , or approximately 0.5% by weight to approximately 3% by weight, approximately 0.5% by weight to approximately 2% by weight, approximately 0.5% by weight to About 1% by weight, about 1% to about 4% by weight, about 1% to about 3% by weight, about 1% to about 2% by weight It may contain %, approximately 2% to 4% by weight, or approximately 3% to 4% by weight of acrylate. ru.

[0038] Based on the total weight of ethylene vinyl acetate copolymer having acid and acrylate functional groups In some embodiments, ethylene vinyl acetate having acid and acrylate functional groups The copolymer is approximately 7% to 40% by weight of vinyl acetate, or approximately 7% to 30% by weight of vinyl acetate. Amount%, about 7% to about 20% by weight, about 7% to about 10% by weight, about 10% to about 40% by weight Amount%, about 10% to about 30% by weight, about 10% to about 20% by weight, about 20% to about 4 0% by weight, approximately 20% to 30% by weight, or approximately 30% to 40% by weight of acetate It may include nil.

[0039] Ethylene vinyl acetate copolymers having acid and acrylate functional groups are classified by ASTM When measured according to D792, it is approximately 0.890 grams (g / cm²) per cubic centimeter. cm 3 ) ~ approx. 0.985g / cm 3 It may have a density of. In some embodiments, the acid and Ethylene vinyl acetate copolymer having acrylate functional groups is approximately 0.890 g / cm³ 3 ~Approx. 0.980g / cm 3 , about 0.890g / cm 3 ~Approx. 0.960g / cm 3 , about 0 0.890g / cm³ 3 ~Approx. 0.940g / cm 3 , about 0.890g / cm 3 ~about 0.920 g / cm 3 , about 0.890g / cm 3 ~Approx. 0.900g / cm 3 , about 0.900g / cm 3 ~Approx. 0.985g / cm 3 , about 0.900g / cm 3 ~Approx. 0.960g / cm 3 , about 0 0.900g / cm³ 3 ~Approx. 0.940g / cm 3 , about 0.900g / cm 3 ~about 0.920 g / cm 3 , about 0.920g / cm 3 ~Approx. 0.985g / cm 3 , about 0.920g / cm 3 ~Approx. 0.960g / cm 3 , about 0.920g / cm 3 ~Approx. 0.940g / cm 3 , about 0 0.940g / cm³ 3 ~Approx. 0.985g / cm 3 , about 0.940g / cm 3 ~about 0.960 g / cm 3 , or approximately 0.960 g / cm³ 3 ~Approx. 0.985g / cm 3 It may have a density .

[0040] Ethylene vinyl acetate copolymers having acid and acrylate functional groups are classified by ASTM When measured at 190°C and 2.16 kg according to D1238, approximately 0.5 per 10 minutes. It may have a melt flow rate of approximately 20.0 g / 10 min (grams / 10 min). In that embodiment, an ethylene vinyl acetate copolymer having acid and acrylate functional groups. Approximately 0.5g / 10 minutes to approximately 20g / 10 minutes, approximately 0.5g / 10 minutes to approximately 15.0g / 10 min, approx. 0.5g / 10 min ~ approx. 10.0g / 10 min, approx. 0.5g / 10 min ~ approx. 5.0g / 1 0 minutes, about 0.5g / 10 minutes to about 1.0g / 10 minutes, about 1.0g / 10 minutes to about 20g / 10 min, approx. 1.0g / 10 min ~ approx. 15.0g / 10 min, approx. 1.0g / 10 min ~ approx. 10.0g / 10 minutes, approx. 1.0g / 10 minutes ~ approx. 5.0g / 10 minutes, approx. 5.0g / 10 minutes ~ approx. 20.0g / 10 minutes, approx. 5.0g / 10 minutes ~ approx. 15.0g / 10 minutes, approx. 5.0g / 10 minutes ~ approx. 10. 0g / 10 minutes, approx. 10.0g / 10 minutes ~ approx. 20.0g / 10 minutes, approx. 10.0g / 10 minutes ~ Meltoff of approximately 15.0g / 10 minutes, or approximately 15.0g / 10 minutes to approximately 20.0g / 10 minutes It may have a low rate.

[0041] In some embodiments, one or more printed layers consist of polyolefin and acid and acrylic. This may include a blend with an ethylene vinyl acetate copolymer having a rate functional group. Embodiment Then, one or more printed layers shall be at least 50 weights based on the total weight of one or more printed layers. It may contain % of an ethylene vinyl acetate copolymer having acid and acrylate functional groups. Although not bound by theory, polyolefins and functionalized ethylene polymers are miscible. Rather than being related, it is thought that when blended, they can form separate phases. One or more printed layers, At least 50% by weight of ethylene vinyl acetate copolymer having acid and acrylate functional groups. By including rimer, ethylene vinyl acetate having acid and acrylate functional groups is produced. The polymer can be a continuous phase in the blend, forming one or more printable layers of the digital ink composition. This may allow for proper wetting or fixation. In some embodiments, one or more printed layers , about 50% to about 100% by weight, about 50% to about 80% by weight, about 50% to about 60% by weight Weight%, approx. 60% to approx. 100%, approx. 60% to approx. 80%, approx. 80% to approx. Ethylene vinyl acetate copolymer having approximately 100% by weight of acid and acrylate functional groups It may include.

[0042] Polyolefin and ethylene vinyl acetate copolymer having acid and acrylate functional groups Embodiments of one or more printed layers including a blend with a mar include acids and acrylate functional groups Polyolefins blended with ethylene vinyl acetate copolymers having the said technical component Prepared using homogeneous or heterogeneous catalyst systems known in the field and various commercial polymerization processes. Obtained. In the embodiment, an ethylene vinyl acetate copolymer having acid and acrylate functional groups. - The blended polyolefin is approximately 0.865 g / cm³ 3 ~Approx. 0.940g / cm 3 It may have a density in the range of [value]. In other embodiments, the acid and acrylate functional groups are [value]. Polyolefins blended with ethylene vinyl acetate copolymer have a concentration of approximately 0.865 g / cm³. 3 ~Approx. 0.940g / cm 3 , about 0.865g / cm 3 ~Approx. 0.920g / cm 3 , about 0 0.865g / cm³ 3 ~Approx. 0.900g / cm 3 , about 0.865g / cm 3 ~about 0.880 g / cm 3 , about 0.880g / cm 3 ~Approx. 0.940g / cm 3 , about 0.880g / cm 3 ~Approx. 0.920g / cm 3 , about 0.880g / cm 3 ~Approx. 0.900g / cm 3 , about 0 0.900g / cm³ 3 ~Approx. 0.940g / cm 3 , about 0.900g / cm 3 ~about 0.920 g / cm 3 , or approximately 0.920 g / cm³ 3 ~Approx. 0.940g / cm 3 It may have a density .

[0043] In further embodiments, ethylene vinyl acetate having acid and acrylate functional groups Examples of polyolefins blended with polymers include low-density polyethylene (LDPE), Linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), very low density polyethylene (VLDPE), and single-site catalysts that include both linear and substantially linear low density resins (m-LLDPE) can produce linear low density polyethylene, medium density polyethylene (MDPE), and high density polyethylene (HDPE), but are not limited thereto. In certain embodiments, one or more printed layers may include LLDPE. LLDPE may have a density of about 0.915 grams per cubic centimeter (g / cm³) to about 0.955 g / cm³, 0.915 g / cm³ to about 0.945 g / cm³, 0.915 g / cm³ to about 0.935 g / cm³, or 0.915 g / cm³ to about 0.925 g / cm³. LLDPE may have a melt index of about 0.70 g / 10 min to about 1.0 g / 10 min, about 0.80 g / 10 min to about 1.0 g / 10 min, or about 0.90 to about 1.0 g / 10 min. Various commercial embodiments of ethylene polymers are thought to be suitable for blending with ethylene vinyl acetate copolymers having acid and acrylate functional groups for use in one or more printed layers. For example, suitable ethylene polymers may be commercially available from The Dow Chemical Company under the trademark DOWLEX (trademark) GM 8070. Density Polyethylene: ULDPE), very low density polyethylene ([ VLDPE), linear and substantially linear low density resins (m-LLDPE). Linear low density polyethylene, medium density polyethylene (MDPE), and high density poly ethylene (HDPE) may be included, but are not limited thereto. In certain embodiments, one or more printed layers may include LLDPE. LLDPE may be per cubic centimeter about 0.915 grams (g / cm 3 ) to about 0.955 g / cm 3 , 0.915 g / cm 3 to about 0.945 g / cm 3 , 0.915 g / cm 3 to about 0.935 g / cm 3 , 0.91 5 g / cm 3 to about 0.925 g / cm 3 . LLDPE may be about 0.70 g / 10 min to about 1.0 g / 10 min, about 0.80 g / 10 min to about 1.0 g / 10 min, or about 0.90 to about 1.0 g / 10 min melt index. Various commercial embodiments of ethylene polymers are suitable for blending with ethylene vinyl acetate copolymers having acid and acrylate functional groups for use in one or more printed layers. For example, suitable ethylene polymers may be commercially available from The Dow Chemical Company under the trademark DOWLEX (trademark) GM 8070. under the trademark DOWLEX (trademark) GM 8070.

[0044] Embodiments of the printing system may optionally include one or more additional layers. So, one or more additional layers are a sealing layer, a barrier layer, a tie layer, or a combination thereof. It may include wasabi.

[0045] In some embodiments, the printing system optionally prints one or more sealing layers. It may include. Although not bound by theory, one or more sealing layers are multilayer films. The structure is heat-sealable, encapsulating the product and maintaining one or more optional barrier layers. It may be possible to provide protection. Various commercial embodiments are suitable for one or more sealing layers. It is believed that... For example, a suitable sealing layer is The Dow Chemic AFFINITY (trademark) PL 1888G from al Company, ELITE It is marketed as (trademark) 5401G, DOWLEX (trademark) 2045, and LDPE 611A. obtain.

[0046] In some embodiments, the printing system optionally includes one or more barrier layers. Obtained. In the embodiment, one or more core layers are one or more printed layers and one or more barrier layers. It can be positioned in between. Although not bound by theory, one or more barrier layers can be chemically resistant. It may provide chemical properties and help prevent the permeation of moisture, light, and oxygen. In embodiments The barrier layer consists of one or more polyamides, ethylene vinyl alcohol, or It may contain polyvinylidene chloride (PVDC). Various commercial embodiments include one or more berries. It is considered suitable for the A layer. For example, a suitable sealing layer is U from BASF. LTRAMID C33, EVAL from Kuraray, SK Chemicals? SARAN, and E from The Dow Chemical Company It may be marketed as LITE(trademark) 5960G and XUS 59900.94.

[0047] In some embodiments, the printing system optionally uses a polyolefin film. It may include one or more tie layers that can adhere to one or more barrier layers. For example, Suitable Thai products include BYNEL (trademark) 41E710 and AMPLIFY (trademark) TY 1 It can be sold commercially as the 451B, etc.

[0048] Here, embodiments of printing methods utilizing the printing systems described herein will be referenced in detail. do.

[0049] As described above, the embodiments of the printing method described herein involve using an ink composition in a multilayer fill This may include transferring to the printing layer of the ink. The ink composition is a band dispersed in a hydrocarbon liquid. The multilayer film may contain electrolyzed ink particles, and the polymer core layer may contain an electrolyzed ink particle. It may include one or more adjacent printed layers, one or more of which contain at least 50% by weight of acid and also comprises an ethylene vinyl acetate copolymer having acrylate functional groups.

[0050] In this embodiment, the printing method can utilize a digital printing press. Various commercial embodiments of the machine are considered suitable. For example, suitable digital printing The device may be sold by HP under the Indigo® trademark.

[0051] In digital printing methods, a laser array is used to create photosensitive photographic imaging plates. An image to be printed on the board (i.e., a printed image) can be constructed. In this embodiment, The printed image may be formed on the photographic imaging plate as an electrostatic field. Charged particles can be attracted to an electrostatic field established on a photographic imaging plate. The charged particles of the ink composition can then be placed on a photographic imaging plate. In conventional printing methods that use etched plates, the ink is, The ink is attracted to the substrate by the physical movement of the ink from the cylinder. In the embodiment of the printing method described, the ink composition is physically transferred from the ink tray to the cylinder. It is attracted to the photographic imaging plate not by movement, but by electric charge.

[0052] Once the ink composition is placed on the photographic imaging plate, the placed I The ink composition is on a heated blanket and a photographic imaging plate. The heat is transferred directly to the heated blanket through direct contact between them. A blanket is sometimes also called a "thermal blanket." Above, the ink particles of the ink composition can be melted into a smooth ink film. Then, A heated blanket can transfer the ink film onto a multilayer film. The heated blanket acts as a shock absorber and pressure pad, and the ink film This ensures uniform transfer to the multilayer film. In further embodiments, The heated blanket transfers the ink film to one or more printing layers of the multilayer film. It is possible.

[0053] In this embodiment, the heated blanket is heated to a temperature of approximately 100°C to approximately 200°C. In some embodiments, the heated blanket can be heated to approximately 100°C to approximately 180°C. Approximately 100°C to 160°C, approximately 100°C to 140°C, approximately 100°C to 120°C, approximately 12 0℃ to approximately 200℃, approximately 120℃ to approximately 180℃, approximately 120℃ to approximately 160℃, approximately 120℃ to approximately 140℃, approximately 140℃ to approximately 200℃, approximately 140℃ to approximately 180℃, approximately 140℃ to approximately 160℃ Approximately 160°C to 200°C, approximately 160°C to 180°C, or approximately 180°C to 200°C It can be heated to a certain temperature.

[0054] The printing system may include one or more additional steps. In some embodiments, The printing method may not include pre-transfer heating. In other embodiments, the printing method is pre This may include heating. In some embodiments, the ink composition may be supplied in a concentrated form. The ink composition may need to be diluted so that it can be printed. When supplied in a reduced form, the printing method involves supplying the concentrated ink composition to an ink supply tank. The concentrated ink composition is diluted, and the diluted ink composition is combined with a carrier fluid and dispersed in the liquid. This may include forming an ink composition containing charged ink particles.

[0055] Test method The test methods include the following: Melt Index (I2) To test the melt index (I2), the ethylene polymer sample is A Measurements are taken at 190°C and 2.16 kg according to STM D1238. The value is reported in g / 10 mins. This indicates that this corresponds to the grams eluted per 10 minutes. Propylene polymers are AS Measured at 230°C and 2.16 kg according to TM D1238.

[0056] density To test the density, the sample was prepared and measured according to ASTM D4703. And, grams per cubic centimeter (g / cc or g / cm 3 ) will be reported. The measurement is This is performed within one hour of sample compression using ASTM D792, Method B. .

[0057] ASTM D1525 (Vicat softening point) The Vicat softening point is determined by the controlled test conditions specified in ASTM D1525 for the test specimen. In this case, when subjected to a heating rate of 120°C / hour and a load of 10N, the specified needle penetrated. It is used to determine the temperature at which it occurs.

[0058] ASTM 2252-03 (Ink fixed) ASTM2252-03 is a method for using tape to apply ink to flexible packaging materials. This is a standard test used to evaluate the tackiness of coatings. ASTM 225 2-03 is a flexible tape that may not damage the surface during application and removal. Can be used as packaging material. ASTM 2252-03, 3M No. 610 To do this, use cellophane tape, office adhesive tape, or other adhesive tape known on site. Tape can be used. For ASTM 2252-03, the tape is approximately 19mm to 25m long. It has a width of m (approximately 3 / 4 inch to 1 inch).

[0059] To perform ASTM 2252-03, first place the sample to be tested on a flat surface. The sample should be laid flat and smooth, free from wrinkles, folds, or creases. Then, Sufficient length to cover the desired printed (or coated) area on the sample. The tape is cut. When testing a large area, use several short pieces of tape. It is also possible to do this. The tape will move smoothly and uniformly without wrinkles forming on the tape or sample. It is then attached to the sample. Next, the surface of the tape is (i.e., with your thumb or index) Rub it with your finger to ensure that it is completely adhered to the sample and that there are no air bubbles on the surface. Next, hold the sample flat against the surface (i.e., with one hand) and extend the tape approximately 120°. Peel it off at an angle of ~150 degrees (i.e., with your other hand). For each sample to be tested, It is necessary to keep the setup time of the tape (the amount of time the tap remains on the sample) constant. There is a need for it. Tape typically travels at a speed of approximately 305-460 mm (12-18 inches) per second. It is lifted and pulled back in a uniform and moderate motion.

[0060] When the tape is peeled off the sample, the printed or coated gums on the sample The tape is inspected for any residue or chips. The coating is also inspected. As an aid to visual inspection, a reference standard, i.e., a control, is used. It can be used to create and determine the degree of transcription. Then, mutually agreed reference The results characterizing the degree of adhesion are recorded using light. Multiple colors of ink are present. In some cases, the results may differ for each color depending on the ink composition, and if reported in such a way... There is a match.

[0061] ASTM F904 (Adhesive) ASTM F904 is used to perform adhesive strength and heat resistance tests. To perform ASTM F904, heat or a solvent is used to break down the ply. The separation is initiated mechanically. Then, the separated line of the test specimen is subjected to an Instron tensile testing machine. Place it on the grip of model number 4442. Then separate the grip and further... The force required to separate them is defined as the adhesive strength. [Examples]

[0062] The following examples illustrate the features of the Disclosure and do not limit the scope of the Disclosure. This is not intended to be the case. The following experiments demonstrate the properties of the embodiments of the printing system described herein. I analyzed Noh theater.

[0063] Example 1 - Generation of control sample, sample 1, and comparative samples A-I Control sample (film with primer) The control sample used was a multilayer film containing a primer. Based on the total weight of the multilayer film, it has 80% by weight of layer A and 20% by weight of layer B. It was a two-layer inflatable film prepared to have a general-purpose layer A / layer B. Layer A was Based on the total weight of layer A, 80% by weight of ELITE(trademark) 5410 (The Dow (Available from Chemical Company, Midland, MI) and 20-weight Quantity % of LDPE 219M (The Dow Chemical Company, Mi Includes a blend of (available from dland, MI). Layer B is based on the total weight of Layer B. 100% by weight of DOWLEX® GM 8070 (The Dow Chemical) Includes (available from Company, Midland, MI). Then, primer 0.1-0.4 grams / square meter (gsm) (DigiPrime, Michelin) (Available from man, Inc.) was applied to layer B before printing.

[0064] The control sample was produced using a cast extruder and the following process conditions. [Table 1]

[0065] Sample 1 (Multilayer film with printed layer) Sample 1 is based on the total weight of the multilayer film, with 80% by weight of layer A and 20% by weight. It was a two-layer film prepared to have a general formula layer A and layer B having % of B.

[0066] Layer A, the core layer of the multilayer film layer, is 80% ELIT based on the total weight of Layer A. E(trademark) 5410 (The Dow Chemical Company, Midla (Available from nd,MI) and 20% by weight LDPE 219M (The Dow C Contains a blend from Chemical Company (available from Midland, MI). It was. Layer B of Sample 1 is approximately 18% vinyl acetate and 2% isobutyl acrylate. , and ethylene vinegar having an acid and acrylate functional group containing 2% methacrylic acid. It was a vinyl acetate copolymer. Ethylene vinyl acetate having acid and acrylate functional groups. The copolymer is produced by extruding 80% by weight of ethylene vinyl acetate polymer using a single-screw extruder. With weight % ethylene isobutyl acrylate and methacrylate terpolymer at 200°C Prepared for melt blending. Ethylene vinyl acetate polymer is 23% by weight of vinyl acetate. It contains nyl, and when measured at 190°C and 2.16 kg, it has a melt index of 2 g / 10 min. It had a tex. Ethylene isobutyl acrylate methacrylate polymer is 1 Melt index of 0g / 10 min and 10% by weight of isobutyl acrylate, and It contained 10% by weight of methacrylic acid.

[0067] The film for Sample 1 was produced using a cast extruder and the following process conditions. It was done. [Table 2]

[0068] Comparison Samples A-I (Multilayer films with comparison printing layers) Comparative samples A-I are based on the total weight of the multilayer film, with 80% by weight of layer A and Prepared to have a general formula A / B with 20% by weight of B. Layer A, each multilayer film The core layer of the layer is 80% by weight of ELITE(trademark) 5410(T) based on the total weight of layer A. Available from Dow Chemical Company, Midland, MI. ) and 20% by weight of LDPE 219M (The Dow Chemical Com It included (available from Pany, Midland, MI). Layer B of each film was the surface It contained 100% by weight of a polar resin functionalized according to the composition provided in 3. [Table 3]

[0069] The film was produced using a cast extruder and the following process conditions. [Table 4]

[0070] Example 2 - Performance analysis of control sample, sample 1, and comparative samples A-I In Example 2, the ink was used for the control sample, as well as for Sample 1 and Comparative Sample A. ~Digital printing was performed on the I printing layer. To carry out digital printing, a voltage difference radar was used. Using a siphon, the plate cylinder was charged, and the spectrum of the desired image was created. Next Next, the ink is applied to a charged cylinder, and the ink adheres to the area where a voltage difference is observed. The ink was dried and the carrier was removed. Then, a heated blanket set to 105°C was used. The ink was transferred to the plate, and the plate cylinder was discharged. Pressure was applied to the flexible substrate under tension. By adding this, the image was heat-transferred using a blanket. Control sample, sample 1. The ink compositions printed on comparative samples A-I are Hewlett-Pack It is sold commercially by ard Company as Electroink.

[0071] Digital printing has been completed on the control sample, sample 1, and comparison samples A-I. Then, fill using 3M tape in accordance with ASTM 2252-03 as described herein. The ink fixation of the ink was tested. The results of the ink fixation test, ASTM 2252-03, are shown in Table 5. It is summarized here.

[0072] The adhesive strength of the control sample, sample 1, and comparative samples A-I was also determined by heat sealing. The adhesive strength of the control sample, sample 1, and comparative samples A-I was tested before and after the experiment. To test this, each printed film was coated with a solvent-based adhesive, ADCOTE®. 577 (The Dow Chemical Company, Midland, MI) Laminated to a biaxially oriented polypropylene film (available from [source]). After curing, as specified herein Adhesion strength was measured before and after heat sealing according to the ASTM F904 standard. The results for the adhesive strength of Sample, Sample 1, and comparative samples A-I are summarized in Table 5. It is. [Table 5]

[0073] As shown in the results in Table 5, control sample, sample 1, comparison sample A, and While comparative sample F passed the ink fixation test, ASTM 2252-03, the comparison Samples B-E and G-I failed the test. Passing the ink fixation test means... The control sample, comparison sample A, and comparison sample F have different ink compositions in their printed layers. It was shown that it can adequately retain [the substance].

[0074] The results in Table 5 above show that when delamination is accelerated, Sample 1 is the control sample, and the comparison is made. It further demonstrated that it delivered higher adhesion than sample A and comparative sample F.

[0075] Example 3 - Effect of corona treatment on Sample 1 and Comparative Sample A In Example 3, Sample 1 and Comparative Sample A were compared with Sample 1 and Comparative Sample A. Immediately after the production of film A, it was subjected to corona treatment in-line at 1-2 kW. Then, in order to observe the effect of corona treatment on ink adhesion, the film was used immediately before printing. The sample was processed twice at 1kW. Sample 1 and the comparative sample were processed as described in Example 2. Ink was digitally printed onto the printing layer of sheet A.

[0076] Once digital printing of Sample 1 and Comparison Sample A onto the printing layer is complete, the film The ink fixation was attempted as described in Example 3 according to ASTM 2252-03. The following tests were conducted: Ink fixation tests were performed on corona-treated and untreated sample 1 and comparison sample A. The results are summarized in Table 6. [Table 6]

[0077] As shown in the results in Table 6, when comparative sample A was corona-treated, the film The ink fixation was severely affected, causing the tape to fail the test. However, the sample Sample 1 passed the tape test in both corona-treated and untreated conditions. Therefore, these The results showed that the print layer of Sample 1, whether corona-treated or untreated, had a sufficient ink composition. Unlike comparative sample A, it was not severely affected by the coronavirus treatment. This indicates that.

[0078] Example 4 - Generation of a printed layer containing a blend Samples 2-5 and comparative samples J-N (multilayer films with printed layers) In Example 4, a seven-layer film containing a blend of ethylene-based polymer and polar resin was produced. The printed layer was tested by performing the following. Each film was approximately 100 microns thick, approximately 1 It was 2 inches wide (approximately 30.48 centimeters).

[0079] The layers extruded through extruders G-C were samples 2-5 and comparative samples J-N. It was the same for each film. Extruders C, D, and E used HDPE (The Dow It is commercially available from Chemical Company as XUS 59900.94. (and LDPE (from The Dow Chemical Company AGIL) It included (marketed as ITY(trademark) 1021). Extruders F and G were , DOWLEX(TM) 8070G (The Dow Chemical Compan (Available from y) included. Films of samples 2-8 and comparative samples J-N. The layers are then provided in Tables 7 and 8. [Table 7]

[0080] Samples 2-5 and comparison samples J-N differ in their printed layers and were produced using extruders A and B. It was then extruded. Samples 2-5 are LLDPE (The Dow Chemical). (Commercially sold by the company as DOWLEX (trademark) 8070G), low melt Index Copolymer (VE from The Dow Chemical Company) (Sold as RSIFY(trademark)2000), or HDPE (The Dow Commercially available from Chemical Company as VERSIFY(trademark) 2000. Blended with various amounts of ethylene-based polymers (including those that have been used), acids and acrylics It contained an ethylene vinyl acetate copolymer having a functional group. Acids and acrylates Ethylene vinyl acetate copolymer having functional groups has acid and acrylate functional groups Based on the total weight of the ethylene vinyl acetate copolymer, it is approximately 18% vinyl acetate and 2% iso It contained butyl acrylate and 2% methacrylic acid. (Image of the printed layer of comparative sample M) This is ethylene vinyl acetate copolymer (The Dow Chemical Company) It contained (commercially sold as ELVAX(trademark) 3128 from y). Comparison sample The printing layer of N contained LLDPE (commercially available as DOWLEX (trademark) 8070G from The Dow Chemical Company). The composition of the printing layer of each of Samples 2 to 5 and Comparative Samples J to N is subsequently provided in Table 8. and each of Comparative Samples J to N is subsequently provided in Table 8.

Table 8

[0081] Performance Analysis of the Printing Layer Containing Example 5 - Blend In Example 5, the image was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N. To perform digital printing, a plate cylinder was charged using a charger with a voltage difference to create the spectrum of the target image. Subsequently, the ink was applied to the charged cylinder and made to adhere to the locations where a voltage difference was seen. The ink was dried to remove the carrier. Then, the ink was transferred to a heating blanket set at 105 °C, and the plate cylinder was discharged. The image was thermally transferred using a blanket by applying pressure to a flexible substrate under tension. This process was repeated in a half - rotation loop to digitally print onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used.

[0082] Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. Once the ink composition was digitally printed onto the printing layers of the control sample, as well as Samples 2 to 5 and Comparative Samples J to N, an ink fixation test was performed in accordance with ASTM 2252 - 03 using 3M tape. For the trials of the ink fixation test, each painted sample immediately after digital printing, each sample 10 minutes after digital printing, and each sample 60 minutes after digital printing were used. The tests included testing of each sample. The results of the ink fixation tests are summarized in Table 9. .

[0083] Adhesion strength of the printed layers of the control sample, as well as samples 2-5 and comparative samples J-N. The degree of testing was also performed in accordance with ASTM F904 as described herein. Control samples, as well as The adhesive strength results for the printed layers of samples 2-5 and comparative samples J-N are also summarized in Table 9. It is. [Table 9]

[0084] As shown in the results in Table 9, samples 2 and 3 underwent ink fixation tests, AST. I passed M 2252-03, but failed samples 4, 5, and comparative samples J-N. As shown in Table 9, both samples 2 and 3 had approximately 18% VA. 50 wt of acid and acrylate functional groups having 2% iBA and 2% MAA The printed layer contained more than % ethylene vinyl acetate copolymer. These results suggest that In the case of the control sample, the use of primers increases the complexity of the process, which is related to the process. Extra costs, internal / external (wrap seal) seals required in package design It became clear that there were drawbacks, including a decrease in the sealing of the joint.

[0085] It will be apparent that modifications and changes are possible without departing from the scope of this disclosure as defined in the attached "Claims." More specifically, while certain aspects of this disclosure are recognized as preferred or particularly advantageous herein, this disclosure is intended not to be limited to these aspects. The present invention includes the following embodiments. Section 1. A printing system, An ink composition containing charged ink particles dispersed in a liquid, A multilayer film, and the multilayer film is Polymer core layer, The polymer core layer comprises one or more printed layers adjacent to the polymer core layer, wherein the one or more printed layers contain at least 50% by weight of an ethylene vinyl acetate copolymer having acid and acrylate functional groups. A printing system comprising an ethylene vinyl acetate copolymer having an acid and acrylate functional group, comprising 0.5% to 4% by weight of methacrylic acid or acrylic acid, 0.5% to 4% by weight of acrylate, 7% to 40% by weight of vinyl acetate, and the remainder of ethylene, based on the total weight of the ethylene vinyl acetate copolymer having an acid and acrylate functional group. Section 2. The ethylene vinyl acetate copolymer having the aforementioned acid and acrylate functional group is present at 0.890 g / cm³. 3 ~0.980g / cm 3 The printing system according to item 1, having the density of [a certain value]. Section 3. The printing system according to any one of the preceding items, wherein the ethylene vinyl acetate copolymer having the acid and acrylate functional groups has a melt flow rate of about 0.5 grams per 10 minutes (g / 10 min) to about 20.0 g / 10 min when measured at 190°C and 2.16 kg according to ASTM D1238. Section 4. The printing system according to any one of the preceding items, wherein the ethylene vinyl acetate copolymer having the acid and acrylate functional groups has a melt flow rate of about 1.0 g per 10 min (g / 10 min) to about 10.0 g / 10 min when measured at 190°C and 2.16 kg according to ASTM D1238. Section 5. The printing system according to any one of the preceding claims, wherein the one or more printing layers further comprise a linear low-density ethylene polymer. Section 6. The printing system according to any one of the preceding items, wherein the printing system passes an ink fixation test according to ASTM 2252-03. Item 7. The printing system according to any one of the preceding items, wherein the polymer core layer contains an ethylene-based polymer having a secant modulus of elasticity of 2% exceeding 150 MPa. Item 8. The printing system according to any one of the preceding items, further comprising one or more of a sealing layer, a barrier layer, and a tie layer, or a combination thereof. Item 9. A printing method comprising: transferring an ink composition to a printing layer of a multilayer film, wherein the ink composition contains charged ink particles dispersed in a liquid, the multilayer film includes a polymer core layer and one or more printing layers adjacent to the polymer core layer, the one or more printing layers contain at least 50% by weight of an ethylene vinyl acetate copolymer having an acid and an acrylate functional group, and the ethylene vinyl acetate copolymer having an acid and an acrylate functional group contains 0.5% to 4% by weight of methacrylic acid or acrylic acid, 0.5% to 4% by weight of acrylate, 7% to 40% by weight of vinyl acetate, and the balance ethylene, based on the total weight of the ethylene vinyl acetate copolymer having an acid and an acrylate functional group. Item 10. The ethylene vinyl acetate copolymer having an acid and an acrylate functional group has a density of 0.890 g / cm 3 ~0.980 g / cm 3 The printing method according to item 8. Item 11. The ethylene vinyl acetate copolymer having an acid and an acrylate functional group has a melt flow rate of about 0.5 grams per 10 minutes (g / 10 min) to about 20.0 g / 10 min when measured at 190 °C and 2.16 kg according to ASTM D1238. The printing method according to item 8 or 9. Item 12. The printing method according to any one of claims 8 to 10, wherein the ink composition is transferred directly to the printing layer of the multilayer film without a primer. Section 13. A printing method according to any one of sub-sub Section 14. The printing method according to any one of claims 8 to 12, wherein the core layer of the multilayer film comprises an ethylene-based polymer having a secant modulus of 2% and exceeding 250 MPa. Section 15. The printing method according to any one of claims 8 to 14, wherein the polymer core layer comprises an ethylene-based polymer having a secant modulus of 2% and exceeding 250 MPa.

Claims

1. Printed articles, An ink composition containing charged ink particles dispersed in a liquid, A multilayer film, and the multilayer film is Polymer core layer, The polymer core layer comprises one or more printed layers adjacent to the polymer core layer, wherein the one or more printed layers contain at least 50% by weight of an ethylene vinyl acetate copolymer having acid and acrylate functional groups. The ethylene vinyl acetate copolymer comprises, based on the total weight of the ethylene vinyl acetate copolymer, 0.5% to 4% by weight of methacrylic acid or acrylic acid, 0.5% to 4% by weight of acrylate, 7% to 40% by weight of vinyl acetate, and the remaining ethylene. The one or more printed layers further comprise a linear low-density ethylene polymer, A printed article in which the ink composition is attached to the printing layer.

2. The ethylene vinyl acetate copolymer having the acid and acrylate functional groups was measured according to ASTM D792 at 0.890 g / cm³. ３ ~0.980g / cm ３ A printed article according to claim 1, having the density of [a certain value].

3. The printed article according to claim 1 or 2, wherein the ethylene vinyl acetate copolymer having the acid and acrylate functional group has a melt flow rate of about 0.5 grams per 10 minutes (g / 10 min) to about 20.0 g / 10 min when measured at 190°C and 2.16 kg according to ASTM D1238.

4. The printed article according to claim 1 or 2, wherein the ethylene vinyl acetate copolymer having the acid and acrylate functional group has a melt flow rate of about 1.0 g per 10 min (g / 10 min) to about 10.0 g / 10 min when measured at 190°C and 2.16 kg according to ASTM D1238.

5. The printed article according to any one of claims 1 to 4, wherein the printed article passes an ink fixation test in accordance with ASTM 2252-03.

6. The printed article according to any one of claims 1 to 5, wherein the polymer core layer comprises an ethylene-based polymer having a secant modulus of 2% with a secant modulus of 150 MPa or greater, as measured according to ASTM D882.

7. A printed article according to any one of claims 1 to 6, further comprising one or more sealing layers, barrier layers, tie layers, or combinations thereof.

8. The ethylene vinyl acetate copolymer comprises, based on the total weight of the ethylene vinyl acetate copolymer, 0.5% to 4% by weight of methacrylic acid or acrylic acid, 0.5% to 4% by weight of acrylate, 10% to 20% by weight of vinyl acetate, and the remaining ethylene. The printed article according to any one of claims 1 to 7, wherein the printed article passes an ink fixation test in accordance with ASTM 2252-03.

9. A printing method, This includes transferring an ink composition to a printing layer of a multilayer film. The ink composition comprises charged ink particles dispersed in a liquid, A printing method wherein the multilayer film comprises a polymer core layer and one or more printing layers adjacent to the polymer core layer, the one or more printing layers comprising at least 50% by weight of an ethylene vinyl acetate copolymer having acid and acrylate functional groups, the ethylene vinyl acetate copolymer comprising 0.5% to 4% by weight of methacrylic acid or acrylic acid, 0.5% to 4% by weight of acrylate, 7% to 40% by weight of vinyl acetate, and the remaining ethylene, based on the total weight of the ethylene vinyl acetate copolymer, and the one or more printing layers further comprising a linear low-density ethylene polymer.

10. The ethylene vinyl acetate copolymer having the acid and acrylate functional groups was measured according to ASTM D792 at 0.890 g / cm³. ３ ~0.980g / cm ３ The printing method according to claim 9, having a density of the above.

11. The printing method according to claim 9 or 10, wherein the ethylene vinyl acetate copolymer having the acid and acrylate functional group has a melt flow rate of about 0.5 grams per 10 minutes (g / 10 min) to about 20.0 g / 10 min when measured at 190°C and 2.16 kg according to ASTM D1238.

12. The printing method according to any one of claims 9 to 11, wherein the ink composition is directly transferred to the printing layer of the multilayer film without a primer.

13. A printing method according to any one of claims 9 to 12, wherein a printed material is produced by transferring an ink composition to a printing layer of a multilayer film, and the printed material passes an ink fixation test in accordance with ASTM 2252-03.

14. The printing method according to any one of claims 9 to 13, wherein the polymer core layer comprises an ethylene-based polymer having a secant modulus of 2% with a secant modulus of more than 250 MPa when measured according to ASTM D882.

15. The ethylene vinyl acetate copolymer comprises, based on the total weight of the ethylene vinyl acetate copolymer, 0.5% to 4% by weight of methacrylic acid or acrylic acid, 0.5% to 4% by weight of acrylate, 10% to 20% by weight of vinyl acetate, and the remaining ethylene. The printing method according to any one of claims 9 to 14, wherein a printed article printed by the printing method according to any one of claims 9 to 14 passes an ink fixation test in accordance with ASTM 2252-03.

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