KR102267906B1 - Packaging material and method for preparing the same using ethanol based ink composition - Google Patents

Abstract

Disclosed are a packaging film using an ethanol-based ink composition for manufacturing a packaging material by gravure printing an ink composition on a primary paper, which is a film to be printed, to obtain a printed film, and then laminating it through a solvent-free bonding process, and a method for manufacturing the same. The ink composition, the polyurethane resin composition 10 to 30% by weight, vinyl resin 4 to 10% by weight, pigment 10 to 40% by weight, additives 1 to 5% by weight of the ink consisting of the remaining solvent consisting of ethanol; And 50 to 150 parts by weight of ethanol as a diluting solvent with respect to 100 parts by weight of the ink; and the gravure printing uses a low-depth copper plate having a depth of 12 to 16 μm for 220 to 280 lines.

Description

Packaging material and method for preparing the same using ethanol based ink composition

The present invention relates to a packaging material using an ethanol-based ink composition and a method for manufacturing the same.

More specifically, during gravure printing, a low-depth copper plate method is applied while using an ethanol-based eco-friendly ink instead of a regulated substance harmful to the human body, VOCs (volatile organic compounds), which is a diluting solvent diluted in conventional general-purpose ink, but with an ink composition and printing. It relates to a packaging material using an ethanol-based ink composition for gravure printing of a low depth copper plate method, which can improve workability, print quality, etc., and reduce process costs by optimizing conditions, and a method for manufacturing the same.

Gravure printing, which is an intaglio printing method, is a printing method in which ink is filled in the concave line of a copper plate and transferred to the object to be printed.

In the case of conventional general-purpose inks used for such printing work, MEK (methyl ethyl ketone), EA (ethyl acetate), toluene, xylene, etc. are used as diluent solvents, which are harmful to the human body as VOCs (volatile organic compounds) harmful to the human body, Accordingly, it is subject to regulation by the Chemicals Control Act, and there are many restrictions on storage, management, and handling.

In order to replace this, water-based ink is sometimes used as a diluting solvent, but there is a problem in that a relatively large amount of energy is required for the drying process and the productivity is lowered due to a decrease in the working speed.

In addition, there are cases where an ethanol solvent is used to replace the existing organic solvent, but in order to use ethanol as an organic solvent, an alcohol-soluble urethane resin must be used. Print quality problems such as decreasing persistence.

On the other hand, when using an eco-friendly printing composition and gravure printing, there are cases where the bow is set to 190 to 200 lines and the depth is 14 to 16 μm. However, since the conditions for the copper plate are determined using an ink composition with a high content of urethane resin, it is still It is unsatisfactory in workability, print quality, etc., and needs improvement (Patent Document 1).

Korean Patent Registration No. 1860675

In exemplary embodiments of the present invention, in one aspect, while reducing VOCs (volatile organic compounds) emissions and residual solvent detection amount, the composition of the ink composition and process conditions such as low-depth copper plate conditions are optimized to increase workability and productivity, and , to provide a packaging material using an ethanol-based ink composition for low-depth gravure printing, which reduces the process cost by lowering the printing application amount, and also improves the print quality, and a manufacturing method thereof.

In exemplary embodiments of the present invention, in another aspect, a resin having excellent ethanol solubility in alcohol solvents, particularly when ethanol is used as a base, and having process conditions suitable for ethanol solvents, ethanol base for low-depth gravure printing An object of the present invention is to provide a packaging material using an ink composition and a method for manufacturing the same.

In exemplary embodiments of the present invention, a first step of gravure printing an ink composition on a first paper, which is a film to be printed, to obtain a printing film, wherein the ink composition comprises 10 to 30% by weight of a polyurethane resin composition, Ink consisting of 4 to 10% by weight of a vinyl resin, 10 to 40% by weight of a pigment, 1 to 5% by weight of an additive and the remainder of the solvent consisting of ethanol; And 50 to 150 parts by weight of ethanol as a diluting solvent with respect to 100 parts by weight of the ink; and the gravure printing is an ethanol base, characterized in that it uses a low-depth copper plate having a depth of 12-16 μm for 220-280 lines. Provided is a method for manufacturing a packaging material using an ink composition.

In an exemplary embodiment, the chamber temperature is maintained at 52 ~ 70 ℃ during printing, and the fan speed is 80 ~ 90 m ³ /min.

In addition, in an exemplary embodiment, the production speed during printing may be performed at 240 ~ 260M / min.

In an exemplary embodiment, the polyurethane resin composition includes a polyurethane resin obtained by reacting a urethane prepolymer, an amine-based chain extender, and an aminosilane-based coupling agent.

In an exemplary embodiment, the method further includes a second step of laminating the printed film with a secondary paper fabric using at least one of a solvent-free adhesive and an extrusion resin after drying the print film.

In an exemplary embodiment, the solvent-free type adhesive may be a two-component polyurethane-based adhesive including a main agent and a curing agent.

In an exemplary embodiment, the method further includes a third step of laminating with a tertiary paper fabric using at least one of a solvent-free type two-component adhesive and an extrusion resin after aging after completion of the secondary paper lamination.

In exemplary embodiments of the present invention, there is also a packaging material made of a film laminate, wherein the film laminate includes a printing film in which an ink layer is formed on a first paper feed that is a film to be printed, and the ink layer is a polyurethane resin; a vinyl resin comprising at least one of a vinyl butyral resin and a vinyl acetate resin; and a pigment; provides a packaging material comprising a.

In an exemplary embodiment, the film laminate may be one in which one or more adhesive layers selected from a solvent-free adhesive layer and an extruded resin layer are formed on the printed film, and a secondary paper is further laminated on the adhesive layer. There is no organic solvent residue in the solvent-free adhesive layer and the extruded resin layer.

In an exemplary embodiment, in the film laminate, one or more adhesive layers selected from a solvent-free adhesive layer and an extruded resin layer are formed on the second-grade paper, and the third-grade paper may be further laminated on the adhesive layer. There is no organic solvent residue in the solvent-free adhesive layer and the extruded resin layer.

According to exemplary embodiments of the present invention, a resin having excellent ethanol solubility is used in the case of ethanol as a base among alcohol solvents, and process conditions such as low depth copper plate conditions suitable for the ink composition are used.

Accordingly, it reduces TVOCs (total volatile organic compounds) and TPH (total petroleum hydrocarbons) and reduces the amount of residual solvents detected, thereby reducing harmfulness to the human body and odor, and has the advantage of being eco-friendly, thereby contributing to the improvement of work efficiency. In addition, by using a low-depth laser copper plate, it is possible to reduce the amount of ink used, thereby lowering the process unit cost, providing excellent workability and productivity, and improving the quality of printed matter.

1 is a schematic diagram showing the composition of the laminate in a comparative example of the present invention.
2 to 4 are schematic diagrams showing the composition of the laminate according to exemplary embodiments of the present invention.
Figure 5 shows the result of comparison of appearance quality (color) of Experiment 2 of the present invention, and Figure 5a shows the case of the comparative example, and Figure 5b shows the case of the example.

In the present specification, first-class paper refers to fabrics such as OPP, PET, Nylon, and paper that can print the ink composition on one side by, for example, a gravure method.

In the present specification, the second-grade paper means a fabric that can be laminated with the first-grade paper. For example, fabrics such as air permeation and moisture permeability barrier (VM)CPP, (VM)PET), aluminum, LLDPE, etc. that can be laminated with first-class paper using either a solvent-type adhesive or a solvent-free adhesive and an extrusion resin may be ryu.

In the present specification, the tertiary paper refers to a fabric that can be laminated with the second-grade paper, for example, a fabric such as CPP or LLDPE.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Ink composition composition

The ethanol base ink composition for low-depth gravure printing of exemplary embodiments of the present invention comprises 10 to 30% by weight of a polyurethane resin composition, 4 to 10% by weight of a vinyl resin, 10 to 40% by weight of a pigment, 1 to 5% by weight of an additive and ink consisting of the remainder of the solvent consisting of ethanol; and 50 to 150 parts by weight of ethanol as a diluting solvent based on 100 parts by weight of the ink.

(One) polyurethane resin composition

The polyurethane resin of the polyurethane resin composition may be obtained by reacting a urethane prepolymer, an amine-based chain extender, and an aminosilane-based coupling agent, and is diluted with an alcohol solvent during the reaction to thereby finally reduce the polyurethane resin to a solid content Among them, 10 to 90 wt%, preferably 20 to 60 wt%, may be used.

The urethane prepolymer may be obtained by reacting a polyol with a diisocyanate compound.

The polyol is preferably a polyether polyol containing an ether bond, and as such a polyether polyol, for example, polytetramethylene Ether Glycol (PTMG), polyethylene glycol (Polyethylene Glycol; PEG), poly It may be at least one selected from the group consisting of propylene glycol (Polypropylene Glycol; PPG) and 1,2-butanediol (1,2-Butandiol), and preferably polytetramethyl ether glycol is used alone, or polytetramethyl ether glycol is used alone. Methyl etherglycol and 1,2-butanediol may be used together.

The polyol has an acid value of 1 or less and a number average molecular weight of 500 to 5000 is preferably used. This is because, when the number average molecular weight of the polyol is less than 500, the print transferability of the ink to which the polyurethane resin is applied is poor, and the printed coating film is hard, so that the adhesion to the polymer film is poor. When the number average molecular weight exceeds 5000, when the printed matter is wound on a roll after gravure printing, there is a problem in that a blocking phenomenon occurs between the printing surface and the printed surface, so a polyol having the above-described number average molecular weight range is used. It is preferable to use

More preferably, a polyol having a number average molecular weight of 1000 to 3000 may be used, and in order to further improve the print transferability and initial adhesion of the gravure ink, further suppress the blocking phenomenon, and improve the strength of the printed coating film, different numbers Two polyols having an average molecular weight may be mixed and used.

For example, a first polyol having a number average molecular weight of 1000 to 1500 and a second polyol having a number average molecular weight of 2000 to 3000 may be used together, and the first polyol and the second polyol may be the same type of polyol, and different It may also be a type of polyol.

The diisocyanate compound may be an aliphatic, alicyclic or aromatic diisocyanate, for example, hexamethylene diisocyanate, Isophorone diisocyanate, methylcyclohexane diisocyanate (MethylCycloHexane diisocyanate), Xylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 2,4-toluene diisocyanate, 2 ,6-toluene diisocyanate (2,6-toluene diisocyanate) may be at least one selected from the group consisting of, but is not necessarily limited thereto.

In order to prepare the urethane prepolymer, the diisocyanate compound may be used in an amount of 1 to 3 equivalents based on 1 equivalent of polyol, and more preferably 1.3 to 2.6 equivalents based on 1 equivalent of polyol. If the equivalent weight of the diisocyanate compound to the polyol is insufficient, the adhesion of the printed coating film formed on the substrate may be poor, and if it is excessive, the re-solubility and transferability of the gravure ink will be poor. It is preferable to mix and react the two substances so as to have one equivalent ratio.

The urethane prepolymer thus obtained can react with the chain extender and the coupling agent to form a polyurethane resin, and by reacting with the chain extender and the coupling agent, the adhesion of the gravure ink to the substrate and the strength of the printed coating film can be improved. have.

As the chain extender, an amine-based chain extender is preferably used, for example, ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, diamine At least one selected from the group consisting of cyclohexylmethane 4,4-diamine, diethylene triamine and triethylene teramine may be used, Preferably isophorone diamine can be used.

As the coupling agent, a silane-based coupling agent may be used, and preferably, an aminosilane-based coupling agent including an amine group may be used. For example, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane), N-2-(aminoethyl)-3-aminopropyltriethane N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-phenyl- 3-aminopropyl trimethoxysilane (N-phenyl-3-aminopropyl trimethoxysilane) and N-2-(amino ethyl)-3-aminopropyl methyldimethoxysilane (n-(2-aminoethyl)-3-aminopropylmethyl dimethoxysilane) At least one selected from the group consisting of may be used, but is not necessarily limited thereto.

On the other hand, the amine-based chain extender and the aminosilane-based coupling agent reacting with the urethane prepolymer to prepare the polyurethane resin are the sum of the weight ratio of the amine-based chain extender and the aminosilane-based coupling agent with respect to 100 wt% of the urethane prepolymer. It is preferable that this is 3-12 wt%. When the sum of these weight ratios is less than 3 wt%, the storage stability becomes poor due to the isocyanate groups remaining in the polyurethane resin composition, and the adhesion of the ink coating film to the substrate changes over time, resulting in poor adhesion. When it exceeds 12 wt%, an amine-based chain extender and amino reacting with the urethane prepolymer with respect to 100 wt% of the urethane prepolymer because an odor is generated due to the presence of unreacted amine compounds in the polyurethane resin composition. It is preferable that the sum of the weight ratio of the silane-based coupling agent is 3 to 12 wt%, and the weight ratio of the amine-based chain extender and the aminosilane-based coupling agent to 100 wt% of the urethane prepolymer to secure more stable storage stability and adhesion. It is more preferable that the reaction is carried out so that the sum of them is 5 to 8 wt%.

The polyurethane resin composition may be used in an amount of 10 to 30% by weight in the gravure ink, preferably 15 to 25% by weight, as described above.

If the content of the polyurethane resin composition is insufficient than the above range, problems such as a decrease in the adhesion of the ink and a decrease in the strength of the ink film may occur, and a problem that the solvent remains in the printed matter after printing may occur, and the polyurethane resin When the content of the composition is excessive, the transferability of the ink from the gravure printing plate to the substrate is poor due to the excessive increase in the viscosity of the gravure ink composition, blocking may occur, and the cutting property using a knife is lowered, so that the ink is applied to the gravure printing plate after printing. It is preferable to be included in the above-mentioned weight range because it may remain and cause contamination of the printing plate.

(2) vinyl resin

On the other hand, the vinyl resin is added to increase the dispersibility of the gravure ink composition to obtain effects such as improved adhesion, blocking prevention, and reliability improvement.

As the vinyl resin, at least one of a vinyl butyral resin and a vinyl acetal resin having excellent solubility in alcohol, not a general vinyl resin, is used. In particular, it is more preferable to use a vinyl butyral resin that has excellent adhesion to the film and can increase reliability during printing, and can be used together with vinyl butyral resin and vinyl acetal resin to further improve blocking resistance. have.

In the case of vinyl acetal resin, since the glass transition temperature is high, so blocking resistance can be improved, one of the two vinyl resins can be selected and used as needed, or both types of vinyl resins can be used.

When the content of the vinyl resin is less than 4% by weight, it is difficult to obtain the effect of improving the dispersibility and preventing the blocking of the gravure ink composition, and when it exceeds 10% by weight, the viscosity increases and the transferability of the ink to the substrate becomes poor, and the ink coating film Due to the increase in hardness of the ink coating film is formed on the substrate, warpage occurs and adhesion to the substrate is reduced, so it is preferable to use within the above-mentioned weight range.

(3) pigment

On the other hand, the pigment is added to impart color to the gravure ink composition, and is not limited to the type thereof, such as an organic pigment or an inorganic pigment, and may be appropriately selected and used according to the use or working environment of the gravure ink composition.

The content of the pigment may be included in the gravure ink composition in an amount of 10 to 40% by weight, and when it is less than 10% by weight, it is difficult to express the required color, and when it exceeds 40% by weight, the viscosity of the ink increases, and the dispersibility of the pigment Since problems such as deterioration, aggregation and sedimentation of the pigment may occur, it is preferably used within the above-mentioned weight range.

(4) additives

The additive is added to improve the physical properties and workability of the gravure ink composition, and may be included in a total content range of 1 to 5 wt % in the gravure ink composition.

Additives may include matting agents, adhesion promoters, waxes, and the like.

The matting agent is added to increase the visibility of the printed matter by lowering the glossiness of the gravure ink composition, and a silica-based matting agent may be used, and preferably, silica surface-treated with wax may be used.

The wax is added to increase the rate of solidification after the gravure ink composition is transferred to the adherend to increase the releasability of the gravure ink composition on the gravure printing plate. Paraffin wax, montan wax, sasol wax, polyethylene wax, polypropylene wax, Fischer -Various synthetic waxes such as trowa wax, opi wax, microcrystalline wax, petroleum wax, hydrocarbon wax, myristic acid, palmitic acid, stearic acid, fatty acids and derivatives thereof, mineral wax, carnauba It may be at least one selected from the group consisting of wax, candela wax, and beeswax wax, but is not limited thereto.

The adhesion enhancer is added to improve the adhesion of the gravure ink composition to the substrate. For example, a chlorinated polypropylene resin may be used. In addition, if it is to increase the adhesion of the ink coating film, it is not particularly limited. may be added without

Such additives may be included in a weight range of 1 to 5% by weight, and when included in less than 1% by weight, it is difficult to obtain the effect of improving physical properties by the additive, and when included in excess of 5% by weight, excess additives It is preferable to be included within the above-described weight range because the adhesion, dispersing power, dissolving power in alcohol, and the like of the ink may be reduced by the above.

(5) diluent solvent

On the other hand, in exemplary embodiments of the present invention, the ink (that is, 10 to 30% by weight of the polyurethane resin composition, 4 to 10% by weight of the vinyl resin, 10 to 40% by weight of the pigment, 1 to 5% by weight of the additive and ethanol 50 to 150 parts by weight, preferably 60 to 140 parts by weight, or 70 to 130 parts by weight, or 80 to 120 parts by weight, or 90 to 110 parts by weight, of ethanol as a diluting solvent based on 100 parts by weight of the ink consisting of the remaining solvent Or more preferably, it is prepared in 100 parts by weight.

When the diluent solvent, ethanol, is 50 parts by weight or less, the ink viscosity may increase, transfer failure, and drying failure may occur. If the ethanol content exceeds 150 parts by weight, the ink viscosity may decrease, resulting in poor transfer and color defects.

Manufacture process

First, the preparation of the polyurethane resin composition used in the gravure printing composition will be described.

(1) Preparation of polyurethane resin composition

Polyurethane resin composition, a urethane prepolymer preparation step of preparing a urethane prepolymer by reacting a polyol and a diisocyanate compound; a dilution step of mixing the urethane prepolymer and alcohol; and a polyurethane resin composition preparation step of preparing a polyurethane resin by reacting the urethane prepolymer that has undergone the dilution step with an amine-based chain extender and an aminosilane-based coupling agent.

The urethane prepolymer preparation step is a step of reacting a polyol and a diisocyanate compound, and may be a step of mixing a polyol and a diisocyanate compound and reacting at 60 to 90° C. for 2 to 5 hours, in which case dibutyl to improve reactivity A catalyst such as Dibutyltin dilaurate may be mixed and reacted together.

The dilution step is a step performed to increase the reactivity by improving the dispersibility of the urethane prepolymer and other components in the manufacturing step of the polyurethane resin composition carried out later, and in this case, the dilution is performed by mixing the urethane prepolymer and the alcohol with a weight of 1:1 to 2 It can be carried out by mixing in the range, preferably 1:1.1 to be carried out by mixing in the weight range of 1.7. At this time, it is preferable to use ethanol having good volatility as alcohol and not harmful to the human body and the environment.

Next, the polyurethane resin composition preparation step is a step of reacting the diluting urethane prepolymer with an amine-based chain extender and an aminosilane-based coupling agent, and after mixing each component, 2 to 5 hours at 30-55° C. It may be a step of reacting during the

In this reaction step, alcohol may be further mixed to improve dispersibility, and preferably ethanol may be further mixed and reacted. The polyurethane resin composition obtained through this step may have a solid content of 10 to 90 wt%, preferably 20 to 60 wt%.

(2) gravure Printing ink composition preparation

After preparing the polyurethane resin composition as described above, as described above, 10 to 30% by weight of the polyurethane resin composition, 4 to 10% by weight of the vinyl resin, 10 to 40% by weight of the pigment, 1 to 5% by weight of the additive and ethanol ink consisting of the remainder of the solvent; and 50 to 150 parts by weight of ethanol as a diluting solvent based on 100 parts by weight of the ink; to prepare a gravure printing ink composition.

The viscosity of the ink composition is maintained so that 200 ~ 600 g / cm · s.

(3) Copper plate conditions and print job conditions

The printing process for producing eco-friendly packaging materials is first carried out, followed by the roll-to-roll method, which is a gravure printing method. The cylinder of the concave plate rotates and the ink from the ink pan is transferred to the fabric to be printed.

Here, in exemplary embodiments of the present invention, during gravure printing, the cylinder is carried out in a low-depth copper plate method while using ethanol (EtOH) alone as a diluting solvent for the ink.

In this case, in order to improve the printing characteristics and workability when the ink composition is used, in particular, the copper plate conditions (line and depth) and working conditions (air volume and temperature) are optimized.

Specifically, the cylinder uses a low-depth copper plate having a depth of 12-16㎛ in 220-280 bows in order to deliver the printed part to the printed body during the gravure printing.

In the case of less than 220 cylinders and more than 16㎛ depth, the ink usage is increased and drying failure occurs, and if the cylinder exceeds 280 bows and less than 12㎛ depth, the ink usage is reduced, but color defects occur due to poor ink transfer do.

In addition, the chamber temperature is maintained at 52 ~ 70 ℃ during printing, and the fan speed is maintained at 80 ~ 90 m ³ /min to volatilize the solvent and dry the ink of the printed object.

If the temperature and air volume are lower than the range, the ink does not dry and a defect may occur. If the temperature and air volume are higher than the range, only the surface of the ink is dried and the inner surface of the ink is not dried.

In addition, in an exemplary embodiment, the production speed during printing may be 240 to 260 M/min (that is, forming a printed layer while allowing 240 to 260 M of fabric to pass per unit minute), preferably 250 M/min.

If the speed range is exceeded, the residence time in the drying chamber may decrease, resulting in ink drying failure.

As a first-class paper fabric used as the print subject, OPP, PET, NY, paper, etc. may be used. A printed film is formed by printing on such a first-class fabric using the ink composition described above (first step).

On the other hand, the above-described ink composition is applied to the print object (first paper feed film) and dried, and then the packaging material is prepared by solvent-free adhesion or extrusion coating process. That is, in order to provide additional functionality to the printed film coated with eco-friendly ink, grade 2 or 3 paper products can be manufactured by a laminating process using a solvent-free adhesive or a PE resin extrusion coating process.

Exemplary embodiments of the present invention use not solvent-based processes, but in particular solvent-free processes.

For reference, Figure 1 is a schematic diagram showing a laminate configuration employing a solvent-type process in a comparative example of the present invention.

In the solvent-type process, a solvent-type adhesive that uses an organic solvent such as methanol or EA as a diluting solvent is used for film interlayer adhesion. These solvent-type adhesives have a problem in that the adhesive is diluted in a solvent (solid content is usually about 50 to 70%), and although the adhesive strength is excellent, VOCs are generated. Therefore, in order to prevent the use of the organic solvent as much as possible, a solvent-free adhesive is used as a solvent-free process during bonding, or extrusion coating is used.

In the case of the solvent-free process, there is no solvent itself as 100% solid content, and there is no VOCs because there is no organic dilution solvent itself. On the other hand, in the case of the extrusion coating layer, since the extruded resin is diluted in water (typically about 5 to 10% of solid content), VOCs do not occur.

Specifically, after drying the print film, it is laminated with a second-grade paper using at least one of a solvent-free type two-component adhesive and an extruded resin (second step). Next, after the completion of the secondary paper lamination, for example, after aging in an aging room at 42 ~ 45 ℃, using at least one of a solvent-free type two-component adhesive and an extrusion resin may further include a third step of laminating with the tertiary paper fabric.

The second grade paper may be used with a fabric to which functionality such as aluminum, VMPET (VM: vacuum metalizing), nylon (NY), etc. having the function of air permeation and moisture permeability barrier (barrier property) and pinhole resistance.

The 3rd grade paper may be composed of functional fabrics such as CPP, VMCPP, and LLDPE as a sealant layer.

On the other hand, the 2nd and 3rd grade paper may be adhered to the printing film by a non-dry solvent lamination method. At this time, it can be laminated with a two-component (subject, curing agent) solvent-free polyurethane adhesive, and at this time, the aging conditions (50~60℃, 24hr~48hr) should be observed so that sufficient curing can occur.

The main agent that can be used as the two-component (main, curing agent) solvent-free polyurethane-based adhesive is a polyol component, and the curing agent is an isocyanate component.

On the other hand, it can be adhered by a polyethylene resin extrusion process, and in this case, after applying an aqueous type anchor coating agent to the printing film, for example, using a polyethylene resin melt-extruded at 320 ~ 330 ° C. can

As the anchor coating agent, an isocyanate-based or polyethyleneimine-based material may be used. 90 to 95% by weight of distilled water may be mixed with 5 to 10% by weight of the anchor coating agent.

The thickness of each sheet of paper or the amount of resin applied should be adjusted according to the physical properties and functions according to the application purpose.

film on packaging laminate Configuration

In exemplary embodiments, a packaging material made of a film laminate (or laminate), wherein the film laminate includes a printing film in which an ink layer is formed on a first paper feed, which is a film to be printed, and the ink layer includes a polyurethane resin; a vinyl resin comprising at least one of a vinyl butyral resin and a vinyl acetate resin; and a pigment;

In an exemplary embodiment, the film laminate may be one in which one or more adhesive layers selected from a solvent-free adhesive layer and an extruded resin layer are formed on the printed film, and a secondary paper is further laminated on the adhesive layer.

Alternatively, the film laminate may be one in which one or more adhesive layers selected from a solvent-free adhesive layer and an extruded resin layer are formed on the second-grade paper, and the third-grade paper is further laminated on the adhesive layer.

In the above, there is no organic solvent residue in the solvent-free adhesive layer and the extruded resin layer.

2 to 4 are schematic diagrams showing the laminate configuration according to exemplary embodiments of the present invention.

Specifically, it may be composed of 1st grade paper / printing layer / solvent-free adhesive layer / 2nd grade paper / solvent-free adhesive layer / 3rd grade paper (see FIG. 2).

Alternatively, it may be composed of 1st grade / printing layer / anchor coating layer / polyethylene extrusion coating layer / 2nd grade / anchor coating layer / polyethylene extrusion coating layer / 3rd grade paper (see Fig. 3).

Alternatively, it may be composed of 1st grade / printing layer / solvent-free adhesive layer / 2nd grade / anchor coating layer / polyethylene extrusion coating layer / 3rd grade (see Fig. 4).

In the above embodiments, the layer configuration was made up to grade 3, but if necessary, the layer configuration can be made only with grades 1 and 2, and of course, products of grade 4 or higher can also be manufactured.

Exemplary embodiments of the present invention are described in more detail through the following examples. The embodiments disclosed herein are merely illustrative for purposes of explanation, and the embodiments of the present invention may be embodied in various forms and should not be construed as being limited to the embodiments described herein.

[Experiment 1]

<Examples and Comparative Examples>

In this Example and Comparative Example, as described in Table 1 to be described later, except that the ink component composition was different, the preparations were the same. That is, an ink layer was formed through gravure printing using each ink composition on the first-grade paper, which is the printed object, and was laminated through a solvent-free laminating process when laminating the second- and third-grade papers.

The solvent-free adhesive has a solid content of 100%, and a polyurethane adhesive of a polyol base and an isocyanate curing agent two-component type was used, and the coating amount (based on WET) was 1.8 g/m ² .

In Comparative Example 1 and Examples 1 to 3, in common, the first grade used OPP, the second grade used VMCPP, and the third grade used CPP.

After forming the printed layer on the first grade paper, it was dried for about 12 hours and then laminated with the second grade fabric and solvent-free lamination process. The aging room temperature was maintained at 42-45°C. For reference, aging is a process of storing the fabric in a separate aging room for hardening after completion of the process, and the drying means an operation in which dry chamber conditions are applied to the fabric during the process operation.

In order to transfer the printed part to the printed body during the gravure printing, a low-depth copper plate having a depth of 16㎛ with 250 bows was used as the cylinder.

In addition, the chamber temperature was maintained at 70 °C during printing, and the fan speed was maintained at ^{80 ~ 90 m 3 /min.} In addition, the chamber speed during printing was set to 250M/min.

The print chamber size is 1500 mm [width] x 1050 mm [length] x 1970 mm [height].

The table below shows the ink composition in each of Examples and Comparative Examples.

Ingredients (g) Example 1 Example 2 Example 3 comparative example polyurethane resin composition 20.5 20.5 20.5 20.5 polyvinyl butyral resin 5.3 - 3.8 - polyvinyl acetal resin - 5.3 1.6 - Rutile titanium dioxide (pigment) 31.3 31.3 31.3 31.3 ethanol 39.1 39.1 39.0 44.4 additive 3.8 3.8 3.8 3.8 Sum 100.0 100.0 100.0 100.0 diluent solvent ethanol 100.0 100.0 100.0 100.0

<Result>

Experiments were performed to measure initial adhesion, print film strength, and blocking resistance of the ink composition for gravure printing, and the results are as follows.

Initial adhesion evaluation

^{After printing the ink composition in an amount of 5 g/m 2} on a corona-treated stretched polyethylene film (OPP), a polyethylene terephthalate film (PET) and a nylon film (Nylon) using a bar coater, 40 to 50 A test specimen was prepared by drying at ℃ for 30 seconds. After one day of printing, the cellophane tape was attached to the printing surface and sharply removed at an angle of 60 degrees, and then the peeling state of the printed coating film was evaluated, and the results are shown in Table 2. The evaluation criteria are as follows.

◎: Ink does not peel off at all from the printing surface

○: More than 70% of ink remains on the printed side

△: 30% or more of ink remains on the printed side

X: Less than 30% of ink remains on the printed side

Dry laminate strength evaluation

A test specimen is prepared in the same way as the initial adhesion evaluation, a two-component polyurethane adhesive ^{is applied to the printing surface in an amount of 3 g/m 2} , a non-stretched polypropylene film is laminated, and then heat treated in an oven at 60° C. for 3 days After that, it was taken out and cut into a size of 15 mm in width. Then, the T-type peel strength at a speed of 300 mm/min of each film cut using a universal testing machine was measured, and the results are shown in Table 2.

blocking resistance evaluation

Five sheets of PET film having the ink composition printed on both sides were laminated, and 1 kg/cm ² pressure was applied at a temperature of 60° C. and left for 24 hours, and then the degree of peeling of the printed layer was visually observed, and the According to the blocking resistance was evaluated.

◎: no change

○: There is a slight surface change

△: 20% or less partially peeled off

X: Exceeding 20% peeled

Test Items film type Example 1 Example 2 Example 3 comparative example initial adhesion OPP ◎ ○ ◎ △ PET ◎ ○ ◎ ○ nylon ◎ ○ ◎ ○ Dry Laminate Strength (g/mm) OPP 280 210 260 130 PET > 650 > 550 > 650 400 nylon 410 360 380 310 blocking resistance PET ○ ◎ ◎ △

As can be seen from Examples, when a vinyl butyral resin or a vinyl acetal resin vinyl resin is included in the ink composition for gravure printing, the adhesion and blocking resistance of the ink composition to the adherend surface are improved, especially with the vinyl butyral resin When all of the vinyl acetal resin was used, the effect was further improved.

On the other hand, in the case of the comparative example in which the vinyl resin was not included, ink adhesion and laminate strength were significantly reduced, and it was determined that blocking resistance was also somewhat poor.

[Experiment 2]

<Examples and Comparative Examples>

Example 1 of Experiment 2 is the same as Example 1 of Experiment 1. That is, as in Example 1 of Experiment 1, a low-depth copper plate was used for the ethanol-based ink, and a solvent-free laminating process was performed.

On the other hand, in Experiment 2, as a comparative example, an ink layer was formed using a general-purpose ink using an existing organic solvent as a diluent solvent, and the copper plate was applied to the low-depth copper plate of Example 1 (line: 250 lines, depth: 12 to 16 μm), but the conventional Herio copper plate (line: 175 lines, depth: 22 ~ 27 μm) was used in the same manner as in Example 1 of this experiment 2.

The general-purpose ink of Experiment 2 is a known ink that contains vinyl resin and urethane resin as resins, MEK, EA, and dry solvent as residual solvents, and uses MEK and EA as diluents in a weight ratio of 5:5.

<Result>

The amount of TVOC (total organic volatile compounds) detected in the packaging materials prepared in Examples and Comparative Examples of Experiment 2 is shown in Table 3 (this was obtained by requesting the Korea Polymer Testing Laboratory), and the amount of residual solvent detected in the printing process It is shown in Table 4, and the roughness according to the ink application is shown in Table 5. In addition, the adhesive strength of the laminate (finished product) is shown in Table 6.

For the detection of residual solvent in Table 4, GC-Agilent 7890B was used as an analysis device, and 0.2 μl of THF was injected after collecting a 10x25 (cm) sample from each sample, and the sample was heated for 30 minutes, then injected and analyzed into the device. . The analysis method was YCC-GC Method.

Table 5 shows the results of measurement (3K magnification) by SEM (scanning electron microscope) after sectioning the sample.

The adhesive strength in Table 6 was measured using a universal testing machine, and the peel strength measurement speed was 300 m/min, and the peel angle was 180 degrees. The sealing conditions for heat bonding strength are 140 degrees/0.5 seconds.

division TVOC [μg/g] compared to comparative example
reduction rate comparative example 1,877 - Example 96 94.9%

division M-
OH Et-OH IPA MEK EA T/O PM PMA TOTAL comparative example
prepare
reduction rate comparative example 0 0 0.09 0.52 0.32 0 0.44 0 1.37 - Example 0 0.42 0 0 0 0 0 0 0.42 69.3%

As can be seen from Tables 3 and 4 above, it can be seen that the detection amount of TVOC (total organic volatile compounds) is reduced by 94.9% and the detection amount of residual solvent by 46.7% compared to the comparative example using general-purpose ink. On the contrary, it can be seen that it is eco-friendly.

division Coating amount Thickness average value [nm] compared to comparative example
reduction rate comparative example 966 - Example 661 31.6%

As shown above, it can be seen that the application amount is reduced to 31.6% by using the low-depth copper plate.

division Peeling Strength [gf] Thermal bonding strength [gf] comparative example Impossible to peel after aging 1799.82 Example Impossible to peel after aging 1760.51 Evaluation contents No significant difference in physical properties

On the other hand, the visual quality (color) comparison results confirmed with the naked eye are shown in FIGS. 5A (Comparative Example) and 5B (Example), respectively. As can be seen from FIG. 5 , the primary color part (blue, black) and spot color (ultramarine) colors were improved in the case of the example as a result of the appearance quality evaluation.

Furthermore, in the case of the embodiment of the present invention, it was possible to supplement the workability (production speed, reading, pressing, etc.) by improving the printing conditions.

Although non-limiting and exemplary embodiments of the present invention have been described above, the technical spirit of the present invention is not limited to the accompanying drawings or the above description. It will be apparent to those skilled in the art that various types of modifications are possible within the scope of the present invention without departing from the spirit of the present invention, and also, such modifications will fall within the scope of the claims of the present invention.

Claims (10)

Comprising a first step of obtaining a printed film by gravure printing the ink composition on the first paper, which is a film to be printed,
The ink composition comprises 10 to 30 wt% of a polyurethane resin composition, 4 to 10 wt% of a vinyl resin composed of polyvinyl butyral resin and polyvinyl acetal resin, 10 to 40 wt% of a pigment, 1 to 5 wt% of an additive, and ethanol ink consisting of the remainder of the solvent consisting of; and 50 to 150 parts by weight of ethanol as a diluting solvent for gravure printing with respect to 100 parts by weight of the ink.
The gravure printing is a packaging material manufacturing method using an ethanol-based ink composition, characterized in that using a low-depth copper plate having a depth of 12-16㎛ for 220-280 bows.
The method of claim 1,
When printing, the chamber temperature is maintained at 52 ~ 70 ℃, the fan speed is 80 ~ 90 m ³ /min, the method.
The method of claim 1,
A method of performing printing at a production speed of 240 to 260 M/min.
The method of claim 1,
The polyurethane resin composition comprises a polyurethane resin obtained by reacting a urethane prepolymer, an amine-based chain extender, and an aminosilane-based coupling agent.
The method of claim 1,
The method further comprises a second step of laminating the printed film with a secondary paper fabric using at least one of a solvent-free adhesive and an extruded resin after drying the print film.
6. The method of claim 5,
The solvent-free type adhesive is a two-component polyurethane-based adhesive comprising a main agent and a curing agent, the method.
6. The method of claim 5,
The method further comprises a third step of laminating with a tertiary paper fabric using at least one of a solvent-free type two-component adhesive and an extrusion resin after aging after completion of the secondary paper lamination.
delete The method of claim 1,
The packaging material is a packaging material consisting of a film laminate,
In the film laminate, one or more adhesive layers selected from a solvent-free adhesive layer and an extruded resin layer are formed on a printing film in which an ink layer is formed on a first paper feed, which is a film to be printed,
2nd grade paper is further laminated on the adhesive layer,
The method of claim 1, wherein the solvent-free adhesive layer and/or the extruded resin layer are free of organic solvent residues.
10. The method of claim 9,
In the film laminate, one or more adhesive layers selected from a solvent-free adhesive layer and an extruded resin layer are formed on the second-grade paper, and the third-grade paper is further laminated on the adhesive layer,
The method of claim 1, wherein the solvent-free adhesive layer and/or the extruded resin layer are free of organic solvent residues.

Images