KR101557873B1 - Aqueous Gravure Ink Composition For PVC Sheet And PVC Decorative Sheet Using The Same - Google Patents

Aqueous Gravure Ink Composition For PVC Sheet And PVC Decorative Sheet Using The Same Download PDF

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KR101557873B1
KR101557873B1 KR1020140034514A KR20140034514A KR101557873B1 KR 101557873 B1 KR101557873 B1 KR 101557873B1 KR 1020140034514 A KR1020140034514 A KR 1020140034514A KR 20140034514 A KR20140034514 A KR 20140034514A KR 101557873 B1 KR101557873 B1 KR 101557873B1
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ink composition
sheet
weight
thickener
pigment
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KR1020140034514A
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KR20150111088A (en
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정성돈
쇼우 치안 왕
강상수
전봉록
이승환
이은우
김현직
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케이에스씨비 주식회사
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Priority to KR1020140034514A priority Critical patent/KR101557873B1/en
Priority to PCT/KR2014/002723 priority patent/WO2015147359A1/en
Priority to CN201410331061.6A priority patent/CN104946009A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/102Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment

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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)

Abstract

The present invention discloses an aqueous gravure ink composition for PVA sheet which is gravure printed on a PVA sheet which is a print. The ink composition according to the present invention comprises: methanol; Water-dispersed polyurethane (PUD) containing an emulsifier for compatibility with methanol; Thickener; Silica; And pigments. And an aqueous gravure ink composition for a PVA sheet. According to the present invention, since the ink composition is dried quickly during gravure printing, the productivity of gravure printing is improved, and environmental pollution and human hazard due to the use of the organic solvent can be prevented because it is an aqueous ink composition.

Description

Technical Field [0001] The present invention relates to a water-based gravure aqueous ink composition for a pebblesheet and a pvc seed decolorate using the same,

The present invention relates to a gravure printing ink composition, that is, a gravure ink composition, and more particularly to an aqueous gravure ink composition for printing on PVC (Polyvinyl Chloride) sheet and a PVDECO sheet using the same.

Gravure printing is a printing process in which a cylinder of metal is rotated to cause ink to adhere to the film surface of the printing film. In the gravure printing, the color density is determined according to the depth of the main point, and the type of color depends on the number of cylinders used in the previous step. The printing medium (printing body) to be supplied for gravure printing is generally in the form of a roll or a film, i.e., a sheet, and the gravure printing is suitable for high-speed and high-volume printing with a quality of photographs.

The ink composition used in the gravure printing, that is, the gravure ink composition includes a pigment, a resin (ink binder), a solvent and an additive, and a hydrocarbon organic solvent such as toluene, xylene, cyclohexanone, etc. is mainly used as the solvent .

A decorative sheet (decorative sheet) for finishing the surface of floor, wall, furniture or the like is produced by the above-mentioned gravure printing, various sheets such as floor coverings, wall paper, furniture film, etc. More specifically, Is released into the atmosphere in the ink drying process to cause air pollution, and it causes many problems such as deterioration of the residential environment or work environment such as irritation to the eyes or skin, and a risk of fire.

In recent years, there has been a growing interest in environmental protection, work environments, and indoor living environments, and laws for prohibiting or restricting the use of organic solvents have been established in various countries. Thus, the use of organic solvents is limited.

Therefore, it is required to apply an aqueous gravure ink composition having little or no human stimulation to the gravure printing, but in the case of the aqueous ink composition, the drying speed is slow during the gravure printing process and the productivity of the gravure printing is greatly deteriorated. And the manufacturing cost of the ink composition itself is further increased as compared with the case of using an organic solvent. In particular, dryness which inhibits mass production of a gravure print becomes a problem.

Published Japanese Patent Application No. 10-2006-0002571, published on Jan. 7, 2005, Water-based ink and ink recording method Registered Patent Publication No. 10-0938199, Jan. 21, 2010 Registration Announcement, Gravure Printing Ink Composition and Manufacturing Method

It is an object of the present invention to provide an aqueous ink composition for gravure printing having a high drying speed, that is, a quick drying aqueous gravure ink composition and a PVD deco sheet using the same.

Another object of the present invention is to provide an aqueous gravure ink composition having no or low tackiness (tacky), and further having excellent adhesion force (coating adhesion force) of a coating film for protecting a printing surface and a PVDECO sheet using the same .

One embodiment of the present invention for solving the above-mentioned object is an aqueous gravure ink composition for PVA sheet which is gravure printed on a PVA sheet of paper to be printed, comprising: methanol; Water-dispersed polyurethane (PUD) containing an emulsifier for compatibility with methanol; Thickener; Silica; And an aqueous gravure ink composition for a PVA sheet comprising a pigment.

The amount of the methanol is 54 to 129 parts by weight, the amount of the thickener is 1.8 to 28.6 parts by weight, the amount of silica is 1.8 to 11.5 parts by weight, and the amount of the pigment is 1.8 to 22.9 parts by weight based on 100 parts by weight of the water-dispersed polyurethane. The pigment is an organic pigment but is not limited thereto.

The thickener includes polyvinyl pyrrolidone (PVP).

The aqueous gravure ink composition for a PVA sheet may further include at least one of an antifoaming agent, a leveling agent, and a dispersant. The additive is contained in an amount of 1.8 to 8.6 parts by weight based on 100 parts by weight of the water-dispersed polyurethane.

A more specific embodiment of the present invention is an aqueous gravure ink composition for PVA sheet which is gravure-printed on a PVA seed sheet as a print, comprising: 30 to 45% by weight, based on 100% by weight of the aqueous gravure ink composition for PVA sheet; 1 to 10% by weight of a thickener, 1 to 4% by weight of silica, and 1 to 8% by weight of a water-dispersible polyurethane containing 35 to 55% by weight of an emulsifier for compatibility with methanol, There is provided an aqueous gravure ink composition for a PVA sheet comprising an organic pigment.

The aqueous gravure ink composition for PVA sheet may further comprise 1 to 3% by weight of an additive based on 100% by weight of the aqueous gravure ink composition for PVA sheet. The thickener includes polyvinyl pyrrolidone (PVP). The particle size of the silica is 1 to 10 mu m.

Another embodiment of the present invention is a method of manufacturing a semiconductor device comprising: a PVDC sheet; And an ink layer which is gravure printed on the fibrous sheet by the above-mentioned aqueous gravure ink composition for a fibrous sheet to form a pattern.

The PVD deco sheet may further include a coating layer covering the ink layer and coating the surface of the PVD deco sheet. The coating layer may be a lamination coating or a clear coating.

According to the present invention, since the ink composition is dried quickly during gravure printing, the productivity of gravure printing is improved, and environmental pollution and human hazard due to the use of the organic solvent can be prevented because it is an aqueous ink composition.

According to the present invention, since the ink composition can be prevented from sticking to the second degree by the second degree transferred onto the substrate (the fibrous sheet) in the first degree printing process or due to the tacky property, The productivity can be improved and the print quality can be improved.

Further, according to the present invention, since stickiness (tackiness) of the printed surface is prevented, the phenomenon of adhesion of the interlayer boundary surface when the PVC decorative sheet is rolled up can be prevented, and furthermore, the lamination film (coating film) The surface quality of the PVD decor sheet can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing an example of a PVDECO sheet produced using an aqueous gravure ink composition for a PVDF sheet according to the present invention. FIG.
2 is a cross-sectional view schematically showing the decor sheet shown in Fig.
3 is a flow chart schematically showing a process for producing an aqueous emulsion-containing water-dispersed polyurethane.

Hereinafter, preferred embodiments of the aqueous gravure ink composition for PVS sheet according to the present invention will be described in detail.

The aqueous gravure ink composition for a photovoltaic sheet according to an embodiment of the present invention may include methanol, polyurethane dispersant (PUD), thickener, Silica, and pigments, and these components can be mixed with water.

The methanol functions as a solvent together with water, preferably distilled water, and the water-dispersed polyurethane (hereinafter referred to as 'PUD') functions as an ink binder to increase ink viscosity according to the specification of the product to be thickened, Silica is a component that minimizes or prevents the tacky of the printed surface after drying.

As well known, the above-mentioned pigment is a component for color or colorless color implementation, and includes an inorganic pigment and an organic pigment. In this embodiment, an example in which an organic pigment is applied as the pigment is described.

The types of the organic pigments vary and the organic pigments applied to the deck sheet are those having good light resistance and heat resistance. More specific examples of the organic pigments include CI Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 53: 1, 53: 2, 57: 1, (CI Pigment Yellow 1, 3, 83), CI Pigment Orange 16, CI Pigment Blue 15: 3, 15: 6, CI Pigment Green 7 ), Anthraquinone (Indanthrene Blue CI Pigment Blue 60), Thioindigo Magenta CI Pigment Vilot 38, Perinone Orange CI Pigment Orange 43, Perylene Maroon CI Pigment Red 179, (Quninacridone Red CI Pigment Violet 19), CI Pigment Red 177, and CI Pigment Green 36, and the organic pigment is not limited thereto.

Since the drying time of the ink composition in the gravure printing is a factor that significantly affects the productivity of the printing, fast drying (quick drying property) of the ink composition is directly related to productivity, and the aqueous gravure ink composition is quick drying, for example, However, it has been difficult to satisfy fast drying property due to the characteristics of the aqueous ink composition.

More specifically, in the case of a PVC sheet (PVC film), which is one type of the substrate to be used for gravure printing, the thickness is 0.6 mm to 2.0 mm, and the thickness generally used is 0.8 to 1.5 mm. When the thickness of the PVC sheet is 1.5 mm, the ink composition is dried at a temperature of 60 ° C or lower in the printing process, and when the thickness of the PVC sheet is 0.8 mm, the ink composition should be dried at a temperature of 45 ° C or lower in the printing process It is a situation. This is because when the ink composition is dried at a temperature higher than the above-mentioned temperature, the PVC sheet is stretched by thermal deformation and the surface smoothness is deteriorated.

As described above, since the printing speed in the gravure printing is directly related to productivity, it is necessary to print at a speed of at least 30 m / min. Although the printing speed is different for each gravure printer, (Dry Zone) for about 30 to 45 seconds.

The printing conditions, especially the drying conditions, which are required in the market, are 45 seconds or less, for example 30 to 45 seconds, at a temperature of 60 占 폚 or less when the thickness of the PVC sheet to be printed is 1.5 mm and the thickness of the PVC sheet is 0.8 mm The drying time is 45 seconds or less, for example, 30 to 45 seconds at a temperature of 45 ° C or less, and the shorter the drying time, the higher the productivity.

Typical gravure printing presses can print from 1 degree to 8 degrees. When the printing speed is faster than the ink drying time, the ink transferred to the printing body is not hardened at 2 degrees after the 1 degree printing. It may cause printing defects. Therefore, the drying property, that is, the quick drying property, is a factor that affects the productivity of printing and the quality of printing.

In the present embodiment, the amount of the methanol is 54 to 129 parts by weight, the amount of the thickener is 1.8 to 28.6 parts by weight, the amount of the silica is 1.8 to 11.5 parts by weight, and the amount of the pigment is 1.8 to 22.9 parts by weight based on 100 parts by weight of the PUD . The pigment is an organic pigment but is not limited thereto. The thickening agent is preferably polyvinyl pyrrolidone (PVP), but is not limited thereto.

The polyvinylpyrrolidone (hereinafter abbreviated as 'PVP') increases the viscosity of the ink proportionally as the content of the ink increases, and when the PVP is used as a thickener, when the decor sheet is coated after gravure printing, For example, the adhesion of transparent PVC film for lamination coating (coating adhesion) is also excellent.

If the content of methanol is less than the above range, the drying is slow and dryness can not be satisfied. If the content is more than the above-mentioned range, the content of the PUD relatively becomes relatively low and the adhesion of the material (substrate to be printed; PVC sheet) And the print quality deteriorates at the time of printing.

When the content of the thickener is less than the above range, it is difficult to secure the viscosity and the printing workability is poor. If the content of the thickener is higher than the above range, the above-mentioned range is preferable because the production cost is increased. However, the range is not necessarily limited thereto. The viscosity of the ink composition is preferably 50 cps or more, more preferably 80 cps to 300 cps, but printing is not impossible even if it is 50 cps or less.

Next, the silica has an effect of increasing the viscosity of the ink composition and an effect of preventing blocking (anti-stickiness effect).

If the content of the silica is less than the above range, tacky phenomenon may occur after drying. More specifically, after drying for 45 seconds at 60 ° C in a dry oven, the surface (printing surface) It is possible to confirm the stickiness, but it can be confirmed through experiments that the stickiness of the printed surface appears when the content of silicon is small. On the contrary, if the content of the silica is higher than the above-mentioned range, the adhesion of the lamination coating may be weakened, so that the above-mentioned range is preferable, but the range is not necessarily limited to the above-mentioned range.

And the particle size of the silica is preferably 1 탆 to 10 탆. When the particle size of the silica is less than 1 탆, it is difficult to secure the blocking effect. When the particle size of the silica is more than 10 탆, the roll mesh (Roll Mesh) ) Can be blocked.

Blocking generally means that the ink composition is sticky at a certain temperature or higher, and when the decor sheet is rolled after printing, the interlayer contact surface (interlayer boundary surface) of the decor sheet is stuck and does not fall off well. More specifically, if there is tackiness on the printed surface when the material (PVC sheet) goes beyond 2 degrees after printing at 1 degree, the material can stick to the second degree at 2 degrees of printing, Even when rolled in roll form, it is preferable to prevent stickiness on the printed surface since the interlayer contact surface of the decor sheet may adhere.

If the content of the pigment is less than the above range, the color strength (color staining) is lowered. If the content is higher than the above range, the manufacturing cost may increase and the viscosity may be increased to deteriorate the workability. It is not.

The ink composition may further include at least one of an antifoaming agent, a leveling agent, and a dispersant. More specifically, the amount of the additive is 1.8 to 8.6 parts by weight based on 100 parts by weight of the water-dispersed polyurethane, but is not limited thereto.

The PUD contains an emulsifier to improve compatibility with methanol. The emulsifier may increase the content of methanol in the ink composition, thereby shortening the drying time. When the two materials are mixed, it means that there is no change in the physical properties of the ink. When the compatibility is poor, the transparent ink binder becomes turbid, the viscosity of the ink is not stabilized, ), And particles such as pigment and silica may precipitate.

More specifically, the ink composition may include 30 to 45% by weight of methanol based on 100% by weight of the total composition, 35 to 55% by weight of an emulsifying agent for compatibility with methanol 1 to 10% by weight of thickener, 1 to 4% by weight of silica, and 1 to 8% by weight of organic pigment. The ink composition may further include 1 to 3% by weight of an additive, and the distilled water may be mixed with water, specifically, distilled water as a remainder together with the components so that the total weight may be 100. [ The thickener preferably includes polyvinyl pyrrolidone (PVP) as described above.

If the content of the water-dispersed polyurethane (including the emulsifier) is less than 35% by weight based on the total weight, the printing quality (ink adhesion) may deteriorate. If the content is more than 55% by weight, And it can be confirmed that an aqueous gravure ink composition excellent in both ink viscosity stability, dryness, tackiness, and coating adhesion can be produced when the content of each component is within the above range.

Referring to Figs. 1 and 2, the present invention relates to an ink-jet printer comprising a PVC sheet 11 as a print and an ink layer 12 which is gravure printed on the PVC sheet 11 by the ink composition described above to form a pattern Wherein the ink layer 12 is covered by a coating layer 13 so that the surface of the decor sheet 10 can be coated with the coating layer 13.

The coating layer 13 may be a lamination coating layer or a clear coating layer made of a urethane two-component type. Examples of the lamination coating layer include a transparent PVC film.

For reference, in a typical decor sheet, the thickness of the PVC sheet 11 is 0.6 mm to 2 mm. In general, a PVC sheet 11 having a thickness of 0.8 to 1.5 mm is used for gravure printing, and the thickness of the ink layer 12 is 3 m And the thickness of the lamination coating layer 13 is 0.8 mm to 3 mm. At this time, the adhesion force (coating adhesion force) of the coating layer 13 is required to be 1.8 kgf / in or more.

Hereinafter, one embodiment of the PUD containing the emulsifier will be described with reference to FIG.

The method of producing the PUD according to an embodiment of the present invention includes the steps of preparing a prepolymer for preparing a prepolymer, a neutralizing step of adding a neutralizing agent to the prepolymer, and adding an emulsifier to obtain a water-dispersed polyurethane (PUD) PUD < / RTI > In this embodiment, the PUD is performed in almost the same manner as the generally known PUD production process, but an example of using PUD containing an emulsifier, which is manufactured through an emulsifier input process after the neutralization step, as an ink binder is disclosed.

In producing a quick-drying ink composition as in this embodiment, PUD having good compatibility with methanol as a solvent is important, which is an important technical feature of the present invention. The prepolymer is prepared by reacting a polyol with dimethylol propionic acid (DMPA), and the DMPA provides an ionic group capable of water dispersion in water.

The above-mentioned polyols are mainly classified into polyester polyols, polyether polyols, and polycarbonate polyols.

Examples of the solvent used in the prepolymer reaction include NMP (N-methylpyrrolidinone) and acetone. In this embodiment, acetone is used as the reaction solvent.

A more specific example of the preparation process of the prepolymer is as follows.

9.74% by weight of a polyol PTMG (Polytetramethylene Glycol, Mw = 2000, Aldrich) and 12.74% by weight of Priplast 3192 (Mw = 2000, Polyester polyol, Croda) were added to a 1 L four-necked flask at room temperature and dimethylolpropionic acid 0.88% by weight of dimethylol propionic acid (DMPA, Pestorp) and 0.01% by weight of dimethylol propionic acid (DMPA, Pestorp) as catalyst were heated to 75 ° C. and stirred. Then, IPDI Isophorone diisocyanate, Asahi Kasei), and the reaction was allowed to proceed at 75 占 폚 for 90 minutes (min). The PTMG is a polyether polyol and the Priplast 3192 is a polyester polyol.

Then, after cooling the temperature of the above-mentioned reaction product to 50 ° C, 9.74% by weight of acetone was added to the reaction product at 50 ° C to obtain an easily water-dispersible viscosity (lower viscosity), and the prepolymer was obtained .

After the acetone is added to the reactant, a neutralization step of neutralizing the prepolymer with a neutralizing agent and finally a step of obtaining a PUD containing an emulsifier are performed.

More specifically, a carboxyl group of DMPA forming an anion is neutralized with a volatile amine such as triethylamine (TEA), and an ionic group (Ionic Group) is formed in the prepolymer. The PUD can be finally prepared through the prepolymer preparation step and the neutralization step, and if necessary, the molecular weight increase can be understood by adding a diamine or the like to the PUD.

In this embodiment, after the neutralization of the prepolymer with a neutralizing agent (TEA) to increase the methanol content in the ink, an emulsifier is added to the composition after the neutralization step so as to enhance compatibility with the alcohol, , And is characterized in that a quick-drying aqueous gravure ink composition is prepared using PUD containing the emulsifier (referred to as 'PUD 1' for distinguishing from general PUD not containing emulsifier).

In the production example of the PUD disclosed in this embodiment, 0.5 wt% of triethylamine (TEA, Junsei Chemical Co.) was used as the neutralizing agent. In the preparation example, the neutralization step includes the step of adding the neutralizer, specifically triethylamine, to the prepolymer and stirring for 30 minutes.

An embodiment of the PUD or PUD 1 in which the compatibility with methanol is improved by introducing an emulsifier into the composition after the above-described neutralization process is obtained.

Examples of the emulsifier include Alkyl phosphate, Ammonium (POE) Alkyl Aryl Ether Sulfate, Sulfosuccinate, and Sodium Dioctyl Sulfosuccinate. In this preparation example, 0.97 wt% of sodium dioctyl sulfosuccinate (DO113L, Was used as an emulsifier.

More specifically, as described above, water (distilled water or water) is added to the composition (secondary composition) into which the emulsifier is added to the composition (primary composition) obtained by adding the neutralizer to the prepolymer and stirring, (At least 800 RPM) of the tertiary composition for water dispersion, and then volatilizing (evaporating) the acetone by distillation under reduced pressure to remove the emulsifier (PUD 1, 35% solids PUD) can be obtained.

In this production example, 58.43% by weight of ion-exchanged water was used as the water. Of course, the PUD used in the ink composition according to the embodiment of the present invention, that is, the PUD containing the emulsifier is not limited to the result of the above-mentioned production example, and the production method is not limited to the above- PUD containing an emulsifying agent for enhancing the properties is possible as a constituent element of the present invention.

For comparison with the ink composition using PUD 1, an example of a general water-dispersed polyurethane (hereinafter referred to as 'PUD 2') containing no emulsifier was prepared.

The preparation method of the PUD 2 and the content of the constituent components are generally known in the art. For example, in order to manufacture an embodiment of the PUD 2, an entire process for manufacturing an embodiment of the PUD 1 described above The content of the ion-exchanged water was adjusted as shown in Table 1 below in order to adjust the total weight of 100. The components and contents of one embodiment of the PUD1 and one embodiment of the PUD 2 were as follows: Table 1 shows the results.

ingredient PUD 1 (% by weight) PUD 2 (% by weight) Priplast 3192 (polio) 12.74 12.74 PTMG (polyion) 9.74 9.74 DMPA (ionic compound) 0.88 0.88 DBTDL (Catalyst) 0.01 0.01 IPDI 7.49 7.49 Acetone 9.74 9.74 TEA (trimethylamine) 0.5 0.5 DO113L (emulsifier) 0.97 Ion-exchange water 57.93 58.9 TOTAL 100 100

Hereinafter, specific examples of the aqueous gravure ink composition according to the present invention will be described, and the following specific examples are merely illustrative of the present invention, and the present invention is not limited to the following examples.

Preparation of Examples and Comparative Examples

Examples of the aqueous gravure ink composition and comparative examples were prepared by mixing the ingredients listed in Table 2 at room temperature in the following Table 2 with the content of [Table 2], and this aqueous gravure ink composition was applied to a thickness of 0.8 mm ) PVC sheet by gravure printing.

ingredient
Example Comparative Example
1-1 1-2 1-3 2-1 2-2 2-3 2-4 2-5 2-6 PUD 1 45 45 45 45 45 45 PUD 2 45 45 45 Methanol 10 35 44.5 10 35 44.5 ethanol 10 35 44.5 Thickener
(PVP K-90)
2 2 2 2 2 2 2 2 2
Silica
(TS-100)
2 2 2 2 2 2 2 2 2
Pigment
(Blue BG)
5 5 5 5 5 5 5 5 5
Defoamer
(Foamex 810)
0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Leveling agent
(BYK-346)
One One One One One One One One One
Distilled water 34.5 9.5 0 34.5 9.5 0 34.5 9.5 0 TOTAL 100 100 100 100 100 100 100 100 100

Examples 1-1 to 1-3 are ink compositions in which PUD (PUD 1) containing an emulsifier is applied as an ink binder and methanol is applied as a solvent. In Comparative Examples 2-1 to 2-3, PUD 2 is applied as a binder and methanol is applied as a solvent. Examples 2-4 to 2-6 of the comparative examples are ink compositions to which PUD 1 is applied as an ink binder and ethanol is applied as a solvent.

In the above Examples and Comparative Examples, the thickener was PVP K-90 from BASF (Germany) as polyvinyl pyrrolidone, and the silica had an average particle size of about 9 μm, ), And the pigment is Blue Pigment 15: 3, a product of CLARIANT (Germany). Next, the antifoaming agent is Foamex 810 of TEGO Corporation as a silicone system, and BYK-346 of BYK Corporation as a silicone leveling agent.

Table 3 below shows the performance (initial viscosity, viscosity stability, dryness, tackiness, lamination coating adhesion) of the examples and comparative examples in Table 2.

Performance
division
Example Comparative Example
1-1 1-2 1-3 2-1 2-2 2-3 2-4 2-5 2-6 Initial viscosity 240 cps 90cps 65cps 320cps 110cps 100 cps 280cps 120 cps 90cps Ink viscosity
stability
stability stability stability Viscosity increase Viscosity increase Viscosity increase stability stability stability
Drying 1 Non-drying dry dry Non-drying dry dry Non-drying Non-drying Non-drying Drying 2 Non-drying dry dry Non-drying Non-drying dry Taiki
(Tacky)
none none none none none none none none none
coating
Adhesion
1.8kgf / in or more

According to Table 3, the examples (1-1 to 1-3) of the ink composition containing PUD 1 and methanol maintain the ink viscosity stably and are stable at 45 ° C in a dry oven at a temperature of 60 ° C. (Adhesion of the printed surface to the transparent PVC film when the laminate is coated with a transparent PVC film after the gravure printing on the PVC sheet) is not less than 1.8 kgf / in It was excellent. The ink viscosity stability is the same as that in the following table as a value obtained by confirming the change in ink viscosity after storing the ink composition at 50 캜 for 7 days.

However, in the case of Example 1-1 in which the content of methanol is 10% by weight, the ink on the printing surface is observed in the test of dryness (120mesh gravure printing, ink drying after each drying condition (temperature X hours) (Unfiltered, not completely dry). Therefore, in the present invention, methanol is contained in an amount of 54 to 128 parts by weight based on 100 parts by weight of the PUD containing the emulsifier, and more specifically, 30 to 45% by weight in the total ink composition.

For reference, drying 1 of [Table 3] was tested after drying for 30 seconds at a temperature of 45 ° C in a dry oven and drying 2 for 30 seconds at a drying temperature of 60 ° C in a dry oven The conditions of the dryness test are the same in the following description. The initial viscosity was determined with a Brookfield viscometer.

On the other hand, according to the embodiments of the ink composition using PUD 2, it was confirmed that the ink viscosity was not stably maintained, and the ink viscosity increased with time, and the ink viscosity was not stable. More specifically, in the case of Comparative Example 2-1, the ink viscosity increased from 320 cps to 480 cps. In Comparative Example 2-2, the ink viscosity increased from 110 cps to 8,000 cps. In the case of Comparative Example 2-3 The viscosity of the ink increased from 100 cps to 15,000 cps, and the viscosity of Comparative Examples 2-2 and 2-3 was relatively higher than that of Comparative Example 2-1.

In Comparative Examples (2-4 to 2-6) of the ink composition containing PUD 1 and ethanol, ink viscosity was stably maintained, and after drying for 45 seconds at a temperature of 60 ° C in a dry oven, No stickiness was observed and coating adhesion was excellent at over 1.8kgf / in, but dryness was found to be problematic.

In conclusion, it can be confirmed from experiments that excellent viscosity stability, fast drying properties, tackiness and coating adhesion are satisfied when PUD 1 and methanol are contained and the content of each component is within the range shown in the present invention .

Next, an aqueous gravure ink composition was prepared by varying the kind and content of the thickener as shown in [Table 4] below, and the aqueous gravure ink composition was applied to a PVC sheet having a thickness of 0.8 mm (0.8 T) A PVC decorative sheet was produced by gravure printing.

ingredient
Example Comparative Example
1-4 1-5 1-6 2-7 2-8 2-9 2-10 2-11 2-12 PUD 1 45 45 45 45 45 45 45 45 45 Methanol 35 35 35 35 35 35 35 35 35 PVP K-90 2 4 6 SN-thickener 624N 2 4 6 Acrysol ASE-60 2 4 6 Silica
(TS-100)
2 2 2 2 2 2 2 2 2
Pigment
(Blue BG)
5 5 5 5 2 5 5 5 5
Defoamer
(Foamex 810)
0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Leveling agent
(BYK-346)
One One One One One One One One One
Distilled water 9.5 7.5 5.5 9.5 7.5 5.5 9.5 7.5 5.5 TOTAL 100 100 100 100 100 100 100 100 100

Table 5 below shows the results of testing the performance of the examples and comparative examples of Table 4. [

Performance
division
Example Comparative Example
1-4 1-5 1-6 2-7 2-8 2-9 2-10 2-11 2-12 Ink viscosity
stability
stability stability stability stability stability stability stability stability stability
Drying 1 dry dry dry dry dry dry dry dry dry Taiki
(Tacky)
none none none none none none none none none
coating
Adhesion
1.8kgf / in or more
1.6kgf / in 1.8kgf / in or more 1.5kgf / in

According to Table 5, Examples (1-4 to 1-6) of the ink composition containing PVP (Polyvinyl Pyrrolidone) as a thickener have excellent ink viscosity stability and dryness, and tackiness (printed surface stickiness) And it was confirmed that the coating adhesion was also excellent.

According to the ink composition examples (Comparative Examples 2-7 to 2-12) using SN-Thickener 624N (SAN NOPCO) and Acrysol ASE-60 (DOW) as thickening agents, ink viscosity stability and dryness And no tackiness was observed. However, it was confirmed that the coating adhesion was slightly lowered as the content of the thickener was increased (Comparative Examples 2-9 and 2-12).

In Table 4 and Table 5, an ink composition containing PVP as a thickening agent was used as an example and an ink composition containing other types of thickener was used as a comparative example. However, in order to compare the performance of the ink composition based on PVP And it is not excluded that other thickening agents other than PVP satisfy the ink viscosity stability, dryness and tackiness, and thus can be applied to the present invention. However, since PVP has excellent adhesion to coating, it can be seen that PVP is more excellent as a thickener for the present invention.

Next, in order to test the effect of the silica, an aqueous gravure ink composition was prepared by varying the content of silica as shown in Table 6 below, and the aqueous gravure ink composition was applied to a material (printable) having a thickness of 0.8 mm (0.8 T) A PVC sheet was produced by gravure printing on a PVC sheet.

ingredient Example PUD 1 1-7 1-8 1-9 1-10 Methanol 45 45 45 45 PVP K-90 35 35 35 35 Thickener
(PVP K-90)
2 2 2 2
Silica
(TS-100)
0.5 2 4 6
Pigment
(Blue BG)
5 5 5 5
Defoamer
(Foamex 810)
0.5 0.5 0.5 0.5
Leveling agent
(BYK-346)
One One One One
Distilled water 11 9.5 7.5 5.5 TOTAL 100 100 100 100

Table 7 below shows data of the performance of the embodiments of Examples 6 to 10 (Examples 1-7 to 1-10).

Performance classification
Example
1-7 1-8 1-9 1-10 Ink viscosity
stability
stability stability stability stability
Drying 1 dry dry dry dry Taiki
(Tacky)
has exist none none none
Coating adhesion 1.8kgf / in or more 1.7kgf / in

According to Table 7, the examples of the ink composition containing silica showed excellent ink viscosity stability and dryness, and it was found that the content of silica in the ink composition of Example 1- 7 showed a tackiness (printed surface tackiness) and the coating adhesion was slightly lower in Example 1-10, which exceeded the content ranges shown in the present invention, indicating that the content of silica affects tachykinin And it can be confirmed that it can affect the coating adhesion.

However, even if the ink composition contains silica, it can be confirmed that the tackiness is improved, and since the ink viscosity stability and dryness are both satisfied regardless of the content of silica, the content of silica is smaller than the content range of the present invention Or higher is not excluded from the applicability of the present invention, and it can be confirmed through experimentation that the tackiness and the coating adhesion force are satisfied in addition to the ink viscosity stability and the drying property when the content of silica is within the range of the present invention.

As described above, according to the present invention, the present invention can be embodied in other specific forms without departing from the spirit and scope of the present invention. It is obvious to them.

Therefore, the above-described embodiments are to be considered as illustrative rather than restrictive, and the present invention is not limited to the above description, but may be modified within the scope of the appended claims and equivalents thereof.

10: PVC Deco Sheet 11: PVC sheet
12: Ink layer 13: Coating layer

Claims (12)

1. An aqueous gravure ink composition for PVA sheet which is gravure printed on a printed sheet of PVA sheet, comprising:
Methanol; Water-dispersed polyurethane (PUD) containing an emulsifier for compatibility with methanol; Thickener; Silica; And a pigment (Pigment).
The method according to claim 1,
Wherein 54 to 129 parts by weight of the methanol, 1.8 to 28.6 parts by weight of the thickener, 1.8 to 11.5 parts by weight of the silica, and 1.8 to 22.9 parts by weight of the pigment are added to 100 parts by weight of the water-dispersed polyurethane. Aqueous gravure ink composition for PVA sheet.
3. The method of claim 2,
Wherein the pigment is an organic pigment. ≪ RTI ID = 0.0 > 21. < / RTI >
The method according to claim 1,
Wherein the thickener comprises polyvinyl pyrrolidone (PVP). 2. The aqueous gravure ink composition according to claim 1, wherein the thickener is polyvinyl pyrrolidone (PVP).
5. The method according to any one of claims 1 to 4,
And an additive for at least one of an antifoaming agent, a leveling agent and a dispersing agent.
6. The method of claim 5,
Wherein the additive is 1.8 to 8.6 parts by weight based on 100 parts by weight of the water-dispersed polyurethane.
1. An aqueous gravure ink composition for PVA sheet which is gravure printed on a printed sheet of PVA sheet, comprising:
Based on 100% by weight of the aqueous gravure ink composition for PVS sheet, 30 to 45% by weight of methanol, 35 to 55% by weight of water-dispersed polyurethane containing an emulsifier for compatibility with methanol, By weight of a thickener, 1 to 4% by weight of silica, and 1 to 8% by weight of an organic pigment.
8. The method of claim 7,
Wherein the composition further comprises 1 to 3% by weight of an additive based on 100% by weight of the aqueous gravure ink composition for a PVA sheet.
8. The method of claim 7,
Wherein the thickener comprises polyvinyl pyrrolidone (PVP). 2. The aqueous gravure ink composition according to claim 1, wherein the thickener is polyvinyl pyrrolidone (PVP).
10. The method according to any one of claims 7 to 9,
Wherein the silica has a particle size of 1 to 10 占 퐉.
Pvc seats;
A PVDEC sheet comprising an ink layer which is gravure printed on the PVDF sheet by the aqueous gravure ink composition for a PVDF sheet according to claim 1 to form a pattern.
12. The method of claim 11,
Further comprising a coating layer covering the ink layer and coating the surface of the PVD deco sheet.
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