JPH091049A - Method for forming patterned film - Google Patents

Abstract

PURPOSE: To form a patterned film of an excellent design in a reduced number of processes, good operability, accuracy, and reproducibility by discharging a colored ink from the nozzle of an ink-jet printer on the surface of an article which is coated with a lower layer colored film in advance and applying the ink in the shape of a pattern. CONSTITUTION: When a substrate (a) coated with a lower layer colored film is carried on a conveyer 1, the front end part is detected by a sensor 12, and a detection signal is sent to a control part 11. Besides, pulses are sent from an encoder 15 to the control part 11, the control part starts counting the pulses by signals from the sensor 12, when the value reaches a set value, reads a pattern from a storage part 10 corresponding to the number of pulses received, sends control signals based on the pattern to a valve controller 8 in sequence, and controls the operation of valves 9 individually by the signals. As a result, an ink 5 which is supplied into a printer head 2 by a prescribed pressure is discharged from a nozzle 3 through the valves 9, and the pattern based on pattern data is depicted on the surface of the substrate (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coating finishing method, and more particularly to a novel method of forming a patterned coating film capable of forming a patterned coating film having excellent design.

[0002]

2. Description of the Related Art Conventionally, decorations such as letters and patterns are provided on the painted surface of automobiles, two-wheeled vehicles, electric appliances, building interior materials and exterior materials, etc., where cosmetic appearance is important, and the design is excellent. In order to form a pattern coating film, characters and patterns are printed on a resin film in advance by heat transfer to the surface after painting, transfer using the sublimation property of the colorant, or different refractive index. It is known that three or more layers of color clear layers are superposed by spraying or the like to give a feeling of depth, or a method of masking and coating several layers to give a two-tone color.

[0003]

However, in each of these methods, there are many steps, and it is difficult to form a desired pattern with good workability, accuracy and reproducibility. An object of the present invention is to provide a method for forming a patterned coating film which can form a patterned coating film excellent in designability with a small number of steps, with good workability, accuracy and reproducibility.

[0004]

Means for Solving the Problems As a result of earnest studies to achieve the above object, the inventors of the present invention have applied a colored ink in a pattern using an ink jet printer, and if desired, further apply a clear coating to the entire surface. It has been found that the above-mentioned objects can be achieved by coating, and the present invention has been completed.

That is, in the method for forming a patterned coating film of the present invention, a colored ink is ejected from a nozzle of an ink jet printer onto a surface of an object having a lower colored coating film applied in advance to apply it in a pattern. A feature is that a clear coating is further applied to the entire surface of the patterned coating film if desired.

Further, in a preferred embodiment of the present invention, the colored ink is a transparent colored ink or an opaque colored ink, or the article to be coated is a metal plate. Further, the method for forming a pattern coating film of the present invention, which is being conveyed by a conveyor, stores in the computer the data of the position to which the colored ink on the surface of the article to be coated on which the lower layer colored coating film is applied in advance, The invention is characterized in that a valve control device is driven by a control signal of the computer to control ink ejection from nozzles of an inkjet printer, and preferably the viscosity of the ink is 2 to 14 mPa · s (20 ° C.). And

The method for forming the patterned coating film of the present invention will be described in detail below. In the method for forming a patterned coating film of the present invention, a metal plate, an inorganic plate, or the like, on which a lower layer colored coating film is previously applied, is used as an object to be coated, particularly a metal plate. As a paint for forming this lower layer colored coating film,
Any of various conventionally known coloring paints such as baking type, normal drying type, active energy ray-curing type organic solvent type, water type and solventless type can be used.

The colored ink used in the present invention may be either a transparent colored ink or an opaque colored ink.
The transparent coloring ink is mainly composed of a resin, a kind and amount of a coloring agent (mainly a dye) and a solvent which do not impair the transparency, and the opaque coloring ink is mainly composed of a resin, a coloring agent and a solvent. The colored inks preferably have a viscosity of 2 to 14 mPa · s (20 ° C.).

As the above resin that constitutes the colored ink,
There is no particular limitation as long as it has good adhesion to the lower colored coating film, and conventionally known ink resins can be used. Specifically, alkyd resin system (polyester resin system), alkyd melamine resin system, acrylic resin system, acrylic melamine resin system, acrylic epoxy resin system, vinyl resin system, acrylic silicone resin system, fluororesin system, silicone resin system, Representative examples include various resins such as chlorinated resin.

Examples of the above-mentioned colorant constituting the colored ink include various colorants such as extender pigments containing a matting agent, color pigments, dyes, pearl pigments, and aluminum flakes.
Further, as the above-mentioned solvent constituting the colored ink, the specific evaporation rate (by a weight method using 100% of positive butyl acetate) is preferably 50 to 380, more preferably 80 to 200.
Use the ones in the range. Solvents having a specific evaporation rate within the above range include aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as ethyl alcohol, isopropyl alcohol and isobutyl alcohol;
Typical examples include ester solvents such as propyl acetate, butyl acetate, secondary butyl acetate and isobutyl acetate; and aliphatic hydrocarbon solvents such as petroleum benzine and rubber volatile oil. In addition, in the present invention, a good result is obtained by mainly using a solvent having a specific evaporation rate within the above range and using a solvent having a specific evaporation rate outside the above range in a range of 20% by weight or less based on the total solvent. Is obtained.

The transparent coloring ink used in the present invention is mainly composed of the above-described resin, the kind and the amount of the coloring agent and the solvent which do not impair the transparency, and the opaque coloring ink is the above-mentioned resin and coloring. It is composed of an agent and a solvent as main components and, if necessary, various additives such as an electric conductivity adjusting agent and a surfactant. The proportion of each component in these cases is suitably 4 to 50% by weight of resin, 1 to 30% by weight of colorant, and 49 to 95% by weight of solvent. It is preferable that this colored ink is obtained by mixing and stirring the above-mentioned components and then filtering and purifying with a filter having a pore size of about 1/10 or less of the diameter of the nozzle of the inkjet printer used in the method of the present invention. Used.

The colored ink used in the present invention preferably has a viscosity of 2 to 14 mPa · s (20
C.), more preferably 4 to 10 mPa · s (20 ° C.). When the viscosity of the colored ink is out of the above range, the ink ejected from the nozzle is unlikely to be a normal dot-shaped ink droplet, which is not preferable. As other properties of the ink, those having a surface tension of 20 to 60 dynes / cm, a specific resistance of 200 to 300 Ωcm, and a specific gravity of 0.7 to 3 are preferable.

The clear paint used in the present invention is not particularly limited as long as it has good adhesion to the lower colored coating film and the ink coating film, and can be appropriately selected from conventionally known clear coating materials. . Specifically, bonding of alkyd melamine resin type, polyester melamine resin type, acrylic urethane resin type, acrylic epoxy resin type, acrylic melamine resin type, acrylic silicone resin type, acrylic fluororesin type, fluororesin type, silicone resin type, etc. Conventionally known clear coatings (including color clear coatings) such as organic solvent type and water-based type using agents can be used, and further, hydroxyl functional acrylic resin or methylated melamine-formaldehyde in the monomer composition. It is of course possible to use a resin obtained by blending an amino-based cross-linking agent such as a resin, or a paint having an aminoalkyd resin as a main component.

The pattern in the present invention includes spots, stripes, letters, various patterns such as floral patterns, and the like. As the inkjet printer used in the present invention, a conventionally known inkjet printer can be used, and as a control system thereof, for example, an on-demand system, a charge control system, a system in which ink is ejected by a thermal head is typical. It is mentioned as a thing.

Next, one embodiment of the method for forming a coating film of the present invention using an on-demand type ink jet printer by opening and closing a solenoid valve will be specifically described with reference to FIGS. 1 and 2. In the figure, reference numeral 1 is a conveyer for carrying a substrate a having a lower colored coating film on its surface and carrying it forward. Above the conveyer 1, a printer head 2 of an inkjet printer (not shown in its entirety) is provided. The printer head 2 has a diameter of 0.1 across the width of the conveyor 1.
A plurality of nozzles 3 having a size of 0.4 mm are provided in parallel in a downward direction at a pitch of 1 to 5 mm. It should be noted that the printer head 2 may be adapted to correspond to the width of the conveyor 1, but a plurality of printer heads 2 may be arranged side by side according to the size of the substrate (that is, the width of the conveyor). Of course, it is also good. The printer head 2 is connected to a pump 6 for feeding the ink 5 in the ink tank 4, and is also connected to the ink tank 4 via a relief valve 7.

Reference numeral 9 is a valve that opens and closes each nozzle 3 provided below the printer head 2, and the valve 9 is individually controlled by the valve controller 8. Reference numeral 10 is a storage unit for pattern data in which a pattern to be printed and a pattern pattern corresponding to the pattern are recorded, and reference numeral 11 is a control unit for issuing a control signal to the valve control device 8 based on the pattern data input from the storage unit 10. (Computer), and reference numeral 12 is a photoelectric tube type sensor including a light projector 13 and a light receiver 14 provided on both sides of the substrate transport path on the conveyor 1, and the substrate a
Is detected and the detection signal is transmitted to the control unit 11. Reference numeral 15 is an encoder connected to the drive roll 16 of the conveyor 1, and is, for example, 3/2000.
A pulse is transmitted to the control unit 11 for each minimum rotation angle of 60 degrees. The above description is for the printer head 2
However, it is also possible to adopt a method in which the printer head 2 is controlled and operated in the width direction or the traveling direction of the substrate a.

Next, an example of the method of the present invention for patterning the surface of a substrate using such an ink jet printer including a control system will be described. When the substrate a is conveyed on the conveyor 1 at a speed of 1 to 60 m / min, preferably 3 to 45 m / min, the sensor 12 detects that the front end of the substrate a has reached a predetermined position of the conveyor 1. Then, the signal is transmitted to the control unit 11. On the other hand, with the operation of the conveyor 1, a pulse is transmitted from the encoder 15 to the control unit 11. The control unit 11 starts counting the pulses based on the signal from the sensor 12, and when the number of pulses reaches a preset value, after that, the pattern pattern is changed according to the number of pulses received in a predetermined range (time). Pattern data is read from the storage unit 10, and control signals (command signals) based on the pattern data are sequentially transmitted to the valve control device 8, and the valve control device 8 individually controls opening and closing of the valves 9 by this signal. As a result, the ink 5 sent into the printer head 2 at a pressure of 0.1 to 0.5 Kg / cm ² passes through the opening of the valve 9 and is ejected from the nozzle 3 to form a pattern based on the pattern data. It is drawn on the surface of the substrate a. In addition, between the surface of the substrate a and the tip of the nozzle 3,
Since they have a distance of about 0.5-4 cm, they do not touch each other, so even if the substrate surface has irregularities,
You can draw patterns without any problems.

When it is desired to form a multicolored pattern,
The printer heads 2 are arranged in a plurality of stages in the conveying direction of the conveyer 1, inks of different colors are supplied to the respective printer heads 2 by the above-mentioned supply method, and those inks are ejected in the same manner as described above. This allows
It is possible to draw a multicolored pattern on the surface of the substrate a. In the method of the present invention, the surface of the substrate is thus patterned by the ink jet printer and then dried.

In the present invention, it is preferable to further apply a clear paint in order to further improve the stain resistance and abrasion resistance of the obtained substrate surface. This clear paint can be applied by means such as ordinary spraying, electrostatic atomization, roll coater and flow coater.

[0020]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. Examples 1 to 7 and Comparative Examples 1 to 3 Using the objects to be coated described in Tables 1 to 4, the lower layer colored coating, patterning and clear coating were performed using the coating materials, inks and coating conditions described in Tables 1 to 4. It was carried out using printing conditions and drying conditions. The articles to be coated, the coating composition, and the ink composition used in Examples and Comparative Examples were as follows. In addition, "part" and "%" in an Example and a comparative example are shown on the basis of weight.

<Substrate 1> Zinc phosphate chemical conversion treated steel plate (thickness 0.8 mm). <Coating object 2> Zinc phosphate chemical conversion treated steel plate (thickness 0.8 m
m), a coated steel sheet obtained by coating an epoxy-based cationic electrodeposition coating so as to have a film thickness of 20 μm on the basis of a cured coating film, and baking and curing.

<Substrate 3> 80 g / m of a solution of hexamethylene diisocyanate burette (heating residue 15%) in butyl acetate / xylene = 1/1 was placed on a gypsum slag perlite plate containing pulp and having a thickness of 12 mm. ^A sealer-treated inorganic plate which is spray coated in an amount of ² (wet) and dried at 100 ° C for 5 minutes.

<Intermediate coating paint B> Titanium oxide 24.0 parts, iron oxide yellow 0.03 parts, carbon black 0.01 parts, phthalocyanine blue 0.06 parts, Almatex 894-2
(Acrylic resin, acid value 2.5-4.5, heating residue 50%,
Mitsui Toatsu Chemical Co., Ltd. product name) 46 copies, Uban 20SE-
60 (n-butylated melamine resin, acid value 1>, heating residue 60%, trade name manufactured by Mitsui Toatsu Chemicals, Inc.) 12.5 parts, n-butanol 5 parts, xylene 3 parts, butyl acetate 6 parts, mono A composition comprising 3 parts of butyl glycol ether and 0.5 part of an additive.

<Intermediate coating paint b> Titanium oxide 3.4 parts, pyrrole red pigment 2.3 parts, perylene red pigment 3.2 parts, Almatex 894-2 53 parts, Uban 20SE-6
0 15.0 parts, n-butanol 3 parts, toluene 9.6
Part, xylene 5.0 parts, butyl acetate 2.0 parts, monobutyl glycol ether 3 parts, and additive 0.5 parts.

<Intermediate coating paint C> Yupika coat AC3402
V (acrylic resin, acid value 13 ± 3, heating residue 50 ± 1.
5%, Japan Yupica product name) 30 parts, titanium oxide 20
Parts, iron oxide yellow 0.1 parts, red iron oxide 0.05 parts, carbon black 0.7 parts, precipitating barium sulfate 16 parts, talc 5 parts, butyl acetate 10 parts, toluene 15 parts, Coronate HX (yellow-free) Modified polyisocyanate resin, NCO content 2
1.1 ± 0.5%, trade name of Nippon Polyurethane Company) 3.5
Composition consisting of parts.

<Intermediate coating paint D> Yupika coat AC3402
V30 parts, titanium oxide 40 parts, iron oxide yellow 0.4 parts, iron oxide red 0.01 parts, carbon black 0.1 parts, butyl acetate 11 parts, toluene 15 parts, Coronate HX 3.5 parts.

<Topcoat i> 18.3 parts of titanium oxide, 0.4 parts of iron oxide, 5.0 parts of kaolin, 2 parts of silicic acid anhydride, Phtalkid M132-60 (alkyd resin, acid value 7>, heating residue 60) ± 1%, Hitachi Chemical Co., Ltd. product name) 50 parts, Uban 20SE-60 13.5 parts, n-butanol 4.
A composition consisting of 0 part, xylene 6.3 parts, and additive 0.5 parts.

<Topcoat ii> Titanium oxide 20 parts, iron oxide yellow 0.5 parts, carbon black 0.05 parts, Hitaroid 3
020 (acrylic resin for urethane, hydroxyl value 25, heating residue 50 ± 1%, trade name manufactured by Hitachi Chemical Co., Ltd.) 63.0
Parts, 5 parts of Coronate HX, 5.0 parts of butyl acetate, 5.5 parts of xylene, and 0.95 parts of additive.

<Ink 1> Acridic 56-112
8 (acrylic resin, acid value 1>, heating residue 50.0 ± 1
%, Trade name of Dainippon Ink and Chemicals, Inc.) 14.5 parts, iron oxide yellow 2.2 parts, carbon black 0.34 parts, toluene 16.5 parts, rubber volatile oil 66.5 parts viscosity 5. 2m
A composition of Pa · s (20 ° C).

<Ink 2> Acridic 56-112
8 21.0 parts, titanium oxide 8.0 parts, pork cutlet 0.5
Part, rust 0.2 part, carbon black 0.3 part, toluene 23.5 parts, silicon oxide 0.1 part, additive 0.4 parts, petroleum benzene 46.0 parts, viscosity 4.7 mPa · s ( 20
° C) composition.

<Ink 3> 0.63 parts of aluminum paste,
Phthalocyanine blue 0.74 part, dioxane diviolet 0.71 part, carbon black 0.01 part, Almatex 894-2 23.6 parts, Uban 20SE-60 6.0 parts, butyl acetate 4.0 parts, n- Viscosity 4.6 mP consisting of 20.0 parts butanol, 3.0 parts glycol monobutyl ether, 30.0 parts toluene, 10.7 parts xylene, 0.61 parts additive.
Composition of a * s (20 degreeC).

<Ink 4> 2.38 parts of colored pearl, 1.36 parts of perylene-based aluminum, Almatex 894-2
20.5 parts, Uban 20SE-60 5.2 parts, butyl acetate 4.0 parts, n-butanol 20.0 parts, glycol monobutyl ether 4.0 parts, toluene 30.0 parts, xylene 11.6 parts, addition Viscosity 4.6mP consisting of 0.96 parts
Composition of a * s (20 degreeC).

<Ink 5> Titanium oxide 9.0 parts, iron oxide yellow 0.4 parts, iron oxide rust 0.2 parts, carbon black 0.1.
3 parts, Phtalkid 132-60 16.0 parts, Uban 20SE-60 5.3 parts, Butyl acetate 4.0 parts, n-Butanol 20.0
Part, 3.0 parts of glycol monobutyl ether, 30.0 parts of toluene, 11.0 parts of xylene, and 0.8 parts of an additive and having a viscosity of 4.1 mPa · s (20 ° C.).

<Ink 6> 15.5 parts of acrylic urethane oligomer (acryl urethane oligomer having an average molecular weight of 500 obtained by addition reaction of 1 mol of isophorone diisocyanate and 2 mol of 2-hydroxyethyl acrylate by a conventional method), 2-ethylhexyl Methacrylate 2
0.6 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.8 parts, Solvent Yellow 88
A composition having a viscosity of 4.3 mPa · s (20 ° C.) consisting of 2.6 parts.

<Ink 7> Acronal YJ3032
(Acrylic resin emulsion, solid content 49 ± 2%, trade name manufactured by Mitsubishi Chemical BASF) 5 parts, EM color yellow (water-dispersed pigment, yellowish brown, particle size 60 μm or less, trade name manufactured by Toyo Ink Co., Ltd.) 6.7 parts, EM color black (carbon black easy dispersion pigment, black, particle size 50 μm or less, trade name of Toyo Ink Co., Ltd.) 1.2 parts, defoaming agent 0.1 part, water 67 parts viscosity 4.7 mPa · s (20 ° C. ) Composition.

<Ink 8> Acridic 56-112
8 28.0 parts, iron oxide yellow 0.6 parts, iron oxide rust 0.2 parts,
Carbon black 0.4 parts, titanium oxide 0.4 parts, silicon oxide 0.1 parts, additive 0.3 parts, rubber volatile oil 10.0 parts, toluene 12.0 parts, petroleum benzene 38.0 parts A composition having a viscosity of 17.6 mPa · s (20 ° C.).

<Clear paint A> ALMATEX 894
-2 71.0 copies, Yuban 20SE-60 25.0
Parts, glycol monobutyl ether 3.0 parts, additives 1.
A composition consisting of 0 parts. <Clear paint B> Utable 2816 (acrylic resin varnish containing hindered amine group, heating residue 50 ± 2%,
Nippon Shokubai Co., Ltd. product name) 84.0 parts, UV absorber 0.4
Parts, silicic acid anhydride 0.6 parts, butyl acetate 6 parts, xylene 9.0
Parts, 8.0 parts of Coronate HX.

<Clear paint C> Acrylic 210E
(Acrylic emulsion, heating residue 49.5 ± 1.5
%, Product name manufactured by Nisshin Arrow Co., Ltd.) 70.0 parts, ethylene glycol monobutyl ether 4.0 parts, Texanol 2.0
Part, talc 4.0 parts, antifoaming agent 0.2 parts, and water 20 parts.

Test Method The coating films obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated in terms of design, initial adhesion, hot water test, secondary adhesion and accelerated weathering resistance according to the following test methods. The results are as shown in Tables 1 to 4. Design: Visual appearance, initial adhesion: Stick cellophane tape on the printed surface,
Rapidly peeling off to visually judge the peeling condition of the print pattern, warm water test: dip the test piece in warm water of 60 ± 3 ° C for 48 hours, and observe the appearance of the coating film after drying at 60 ° C for 4 hours. Next adhesion: After the above hot water test, the peeling condition of the print pattern is visually judged by the same test operation as the initial adhesion, accelerated weather resistance: QUV accelerated baculo test using a QUV accelerated weather resistance tester manufactured by The Q Panel Co., Ltd. by. Test condition: Maximum 3
13nm UV lamp (FS ・ 40, wetting ・
The coating film after the test was evaluated according to the following criteria (entered in the test time tables 1 to 4): ○: color difference ΔE2.0>, gloss retention rate 70% <Δ: color difference ΔE4 0.0 ≧, gloss retention rate 50% ≦ ×: color difference ΔE4.0 <, gloss retention rate 50%>

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

As is clear from the descriptions in Tables 1 to 4, in the case of Comparative Example 1 in which the viscosity of the ink is higher than 14 mPa · s (20 ° C.), the ink droplets ejected from the nozzle are good dots. It was impossible to pattern because it did not become a shape. The recoatability of melamine cross-linked baking coatings such as melamine acrylic and melamine alkyd is generally very poor. Therefore, recoating is usually performed with a similar paint. In the case of Comparative Example 2, since the ink side is a terpene-soluble acrylic resin and the SP value is considerably different from that of the lower colored coating film,
It is considered that phase separation occurs.

Patterning was performed using an ink containing a metallic pigment, but in the case of Comparative Example 3 in which clear coating was not performed thereon, the weather resistance was poor.

[0046]

According to the method for forming a patterned coating film of the present invention, it is possible to form a patterned coating film excellent in designability with a small number of steps, with good workability, high precision and good reproducibility.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of an inkjet printer used in a method for forming a patterned coating film according to the present invention and a control system thereof.

FIG. 2 is a schematic side view of the inkjet printer and a conveyor for transportation.

[Explanation of symbols]

 1 Conveyor 2 Printer Head 3 Nozzle 4 Ink Tank 8 Valve Control Device 10 Pattern Data Storage Unit 11 Control Unit (Computer) a Board

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B05D 7/24 301 B05D 7/24 301M

Claims (7)

[Claims] 1. A method for forming a patterned coating film, which comprises applying a colored ink to a surface of an article to be coated with a lower colored coating film in advance from a nozzle of an inkjet printer to apply the ink in a pattern. 2. The method for forming a patterned coating film according to claim 1, wherein a clear paint is applied to the entire surface of the patterned coating film. 3. The method for forming a patterned coating film according to claim 1, wherein the colored ink is a transparent colored ink. 4. The method for forming a patterned coating film according to claim 1, wherein the colored ink is an opaque colored ink. 5. The method for forming a patterned coating film according to claim 1, wherein the article to be coated is a metal plate. 6. A computer, which stores data of a position where a colored ink is to be applied on the surface of an object to be coated, which has been previously coated with a lower colored coating film, is stored in a computer, and valve control is performed by a control signal of the computer. The method for forming a patterned coating film according to claim 1, wherein the device is driven to control ink ejection from nozzles of the inkjet printer. 7. The ink has a viscosity of 2 to 14 mPa · s (2
It is 0 degreeC), The forming method of the coating film in any one of Claims 1-6 characterized by the above-mentioned.