KR20190106019A - Pcm color steel sheet with multi-texture surface and method for manufacturing the same - Google Patents

Abstract

According to the present invention, a wrinkle portion or a flat portion of a transparent layer are formed according to/corresponding to a specific pattern or design of a printing layer by including an amine wrinkle forming agent in the transparent layer and including an amine wrinkle preventing agent on the specific pattern or design of the printing layer, thereby providing a color steel plate which exhibits a composite texture and a method for manufacturing the same. The color steel sheet exhibiting the composite texture according to the present invention can form a wrinkle portion or a flat portion of the transparent layer corresponding to the specific pattern or design of the printing layer, and thus the surface texture, decorativeness and exterior beauty are excellent. The coating durability is excellent since no difference of thickness exists between the wrinkle portion and the flat portion of the transparent layer. The coating of the transparent layer can be carried out using a flatbed roller, and thus the process is simple and economical.

Description

PCM color steel plate showing composite texture and manufacturing method thereof {PCM COLOR STEEL SHEET WITH MULTI-TEXTURE SURFACE AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a PCM color steel sheet exhibiting a composite texture, and a method for manufacturing the same, and specifically, a PCM color steel sheet and an amine anti-wrinkle agent exhibiting a composite texture formed by matching a specific pattern or pattern of a printed layer with surface wrinkles of a transparent layer. It relates to a method for producing the same using a transparent coating composition containing an ink composition containing and an amine wrinkle forming agent.

Metal coating methods are generally classified into a post-coating method of coating after molding and a pre-coating method of coating before molding. Post-coating method is inexpensive equipment cost, is advantageous for small quantity production, there is a problem that uniform product and mass production is difficult. On the other hand, the pre-coating method has the advantages of stable operation, uniformity of product, reduction of paint loss, low environmental pollution, and mass production in a short time. Here, a steel sheet coated with a metal to be formed by a pre-coating method is called a pre-coated metal (PCM) color steel sheet, and a paint used therein is called a PCM paint.

These PCM color steel sheets (hereinafter referred to as color steel sheets) have a variety of colors and patterns, such as colorful appearance and do not require reprocessing, and have been widely used in home appliances such as washing machines, refrigerators, TVs, construction materials, automobiles, etc. In recent years, the market is expanding for indoor and outdoor interior applications by providing three-dimensional or textured surfaces.

Colored steel sheets are usually composed of a chemical conversion layer, an optional antirust layer, an undercoat layer, a printing layer and a transparent layer on a base steel sheet. Specifically, such a color steel sheet is subjected to chemical conversion treatment such as degreasing treatment to improve the corrosion resistance of the steel sheet on the surface of the base steel sheet, and to the surface treatment to improve adhesion, corrosion resistance and processability of the print layer and / or transparent layer on the surface thereof. And a clear layer (transparent layer), which is a transparent coating layer that improves the protection of the printed layer and the beauty of the appearance, is formed on the surface thereof, and in some cases, the surface is prevented from scratching and adhesion of external contaminants. It can be produced by forming a protective film layer to prevent.

In general, the three-dimensional appearance or texture of the surface of the color steel sheet is coated with a different thickness of the transparent layer depending on the pattern or pattern of the printing layer of the color steel sheet (see, Korean Patent Publication No. 10-2013-005168), or the transparent layer of the color steel sheet Or by using a material such as microparticles, beads, textured particles, etc. (see Patent Document 2), or using a material such as a surface tension regulator, a rheological additive or a wrinkle forming agent in the transparent layer of the color steel sheet. Methods have been developed that are implemented by modifying the surface morphology. However, in the method of realizing a three-dimensional effect by coating the thickness of the transparent layer differently, there is a problem in that the durability of the overall surface is uneven due to the difference in thickness, and the surface texture or touch using microparticles or texture particles, etc. In an implementation manner, these particles may not be completely cleaned on the coating rolls, resulting in afterimage defects in the final product.

On the other hand, the method of realizing wrinkles in the transparent layer of the color steel sheet using the amine-based wrinkle forming agent, has a number of advantages, such as the matting or low gloss effect by the surface wrinkles has been widely used in recent years.

For example, Patent Document 1 (Domestic Patent Publication No. 10-0349085) provides a surface feel with an inorganic filler while implementing surface wrinkles by including an amine in the top coat layer during the production of PCM color steel sheet. The color steel plate which is mentioned is disclosed.

Patent Document 2 (Domestic Utility Model Publication No. 20-2013-0004167) has a lot of pores on the upper surface of the undercoat layer treated on the steel sheet to improve the wrinkle formation of the coating film surface by controlling the rheological behavior of the coating composition. A color steel sheet is disclosed in which a top coat layer containing a rheological additive, which plays an important role, is applied to realize surface wrinkles.

Patent document 3 (Domestic Patent Publication No. 10-2009-0027043) uses a color pigment using a transparent layer coating composition for PCM color steel sheets containing a urethane-modified polyester resin, melamine resin, acid catalyst, amine catalyst and colored organic particles. It is disclosed that a variety of colors can be realized without the use of a, and a low gloss effect can be achieved by uniformly forming a predetermined wrinkle pattern on the surface of the coating film.

In the method for realizing surface wrinkles using a wrinkle forming agent, if the thickness of the transparent layer including the amine-type wrinkle forming agent is small, wrinkles are not well formed, and it is known that wrinkles are well formed only when the thickness is more than a certain thickness. For example, in Patent Document 2, although it varies depending on the composition of the composition and the type of the wrinkle forming agent, when the transparent layer (top coat layer) has a thickness of about 20 µm or more, specifically, about 20 to 30 µm While wrinkles are well formed on the surface, it is disclosed that the surface wrinkles are not well formed when the thickness of the transparent layer is 20 µm or less.

By using this problem, wrinkles may be selectively formed on the surface of the color steel sheet according to a specific pattern or pattern. That is, by coating the transparent layer containing the wrinkle forming agent to have a different thickness according to a specific pattern or pattern, wrinkles can be selectively formed on the surface of the color steel sheet according to the specific pattern or pattern.

On the other hand, in the color steel plate thus formed, a portion where wrinkles are formed on the surface (hereinafter referred to as a "wrinkle portion") and a portion where the wrinkles are not formed on the surface (hereinafter referred to as "flat portion") necessarily have a thickness. It causes a difference, which causes a problem that there is a difference in coating film durability.

In order to solve the problem that the surface durability decreases or becomes inhomogeneous according to the difference in the thickness of the transparent layer, the wrinkle part may be selectively implemented by the transparent layer paint composition containing the wrinkle forming agent, and the flat part may be selected by the transparent layer paint composition that does not contain the wrinkle forming agent. In this way, the apparatus for selectively painting the paint composition can be complicated, making the process cost difficult and practically difficult to apply.

Domestic Patent Publication No. 10-0349085 (2002.05.18) Domestic Utility Model Publication No. 20-2013-0004167 (2013.07.08.) Korean Unexamined Patent Publication No. 10-2009-0027043 (2009.03.16.)

The present inventors have intensively studied how to implement the surface texture by using the amine-type wrinkle forming agent on the surface of the color steel sheet and solve the above problems.

The inventors of the present invention, while studying the color steel sheet having a texture and three-dimensional effect on the surface and its manufacturing method for many years, to form a printing layer with an ink composition containing a HALS (Hindered amine light stabilizer), containing an amine wrinkle forming agent thereon When the transparent layer coating composition was coated to form a transparent layer, it was found that wrinkles were not easily formed on the surface of the transparent layer regardless of the thickness of the transparent layer. Furthermore, an amine compound such as HALS contained in the printed layer was also amine-based. The present invention has been found to act as an anti-wrinkle agent on a transparent layer containing a forming agent.

Further, by using this phenomenon, it is possible to form the wrinkles and flat portions of the transparent layer to match or correspond to a specific pattern or pattern of the printing layer, thereby making the surface texture, decoration and exterior beauty of the color steel sheet more beautiful. In addition, it can be confirmed that the wrinkles and flat portions of the transparent layer can be formed without a substantial difference in thickness, so that the durability of the transparent layer can be homogenized.

In addition, since the formation of wrinkles and flat portions on the surface of the transparent layer can be controlled by the anti-wrinkle agent contained in the printing layer and / or the undercoat layer, the final transparent layer is coated in a roll-to-roll manner. In addition, it has been confirmed that another advantage is that it can be carried out using a flat roller, thereby making the painting process simpler and reducing the process cost.

In the color steel sheet according to the present invention, since the wrinkles or flat portions of the transparent layer correspond to a specific pattern or pattern of the printing layer, the surface texture is realized in a complex manner, and its decorativeness and appearance are more beautiful, and the thickness difference between the wrinkles and the flat portions of the transparent layer is different. Since the coating film durability is homogeneous and the coating of the transparent layer can be performed by a roll-to-roll offset printing method using a flatbed roller, the process is simple and economical.

1 is a view showing a general configuration of a color steel sheet.
2 is a view showing a roller configuration used in a general offset printing process.
Figure 3 is a schematic diagram of the manufacturing process of the color steel sheet having a surface wrinkles according to the prior art, it will be described that the wrinkles and the flat portion is formed according to the thickness of the transparent layer.
4 and 5 is a schematic view of the manufacturing process of the color steel sheet having a composite texture according to the present invention, it will be described that the wrinkles and the flat portion is formed on the surface of the transparent layer according to a specific pattern or pattern of the printing layer.
6 is a photograph showing the surface of a color steel sheet printed with a ring pattern according to the prior art and the present invention, Figure (a) is a color steel sheet according to the prior art that the surface wrinkles are implemented irrespective of the pattern or pattern of the printed layer The surface photograph of (b) is a surface photograph of the color steel sheet according to the present invention in which the surface wrinkles of the transparent layer are implemented to match the pattern or pattern of the printing layer.

The first object of the present invention is a color steel sheet comprising a printed layer and a transparent layer on the base steel sheet comprising at least one chemical conversion treatment layer, rustproof layer, undercoat layer and base layer, and showing a complex texture by the surface wrinkles of the transparent layer To provide;

The printed layer includes a specific pattern or pattern containing an amine anti-wrinkle agent;

The transparent layer contains an amine wrinkle forming agent, and has a wrinkle portion having a surface wrinkle and a flat portion having no surface wrinkle on its surface;

Wrinkles or flat portions of the transparent layer appear in correspondence with a specific pattern or pattern containing a wrinkle inhibitor in the printed layer.

According to a preferred embodiment of the present invention, the above-described printing layer may be formed to have a specific pattern or pattern using the ink composition containing the amine-based anti-wrinkle agent, the above-described transparent layer is a transparent layer containing the amine-based wrinkle forming agent It can be painted using the coating composition.

A second object of the present invention relates to a method for producing a color steel sheet exhibiting a complex texture by the surface wrinkles of the transparent layer, comprising the following steps (1) to (3):

(1) forming a chemical conversion treatment layer, a rust prevention layer, an undercoat layer, and a base layer in order one or more on the base steel sheet;

(2) printing a specific pattern or pattern containing an amine wrinkle inhibitor on the base layer to form a print layer, and optionally drying; and

(3) coating a transparent layer coating composition containing an amine wrinkle forming agent on the printed layer to form a transparent layer, and optionally heating and / or curing.

The preparation method may optionally further comprise the following step (4):

(4) installing a protective film on the transparent layer.

The present invention is explained in more detail below.

<1> color steel sheet

In the present invention, the color steel sheet exhibiting a complex texture by the surface wrinkles of the transparent layer generally includes a base steel sheet, a chemical conversion layer, an antirust layer, an undercoat layer, a base layer, a print layer, and a transparent layer, and further treatment as necessary. It may further comprise a layer and / or coating layer. The rustproof layer and base layer described above may not be provided in some cases.

As the above-described base steel sheet (or base steel sheet), a metal plate itself or a steel plate plated with a non-ferrous metal such as zinc or aluminum on the metal plate may be used, but is not limited thereto. For example, hot dip galvanized steel sheet, alloyed hot dip galvanized steel sheet, electrogalvanized steel sheet, hot rolled aluminum-zinc alloy plated steel sheet, cold rolled steel sheet, zinc hot dip steel, electro-zinc steel, alloy-plate steel, copper sheet, Tin-plate steel or aluminum plates, and the like, but is not limited thereto.

According to a variant of the invention, the base steel sheet may be replaced with tiles, ceramics, building interior materials and building exterior materials.

In this invention, it is preferable to include the well-known chemical conversion film-processed pretreatment layer in order to ensure the adhesiveness of a rustproof primer layer and a basic rustproofness on a base steel plate.

The rustproof layer (or rustproof primer coating layer) described above may be installed in some cases, and it should be able to secure the interlayer adhesion between the base steel sheet and the undercoat layer and exhibit rustproofness for a predetermined time or more. It can apply selectively selectively as appropriate.

The undercoat (or base coat layer) described above is required in technical aspects, such as transferability of the print ink and adhesion to the print layer after the ink is dried, and at the same time serves to implement the background color in terms of design. Base paints may also be suitably and selectively applied to commercially available base paints for PCM printing. The undercoat layer and the base layer may be combined to form one layer, or may be installed separately in each layer.

According to the present invention, the above-described printed layer and transparent layer are formed on a base steel sheet including at least one chemical conversion treatment layer, a rust prevention layer, a bottom coating layer and a base layer, preferably, a conversion treatment layer, an optional rust prevention layer, a bottom coating layer and It may be formed on the base steel sheet including the base layer in sequence, more preferably on the undercoat layer or the base layer.

The above-described printed layer (or ink layer) is formed on the undercoat or base layer mainly by gravure or offset method. According to the prior art, such a printed layer does not affect the surface appearance of the transparent layer, but according to the present invention In addition, certain components (eg, amine wrinkle inhibitors) contained in the print layer may interact with certain components (eg, amine wrinkle agents) contained in the transparent layer, thereby preventing wrinkles of the transparent layer.

The above-mentioned transparent layer (or clear layer) is formed on the printed layer by a gravure or offset method using the transparent coating composition, and in some cases, may be formed on the undercoat layer on which the printed layer is not formed. The dry coating film thickness of a transparent layer is 5-30 micrometers normally, Preferably it is 10-20 micrometers.

In the color steel sheet of the present invention, the above-described printing layer may be printed with the specific pattern or pattern containing the amine-based anti-wrinkle agent in whole or in part; The above-mentioned transparent layer contains an amine-based wrinkle forming agent, and has wrinkles having surface wrinkles and flat portions having no surface wrinkles on its surface; Wrinkles or flat portions of the above-described transparent layer appear / correspond to the specific pattern or pattern of the above-described printed layer.

Specifically, the specific pattern or pattern containing the amine-based antiwrinkle agent described above is printed using the ink composition containing the amine-based anti-wrinkle agent; The above-mentioned transparent layer is coated using a transparent layer coating composition containing an amine-based wrinkle forming agent, and the surface thereof has wrinkles having surface wrinkles and flat portions without surface wrinkles; The wrinkles or flat portions of the above-mentioned transparent layer appear / correspond to the specific pattern or pattern of the above-described print layer formed using the ink composition containing the amine compound.

According to one embodiment of the invention, the amine-based wrinkle forming agent is an amine compound having a boiling point higher than the process temperature (100 to 150 ℃), more preferably a melting point than the process temperature or firing temperature (100 to 150 ℃) Low and boiling point may be selected from the group consisting of amine compounds higher than the process temperature (100-150 ° C.), preferably secondary amines such as dialkylamines, diarylamines, alkylarylamines, N, N-tetraalkylalkylenediamine, 2,5-dialkylpyrrolidine, 2,2,5-trialkylpyrrolidine, 2,2,5,5-tetraalkylpyrrolidine, 2,5-dialkyl Piperidine, 2,2,5-trialkylpiperidine, 2,2,5,5-tetraalkylpiperidine and derivatives thereof may be selected from, but is not limited to these.

According to one embodiment of the invention, the amine anti-wrinkle agent is selected from the group consisting of secondary amine compounds or amine-based light stabilizers (Hindered Amine Light Stabilizer, HALS) boiling point higher than the process temperature (100 to 150 ℃) Dialkylamine, diarylamine, alkylarylamine, N, N-tetraalkylalkylenediamine, 2,5-dialkylpyrrolidine, 2,2,5-trialkylpyrroli Dean, 2,2,5,5-tetraalkylpyrrolidine, 2,5-dialkylpiperidine, 2,2,5-trialkylpiperidine, 2,2,5,5-tetraalkylpiperidine Dean and its derivatives may be selected from, but is not limited to these. The aforementioned tetraalkyl piperidine or derivatives thereof may comprise, for example, the tetraalkyl piperidine compound described in PCT / EP92 / 00023.

In the present invention, Hindered amine light stabilizer (HALS) means a sterically hindered amine light stabilizer, which may be used to suppress the aging phenomenon in paints and plastics, especially polyolefin plastics (Kunststoffe, 74 (1984)). 10, pp. 620-623; Farbe + Lack, Volume 96, 9/1990, pp. 689-693). The tetramethylpiperidine group present in the HALS compound contributes to the stabilizing effect. This kind of compound may have no substituent on the piperidine nitrogen, or may be substituted with an alkyl or acyl group on the piperidine nitrogen. Stereo hindered amines do not absorb in the UV region. They remove the free radicals formed, while UV absorbers do not. Non-limiting examples of HALS compounds that have stabilizing effects and can also be used in the form of mixtures include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 8-acetyl-3-dodecyl -7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5) -decane-2,5-dione, bis (2,2,6,6-tetramethyl-4- Piperidyl) succinate, poly (N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine succinate) or bis (N-methyl-2,2,6 , 6-tetramethyl-4-piperidyl) sebacate.

<2> Printed layer

According to one embodiment of the invention, the printed layer is 10 to 60% by weight polyester resin, 1 to 50% by weight pigment, 35 to 80% by weight organic solvent, 0.1 to 10% by weight amine-based anti-wrinkle agent and 0.1 additive It can be formed using an ink composition containing ˜5% by weight. The printed layer may be printed to have a specific pattern or pattern, for example.

As the amine anti-wrinkle agent described above, a secondary amine compound or an amine ultraviolet stabilizer may be used, and in particular, an amine light stabilizer (HALS) may be used.

polyester  Suzy

The above-mentioned polyester resin may be included in 10 to 60% by weight based on the total weight of the composition, when the content of the polyester resin is less than 10% by weight, the viscosity is too low, such as ink bleeding may reduce print quality and print jobs Workability may deteriorate, such as ink scattering in a thin roll. When it exceeds 60% by weight, there may be a problem such that the drying of the ink is delayed or the viscosity is too high, resulting in poor print workability.

According to one variant of the present invention, other resins (e.g., polyurethane resins, acrylic resins, silicone modified polyester resins, alkyd resins, epoxy resins, fluorine resins, etc.) may be used instead of the above-described polyester resins.

Pigment

In order to guarantee long-term weather resistance of more than 20 years, the above-mentioned pigments are recommended in ceramic pigments having excellent heat resistance, chemical resistance, weather resistance and corrosion resistance, but two or more kinds of pigments such as metallic pigments and organic pigments may be mixed and used depending on color selection. The pigment may be used in an amount of 1 to 50% by weight based on the total weight of the ink composition. When the composition of the pigment is less than 1% by weight, the hiding power may be difficult to achieve a desired color. There may be problems such as falling.

Organic solvents

The organic solvent described above may be a conventional organic solvent known in the art as long as there is no problem in proper viscosity lowering effect and surface appearance, but it is preferable to use a ketone organic solvent having a boiling point of 100 to 200 ° C. Non-limiting examples of the organic solvent include hydrocarbons, aromatic hydrocarbons, ketones, esters, acetates, and the like. The organic solvents may be used alone or in combination of two or more thereof. The organic solvent may use 35 to 80% by weight based on the total weight of the ink composition, when the composition of the organic solvent is less than 35% by weight, the viscosity may be too high, the workability may be lowered, and when it exceeds 80% by weight, the viscosity is too high This may cause problems with long-term storage, such as poor printability or faster pigment deposition during long-term storage of the ink.

UV stabilizer

In general, the weather resistance of the coating film of the color steel sheet can be improved by incorporating an ultraviolet stabilizer in the undercoat layer, the printing layer and / or the transparent layer, preferably the printing layer, of the color steel sheet to block / absorb ultraviolet rays.

In the present invention, an ultraviolet stabilizer may be included in the ink composition of the printing layer, and the content of the ultraviolet stabilizer is not particularly limited, but is preferably 0.1 to 10% by weight based on the total weight of the ink composition. When the content is in the above range, the light and durability of the ink and the clear coating film are improved, and the activation of the amine is prevented in the process of baking the transparent layer due to the stabilizing effect of the UV stabilizer, thereby preventing the complex gloss and texture intended for the transparent layer. It can be implemented. If the content of the UV stabilizer is less than 0.1% by weight, the desired composite texture may not be expected, and when the content exceeds 10% by weight, there may be an increase in raw material costs and workability.

In general, UV stabilizers can be classified into light stabilizers and ultraviolet absorbers.

Non-limiting examples of the light stabilizer, Tinuvin 292, Tinuvin 144, Tinuvin 622LD, Tinuvin 5060 (BASF, Japan), Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-744 (Sankyo, Japan) ) May be mentioned. These light stabilizers may be used alone or in combination of two or more thereof.

Non-limiting examples of the ultraviolet absorber, Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 328, Tinuvin 312 (BASF, Japan), Sumisorb 110, Sumisorb 130, Sumisorb 140, Sumisorb 220, Sumisorb 250, Sumisorb 320, Sumisorb 400 (Sumitomo, Japan) and the like can be mentioned. Such ultraviolet absorbers may be used alone or in combination of two or more thereof.

additive

In addition, the ink composition of the present invention may include an additive in an amount of 0.1 to 5% by weight, for example, it may be selected from the group consisting of a dispersant, a surface protector and the like.

Dispersants include, but are not limited to, Disperbyk 170 of BYK, EFKA 4061 of Evonik, and the like. As surface protective agents, amorphous silica particles or organic substances on Wax can be used. For example, amorphous silicas include Syloid C807, Syloid C812, Syloid 622 (Grace, Germany), GASIL HP-260, GASIL HP-270 (PQ CORPERATION, USA). Etc. may be used, but is not limited thereto. In addition, the organic material on the Wax may be used, such as MPI's MP22XF, BYK's CERAFLOUR 990, but is not limited thereto.

If the content of the additive is less than 0.1% by weight, the flowability of the ink may be reduced, or workability or physical properties such as stickiness or agglomeration of the pigment may be reduced.If the content is more than 5% by weight, the adhesion of the transparent layer may be reduced or the additive may be reduced. This may cause adverse effects such as ink deflection due to injuries, which may cause deterioration of workability and physical properties.

<3> transparent layer

According to one embodiment of the invention, the transparent layer is 20 to 60% by weight polyester resin, 5 to 30% by weight melamine cured resin, 20 to 70% by weight organic solvent, 0.1 to 5% by weight acid catalyst, amine compound It can be coated using a transparent layer coating composition comprising 0.1 to 3% by weight, 0.1 to 10% by weight of particles, and 0.1 to 5% by weight of additives, and the above-described amine catalyst can usually function as an amine wrinkle agent.

Polyester resin

The above-mentioned polyester resin may be included in 20 to 60% by weight based on the total weight of the composition, when the content of the polyester resin is less than 20% by weight, the viscosity is too low, workability is reduced or wrinkles do not occur, such as expected If there is a performance that may not appear and exceeds 60% by weight, the viscosity is too high, there may be a problem such as poor paintability workability or hardening force is lowered durability.

According to one embodiment of the present invention, the above-mentioned polyester resin is selected from urethane-modified polyester resins, by adding a linear polyisocyanate resin to a polyol obtained by the condensation reaction of basic acids and alcohols. It can be synthesized while maintaining isothermal in the range of 60 to 100 ℃. More specifically, an acid component such as a polyhydric carboxylic acid and / or anhydride thereof is reacted with a polyhydric alcohol to form a hydroxyl group-containing polyester resin, and then the hydroxyl group-containing polyester resin and the diisocyanate compound are It can be prepared by reacting under a hydroxyl group excess condition. Specific examples of such urethane-modified polyester resins may refer to those described in Patent Document 3 (Domestic Patent Publication No. 10-2009-0027043).

According to one variant of the present invention, other resins (e.g., polyurethane resins, acrylic resins, silicone modified polyester resins, alkyd resins, epoxy resins, fluorine resins, etc.) may be used instead of the above-described polyester resins.

Melamine resin

The above-mentioned melamine resin serves as a curing agent to harden well with the polyester resin which is the main resin inside and outside the coating film.

The melamine curable resin is a substance obtained for the polymerization of alcohol and formaldehyde, and for example, methoxy melamine resin is a polymerization of methanol and formaldehyde; Butoxy melamine resins can be obtained by polymerization of iso-butanol or normal butanol with formaldehyde.

Non-limiting examples of melamine resins that can be used in the present invention, CYMEL-303, CYMEL-325, CYMEL-327, CYMEL-350, CYMEL-370 (CYTEC), RESIMINE-7550, RESIMINE-717, RESIMINE-730, RESIMINE-747, RESIMINE-797 (SOLUTIA), BE-3717, BE-370, BE-3747 (BIP), BE-630, BE-692 (BIP), RESIMINE-7512, RESIMINE-750, RESIMINE- 755, RESIMINE-757, RESIMINE-751 (SOLUTIA), CYMEL-1168, CYMEL-1170, CYMEL-232 (CYTEC). In the present invention, a hexamethoxymethylmelamine resin having a solid content of 98% was used as a resin manufactured by Meltec, Inc., a US manufacturer.

Melamine cured resin may be contained 5 to 30% by weight based on the total weight of the composition, there is a problem such as low durability of the hardness of the content of the melamine cured resin is less than 5% by weight, when the processability is higher than 30% by weight The expected performance of clear paints does not appear, such as wrinkles or wrinkles.

Organic solvents

The organic solvent may be a conventional organic solvent known in the art as long as there is no problem in proper viscosity lowering and surface appearance, it is preferable to use an organic solvent having a boiling point of 120 to 250 ℃.

Non-limiting examples of the organic solvents include carbon-hydrogen solvents, aromatic hydrocarbon solvents, ketone solvents, ester solvents, acetate solvents, and the like. The organic solvent may be used alone, or may be used by mixing two or more kinds.

The organic solvent may be used 20 to 70% by weight based on the total weight of the coating composition, when the composition of the organic solvent is less than 20% by weight, the viscosity may be too high workability, and when it exceeds 70% by weight This may cause problems in long-term storage, such as poor workability of paint or the rapid precipitation of additives during long-term storage of the paint.

Acid catalyst

The acid catalyst may be a sulfonic acid shielded with a material that can be dissociated by heat, but is not limited thereto. Non-limiting examples of the sulfonic acid include P-toluenesulfonic acid, dodecylbenzenedisulfonic acid, dinonylnaphthalenedisulfonic acid, dinonylnaphthalenesulfonic acid or mixtures thereof. P-toluenesulfonic acid or nonylnaphlenylenesulfonic acid is preferable. The acid catalyst is preferably shielded with a material that can be dissociated by heat. As the shielding material, an amine compound may be used. In the present invention, it may be appropriate to use an amine catalyst having a higher volatility than the acid catalyst in order to cause a difference in curing between the inside and the surface of the coating film due to the difference in volatility between the acid catalyst and the amine catalyst.

The acid catalyst may be used in an amount of 0.1 to 5% by weight based on the total clear paint composition, but is not limited thereto. When the amount of the acid catalyst used is less than 0.1% by weight, curing of the coating film is insufficient according to the working conditions, so that the physical properties of the coating film cannot be maintained, and when it exceeds 5% by weight, curing of the coating film occurs so rapidly that paping the coating film during painting works. Popping may occur or shrinkage of the coating film may occur.

An amine compound

If the amine can be appropriately wrinkles can be used a common amine known in the art, it is preferable to use a high activation.

Amine compounds are classified into primary amines (R-NH ₂ ), secondary amines (R-NH-R), and tertiary amines (R ₃ -N), depending on the number of hydrocarbon groups substituted by hydrogen atoms of ammonia. . At this time, when all hydrocarbon groups are alkyl groups, it is an aliphatic amine, and when one or more of a hydrocarbon group is an aryl group, it is called aromatic amine. Non-limiting examples of amines that can be used may include alkylamines, alkanolamines, polyamines, hydroxyamine compounds, cyclic amines, and the like.

Examples of alkylamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, 2-aminopentane, 3-aminophen Tan, 1-amino-2-methylbutane, 2-amino-2-methylbutane, 3-amino-2-methylbutane, 4-amino-2-methylbutane, hexylamine, 5-amino-2-methylpentane, Primary alkylamines such as heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine and octadecylamine; Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-t-butylamine, dipentylamine, dihexylamine, diheptylamine , Dioctylamine, dinonylamine, didecylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, methyl-sec-butylamine, methyl-t-butylamine, methyl Amylamine, methylisoamylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine, ethylisobutylamine, ethyl-sec-butylamine, ethylamine, ethylisoamylamine, propylbutylamine and propylisobutyl Secondary alkylamines such as amines; It also includes tertiary alkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine.

Examples of alkanolamines include ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, isopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine , N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-aminopropan-1-ol, N-ethyl-2-aminopropan-1-ol, 1-aminopropan-3-ol , N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N -Ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-amino Butan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutane- 4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4- Ol, 2-amino-4-methylphene -1-ol, 2-aminohexan-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-1-aminooctan-4-ol, 1-aminopropane-2, 3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol and 2- ( 2-aminoethoxyl) ethanol.

Examples of polyamines include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, Heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methylethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, tris (2-aminoethyl) amine, tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctane, nonaethylene Decamine and diazabicycloundecene.

Examples of hydroxylamine compounds are hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine, N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine and O-methylhydroxylamine It may include.

Examples of the cyclic amine are pyrrole, 2-methylpyrrole, 3-methylpyrrole, 2-ethylpyrrole, 3-ethylpyrrole, 2,3-dimethylpyrrole, 2,4-dimethylpyrrole, 3,4-dimethylpyrrole, 2 , 3,4-trimethylpyrrole, 2,3,5-trimethylpyrrole, 2-pyrroline, 3-pyrroline, pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, pyrazole, imidazole , 1,2,3-triazole, 1,2,3,4-tetrazole, piperidine, 2-pipecoline, 3-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-ru Pettidine, 2,6-lufetidine, 3,5-lufetidine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-methylpiperazine and morpholine have.

The amine compound may be used in 0.1 to 3.0% by weight based on the total transparent layer coating composition, but is not limited thereto. When the content of the amine compound is less than 0.1% by weight, wrinkles may not occur, and when the content of the amine compound is greater than 3.0% by weight, the degree of curing may be lowered or adversely affect the storage stability of the paint.

particle

According to one embodiment of the invention, the transparent layer coating composition may further include inorganic particles or organic particles having an average particle size of 5 to 40㎛ as texture particles or tactile particles.

Particles that can be used may include one or more selected from amorphous silica, PMMA (polymethyl methacrylate) particles, polyacrylonitrile particles, and the like, but is not limited thereto. By including the particles, desired glossiness and wrinkle shape can be formed on the coating film surface of the transparent layer.

For example, as the amorphous silica, Syloid C807, Syloid C812, Syloid 622 (Grace, Germany), GASIL HP-260, GASIL HP-270 (PQ CORPERATION, USA), SS-415 (S-chemtech, Korea) and the like can be used. have. As PMMA (polymethyl methacrylate) particles, SUNPMMA-S250, SUNPMMA-S400 (Advanced Beauty Sciences, Korea), MH-15FD ^® , MH-20FD ^® , MH-25FD ^® (Kolon Industries, Korea) and the like can be used. . As the polyacrylonitrile particles, TAFTIC ™ A-20, TAFTIC ™ ASF-7 (TOYOBO, Japan) and the like can be used.

The average particle diameter of the particles is not particularly limited, but is preferably 5 to 40 μm. When the average particle diameter of the particles is less than 5, an excessively large amount of particles are added to meet the desired glossiness, which is not preferable due to a high viscosity or a problem of cost increase, and when the average particle diameter exceeds 40 μm, the surface of the coating film is It is not preferable because it adversely affects workability and appearance quality such as being too rough or attracting particles in the roll coating process.

The content of the particles is not particularly limited, but when the content is 0.1 to 10% by weight based on the total weight of the coating composition, the gloss, texture, scratch resistance, etc. of the surface of the coating film may be more exerted.

Preferably, mention may be made of silica, poly (methyl methacrylate), polyacrylonitrile (PMMA) particles as the aforementioned particles.

additive

Examples of the additives mentioned above may include, but are not limited to, leveling agents, surface protectors, viscosity regulators, thickeners, antioxidants, antifoaming agents, dispersants, UV stabilizers, and the like.

The aforementioned additives may be added to the composition in amounts known in the art, for example 0.1 to 5% by weight. If the content of the additive is less than 0.1% by weight, too much bubbles are generated during the painting operation, which may lower workability or lower the smoothness of the surface of the coating film, thereby deteriorating the appearance of the coating film. As a result, a phenomenon such as an increase in properties or a decrease in physical properties due to an overuse may occur.

The aforementioned leveling agent may include, but is not limited to, DSM's DD27 and FTC's LA-45. In addition, an organic material on a wax may be used as the surface protecting agent, but MPI's MP22XF, BYK's CERAFLOUR 990, and the like may be used, but is not limited thereto.

<4> production of color steel sheet

The color steel sheet according to the present invention can be manufactured according to the method in a conventional printed steel sheet manufacturing method, except that the ink composition and the transparent layer coating composition described above are used.

For example, a color steel sheet according to the present invention exhibiting a complex texture by the surface wrinkles of the transparent layer may be produced by a method comprising the following steps (1) to (3):

(1) forming a chemical conversion treatment layer, an optional antirust layer, an undercoat layer, and a base layer in order on the base steel sheet in sequence;

(2) printing an ink composition containing an amine wrinkle inhibitor on the base layer to form a printed layer, and

(3) forming a transparent layer by coating a transparent layer coating composition containing an amine wrinkle forming agent on the printed layer.

The preparation method may optionally further comprise the following step (4):

(4) forming or attaching a protective film layer on the transparent layer.

Preferably, the colored steel sheet according to the present invention may be produced by a method comprising the following steps:

(1) forming a chemical conversion treatment layer, a rust prevention layer, an undercoat layer, and a base layer in order one or more on the base steel sheet;

(2a) printing an ink composition containing an amine wrinkle inhibitor on the undercoat layer to form a printed layer,

(2b) drying the printed layer,

(3a) coating a transparent layer coating composition containing an amine wrinkle forming agent on the printing layer to form a transparent layer,

(3b) heating and curing the transparent layer, and

(4) forming or attaching an optional protective film layer on the transparent layer.

According to one embodiment of the invention, the printing of the printing layer and the painting of the transparent layer may be performed by a printing method selected from the group consisting of offset printing, screen printing, gravure printing, flexographic printing and inkjet printing.

According to one embodiment of the invention, the printed layer may have one or more colors or may be printed at least one degree, preferably at least two degrees, in particular at least three degrees.

For example, the color steel sheet which concerns on this invention is a 1st heating after apply | coating the undercoat coating composition on the base steel plate which has a structure of a base steel plate-chemical conversion layer, or a structure of a base steel plate-chemical conversion layer-rustproof layer. Cooling and drying to form an undercoat layer; Forming an additional base layer, if desired, on the formed undercoat layer; And roll-to-roll printing the above-described ink composition on the undercoat or base layer in a manner such as gravure or offset by at least 1 degree, preferably at least 2 degrees, particularly at least 3 degrees, Optionally drying to form a printing layer: and applying a transparent coating composition on the printing layer, and heating, cooling, and drying the secondary to form a transparent layer.

When the printed layer is partially formed on the base layer, the transparent layer may be entirely formed on the printed layer and the base layer on which the printed layer is not formed.

According to the present invention, the coating of the transparent layer may be carried out by conventional coating methods known in the art, and the process temperature (ie, heating and / or curing temperature) is not particularly limited as long as the coating film is formed and there are no abnormalities in physical properties. Although, the maximum temperature (PMT Peak Metal Temperature) of the base steel sheet is preferably in the range of 200 to 250 ℃. This process temperature can be changed according to the process conditions.

According to one preferred embodiment of the present invention, the coating of the transparent layer may be performed by an offset printing method using a flat plate roller.

 2 is a schematic view showing a roller configuration and an offset printing press used in a general offset printing process. As shown in the figure, the offset printer 110 transfers the pattern roll 111 on which the ink 101 is buried, and the ink 101 attached to the surface of the pattern roll 111, and transfers rubber, silicone or other synthetic resins. The blanket 112 made of a material of the winding and the blanket 112 includes a transfer roll 113 to closely adhere to the printing object 102, such as paper, fabric, glass plate.

The pattern roll 111 is wound around the outer circumferential surface of the printing plate 114, which is designed for printing, and rotates in contact with the transfer roll 113 to transfer ink to the blanket 112.

The transfer roll 113 is rotated by a separate rotation means such as a motor, or rotates by frictional force by the movement of the print object 102, which causes the ink 101 attached to the blanket 112 wound on the outer circumferential surface thereof. By transferring to the print object 102, a desired pattern or the like is printed on the print object 102.

In the prior art, since the thickness of the transparent layer needs to be changed according to the flat part and the wrinkle part, the intaglio of the flat part and the intaglio of the wrinkle part should be formed on the pattern roll 111 by varying the thickness, thus making the process of manufacturing the pattern roll difficult. . In addition, in the case where the flat portion / wrinkle portion is to be matched with the printed pattern / pattern, the ink transferred from the pattern roll 111 to the transfer roll 113 is separated from the pattern or pattern printed on the printing object 102. Not only is it more difficult and more difficult to apply consistently, but also it is not difficult to process such as adjusting / synchronizing the rotational speed of the roller and / or the moving speed of the printing object while checking the pattern for conformity from time to time. On the other hand, in the present invention, since the thickness of the transparent layer according to the flat portion and the wrinkle portion does not have to be different, the thickness of the flat portion and the wrinkle portion may be equally engraved in the pattern roll 111, and further, instead of the engraved roller. It was also possible to apply a transparent layer coating composition using a simple flat plate roller.

Therefore, according to one preferred embodiment of the present invention, the printing of the printing layer and the painting of the transparent layer may be performed by a printing method selected from the group consisting of offset printing, screen printing, gravure printing, flexo printing and inkjet printing. More preferably, the coating of the transparent layer may be performed by an offset printing method using a flat plate roller.

Figure 3 is a schematic diagram illustrating a process of forming the surface wrinkles on the transparent layer of the color steel sheet according to the prior art, it shows that the wrinkles and flat parts are formed on the surface of the transparent layer according to the thickness of the transparent layer. Specifically, Figure (a) of Figure 3 shows a configuration in which a chemical conversion treatment layer, an optional antirust layer, an undercoat layer and any base layer formed on the base steel sheet, Figure (b) is a specific pattern or pattern on the base layer The printed layer shows that the printed layer is formed, and Figure (c) shows that the transparent layer including the wrinkle forming agent is formed on the printed layer so as to have a thickness difference, and the figure (d) shows the heating, cooling, Drying shows that wrinkles are not formed in the thin part but thick parts are formed. For reference, in FIG. 3, the rhombic red symbol represents a wrinkle forming agent.

4 and 5 is a schematic diagram illustrating a process of forming the surface wrinkles on the transparent layer of the color steel sheet according to the present invention, in the case where the thickness of the transparent layer is secured to a certain level, if the HALS (that is, amine-based anti-wrinkle agent) is present in the transparent layer It is shown that the flat portion is formed on the surface of the wrinkles if not present. For reference, in Figs. 4 and 5, the circular blue symbol represents an anti-wrinkle agent, and the rhombic red symbol represents an anti-wrinkle agent.

Specifically, in Figs. 4 and 5, a printed layer containing HALS as an anti-wrinkle agent is printed on the base layer (see Fig. (B)), a transparent layer is formed thereon (see Fig. (C)), heating and And / or when cured, wrinkles are not formed on the surface of the transparent layer on the printed layer containing the anti-wrinkle agent, thereby forming a flat portion, and wrinkles are formed on the surface of the transparent layer on the printed layer that does not contain the anti-wrinkle agent, thereby forming a wrinkled portion ( See figure (d)).

In the present invention, the excellent effect as described above can be more specifically demonstrated by comparing the figures (a) and (b) of FIG. 6.

Figure 6 (a) is a photograph of the surface of the color steel sheet according to the prior art that the surface wrinkles are implemented irrespective of the pattern or pattern of the printed layer, on the printed layer formed to have a tree ring pattern, a wrinkle forming agent It is prepared by applying and curing a transparent layer containing is alternately applied to wrinkles (usually 7 microns or more in height) and flat portions (5 microns or less in height). In the picture of the color steel sheet, the wrinkle part has a matting effect, so the ring pattern of the inside is clearly visible, but the flat part may be bundled without the matting effect, so that the ring pattern of the interior may not be easily seen.

Figure 6 (b) is a photograph of the surface of the color steel sheet according to the present invention in which the surface wrinkles of the transparent layer is implemented so as to match the pattern or pattern of the printed layer, of the printed layer containing the anti-wrinkle agent along the tree ring pattern of the tree On the top, the transparent layer containing a wrinkle forming agent is apply | coated and hardened to a fixed height, and it is manufactured. From the above picture, the wrinkles / flat portions of the surface are formed along the ring pattern, the inner ring pattern and the color (light) are shown delicately and vividly to the outside, and the surface reflection and the surface shine according to the inner ring pattern It appears to be controlled, whereby an aesthetic effect such as gradation is exhibited.

Therefore, the color steel sheet according to the present invention, the pattern, pattern, color, texture, etc. implemented on the surface of the printed layer can be effectively and aesthetically visible to the outside, high visual and design completeness, the transparent layer to protect the printed layer Compared with the prior art, it can be formed with a thick and homogeneous thickness, so that the surface durability is homogeneous overall and the product quality is homogeneous.

Hereinafter, the present invention will be described in more detail. These examples are only for illustrating the present invention in more detail, it is apparent to those skilled in the art that the scope of the present invention is not limited by these examples. In the examples,% means% by weight unless otherwise indicated.

Examples 1-3 and Comparative Example 1

On a substrate made of a base steel plate-chemical conversion layer-preventive layer, a specific pattern or pattern was printed by a roll-to-roll offset method with an ink composition having a composition shown in Table 1 below.

Ink composition Example 1 Example 2 Reference Example 1 Comparative Example 1 Polyester resin 20 20 20 20 Pigment 5 5 5 5 Organic solvents 72.95 70 58 73 UV stabilizer 0.05 3 15 - additive 2 2 2 2 Total weight 100 100 100 100

Polyester resin: SKYBON ES110S (manufacturer: SK chemicals)

Pigment: MA 100 (Manufacturer: Mitsubishi)

Organic solvents: cyclohexanone

UV stabilizers: mixtures of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate

Additive: MP22 WAX (Manufacturer: Micro Powders, Inc. USA)

On the printed layer formed in Comparative Examples 1 and 1 to 3, 40% by weight of polyester resin, 15% by weight of melamine resin, 41% by weight of organic solvent, 1% by weight of acid catalyst, 1% by weight of amine, 1% by weight of particles, A transparent layer paint composition (see Example 8 in Table 3) containing 1 wt% of an additive was applied and heat-cooled-dried at 200 to 250 ° C. to prepare a transparent layer having a thickness of 15 μm.

The physical properties and appearance of the color steel sheets obtained in Examples 1 to 3 and Comparative Example 1 are shown in Table 2 below.

Properties Example 1 Example 2 Example 3 Comparative Example 1 Ink transferable Good Good Bad Good Adhesion Good Good Bad Good Surface dryness Good Good Bad Good Transparent layer appearance No change
(Wrinkling) Has change
(No wrinkles) Has change
(No wrinkles) No change
(Wrinkling)

In Comparative Example 1 (using conventional ink), various physical properties were good, but surface wrinkles were formed in the transparent layer, and no significant change occurred in other appearances. On the other hand, in Example 1, the overall physical properties are good, but the amount of the UV stabilizer, which is a wrinkle inhibitor, is small, so that the surface wrinkles are formed on the transparent layer without any change in appearance. It contained as mentioned above, and the external appearance changed to the transparent layer, and wrinkles were not formed. In Example 3, it can be seen that due to the adverse effect of the excessive use of the UV stabilizer, the use of various physical properties is poor.

Therefore, when the results of Examples 1 and 2 and Comparative Example 1 were combined, it was confirmed that desired technical and design effects can be obtained by appropriately adjusting the amount of the antiwrinkle agent used.

Examples 4-8 and Comparative Example 2

On the substrate of the base steel sheet-chemical conversion layer-rustproof layer, the same treatment as in Example 2 was carried out to form a printed layer, and then the transparent layer coating composition having the composition shown in Table 3 was coated by a roll-to-roll offset method, and 200 Heat-cool-dry at -250 degreeC, and the 15-micrometer-thick transparent layer was produced.

Transparent Layer Coating Composition Comparative Example 2 Example 4 Example 5 Example 6 Example 7 Example 8 Polyester resin 40 40 40 40 52 40 Melamine resin 15 15 15 15 3 15 Organic solvents 43 40 40 40 40 41 Acid catalyst One One One - One One Amine - One One One One One particle One One - One One One additive One - One One One One Total weight 100 100 100 100 100 100

Polyester resin: KPE-410-60 (manufacturer: Samwha paint)

Melamine Resin: CYMEL-303 (Manufacturer: CYTEC)

Organic solvents: KOCOSOL # 100 / KOCOSOL # 150 (Manufacturer: SK Energy)

Acid catalyst: dinonylnaphthalenesulfonic acid

Amine: Thiriethylamine

Particle: SYLOID 622 (Manufacturer: W.R. Grace)

Additive: LA-45 (Manufacturer: FTC)

The physical properties, surface wrinkles and surface texture of the color steel sheets obtained in Examples 4 to 8 and Comparative Example 2 are shown in Table 4 below.

Properties Comparative Example 2 Example 4 Example 5 Example 6 Example 7 Example 8 Wrinkle Forming Agent × ○ ○ × ○ ○ Anti-wrinkle agent ○ ○ ○ ○ ○ ○ Surface texture No wrinkle Poor surface smoothness wrinkle
Heterogeneity No wrinkle Wrinkle Wrinkle Ink
Site pattern No wrinkle Poor surface smoothness Wrinkle nonuniformity No wrinkle No wrinkle No wrinkle Curing degree Good Good Good Bad Bad Good Machinability Good Good Good Bad Good Good Adhesion Good Good Good Bad Bad Good

As can be seen in Table 4, when no wrinkle forming agent was used in the transparent layer (Comparative Example 2), no wrinkles were formed on the entire surface.

On the other hand, in Examples 4 to 8, surface wrinkles or coating film properties are poor (i.e., surface smoothness, wrinkle nonuniformity, and surface wrinkle non-forming) when some components (i.e., additives, particles, or acid catalysts) are not contained. Except) may occur, wrinkles may be formed on the surface corresponding to a specific pattern or pattern of the printed layer, whereby the surface texture may be exhibited delicately and effectively.

The above description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be.

Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is represented by the following claims, and all changes or modifications derived from the meaning of the claims and the scope of the claims should be construed as being included in the scope of the present invention.

The present invention can be used industrially in the field of PCM color steel sheet, ceramics, tiles, home appliances, building materials, automobiles, indoor and outdoor interiors.

110: offset press
101: ink
102: color steel sheet
111: pattern roll
112: blanket
113: transfer roll or transfer roll
114: printing plate

Claims (13)

A PCM color steel sheet comprising a printed layer and a transparent layer on the base steel sheet including at least one chemical conversion treatment layer, a rust-preventing layer, an undercoat layer, and a base layer, and exhibiting a complex texture by the surface wrinkles of the transparent layer,
The printing layer includes a specific pattern or pattern contained in the amine anti-wrinkle agent;
The transparent layer contains an amine wrinkle forming agent, and has a wrinkle portion having a surface wrinkle and a flat portion having no surface wrinkle on its surface;
A wrinkled portion or a flat portion of the transparent layer is formed in correspondence with a specific pattern or pattern containing a wrinkle inhibitor in the printed layer, PCM color steel sheet showing a composite texture. The method of claim 1,
The printing layer comprises an ink composition comprising 10 to 60% by weight of polyester resin, 1 to 50% by weight of pigment, 35 to 80% by weight of organic solvent, 0.1 to 10% by weight of amine wrinkle inhibitor and 0.1 to 5% by weight of additive. PCM color steel sheet showing a composite texture, characterized in that printed using. The method of claim 1,
The transparent layer is 20 to 60% by weight of polyester resin, 5 to 30% by weight of melamine cured resin, 20 to 70% by weight of organic solvent, 0.1 to 5% by weight of acid catalyst, 0.1 to 3% by weight of amine wrinkle agent, 0.1 to particle It is coated using the transparent layer coating composition containing -10 weight% and 0.1-5 weight% of additives, The color steel plate which shows a complex texture. The method of claim 3, wherein
The particle is a PCM color steel sheet showing a composite texture, characterized in that selected from inorganic particles or organic particles having an average particle size of 5 to 40㎛. The method according to any one of claims 1 to 4,
The amine wrinkle forming agent is characterized in that the melting point is lower than the process temperature (100 to 150 ℃), the boiling point is selected from the group consisting of higher than the process temperature (100 to 150 ℃), PCM exhibiting a complex texture Color steel sheet. The method according to any one of claims 1 to 4,
The amine-based anti-wrinkle agent is characterized in that the boiling point is selected from the group consisting of secondary amine compounds or amine-based light stabilizers (Hindered Amine Light Stabilizer, HALS) higher than the process temperature (100 to 150 ℃), showing a complex texture PCM color steel plate. The method of claim 6,
The amine anti-wrinkle agent dialkylamine, diarylamine, alkylarylamine, N, N- tetraalkylalkylenediamine, 2,5-dialkylpyrrolidine, 2,2,5-trialkylpyrrolidine, 2,2,5,5-tetraalkylpyrrolidine, 2,5-dialkylpiperidine, 2,2,5-trialkylpiperidine, 2,2,5,5-tetraalkylpiperidine and PCM color steel sheet showing a composite texture, characterized in that selected from the group consisting of these derivatives. Method for producing a PCM color steel sheet showing a composite texture by the surface wrinkles of the transparent layer, comprising the following steps (1) to (3):
(1) forming a chemical conversion treatment layer, a rust prevention layer, an undercoat layer, and a base layer in order one or more on the base steel sheet;
(2) printing an ink composition containing an amine wrinkle inhibitor on the base layer to have a specific pattern or pattern to form a printed layer, and
(3) forming a transparent layer by coating a transparent layer coating composition containing an amine wrinkle forming agent on the printed layer. The method of claim 8,
The ink composition comprises 10 to 60% by weight of polyester resin, 1 to 50% by weight of pigment, 35 to 80% by weight of organic solvent, 0.1 to 10% by weight of amine wrinkle inhibitor, and 0.1 to 5% by weight of additive.
The transparent layer coating composition is 20 to 60% by weight polyester resin, 5 to 30% by weight melamine cured resin, 20 to 70% by weight organic solvent, 0.1 to 5% by weight acid catalyst, 0.1 to 3% by weight amine wrinkle forming agent, particles 0.1-10 weight% and 0.1-5 weight% of additives characterized by the above-mentioned. The method of claim 8,
The printing of the printed layer and the coating of the transparent layer are performed by a printing method selected from the group consisting of offset printing, screen printing, gravure printing, flexo printing, and inkjet printing. Manufacturing method. The method of claim 8,
Coating of the transparent layer is carried out by an offset printing method using a flat plate roller, a method for producing a PCM color steel sheet showing a composite texture. The method according to any one of claims 8 to 11,
The amine-based wrinkle forming agent is selected from the group consisting of an amine compound having a melting point lower than the process temperature (100 to 150 ℃) and higher than the process temperature (100 to 150 ℃), PCM color showing a complex texture Method of manufacturing steel sheet. The method according to any one of claims 8 to 11,
The amine-based anti-wrinkle agent is characterized in that the boiling point is selected from the group consisting of secondary amine compounds or amine-based light stabilizers (Hindered Amine Light Stabilizer, HALS) higher than the process temperature (100 to 150 ℃), showing a complex texture Method of manufacturing PCM color steel sheet.

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