JP2009241539A - Printed matter and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printed matter which features a feeling of unevenness, a feeling of sophistication and high designability by view and touch and also, is free from a problem of color contamination due to the peeling of a colorant etc. <P>SOLUTION: This printed matter includes at least, a colored base coat layer and a transparent protecting layer formed thereon, laminated on an object to be printed. In addition, the colored base coat layer and the transparent protecting layer contain microparticles, and at least, some of the microparticles contained in the colored base coat layer, are projected from the surface of the colored base coat layer. The average particle size of the microparticles contained in the transparent protecting layer, is greater than the maximum value of height of the microparticle part projecting from the surface of the colored base coat layer, and further, the microparticles in the transparent protecting layer constitute projecting parts on the surface of the transparent protecting layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a printed matter that has aesthetic irregularities on the surface in terms of visual and tactile properties, is excellent in design, and suppresses peeling of the colorant due to wear, and a method for producing the same.

Conventionally, cosmetic materials have been used as interior and exterior materials for buildings such as entrance doors and partitions, interior materials for vehicles, and surface materials for home appliances. As the decorative material, for example, a decorative material obtained by applying a printed pattern to a metal substrate such as a steel plate or a resin-based substrate, or a decorative material obtained by bonding a resin sheet to a substrate such as a steel plate is known.
In recent years, consumers are demanding high-quality products because of their high-quality products, and as a method of imparting a high-class feeling, there have been contrivances such as visually and tactilely imparting a sense of unevenness to cosmetic materials. . As described above, as a method for giving a feeling of unevenness, a method in which resin beads are contained in the surface protective layer has been proposed (see Patent Documents 1 and 2).

JP-A-7-205387 Japanese Patent Laid-Open No. 10-109392

  However, in the decorative materials described in Patent Documents 1 and 2, the protective layer gives a feeling of unevenness, and the internal colored layer (corresponding to the decorative layer in Patent Document 1 and the printed layer in Patent Document 2). There are no irregularities. In recent years, since a cosmetic material having an even higher quality and an excellent design property has been desired, the present inventors do not give a sense of unevenness with a protective layer, but resin beads and the like during the production of an internal colored layer. As a result, the protective layer was made thin while imparting irregularities to the upper surface of the colored layer, giving it a high-class feel and high design. However, although it has a transparent protective layer on the colored layer, some of the resin beads, etc. protruding from the colored layer appear on the surface of the decorative material due to wear of the surface during normal use, and adhere to the resin beads. A new problem has arisen that causes the coloring agent to peel off and cause contamination.

  The present invention has been made under such circumstances, and solves the above-mentioned problems, has a sense of unevenness in terms of visual and tactile sensation, has a high-class feeling and high design properties, and has no color contamination. And it aims at providing the manufacturing method.

As a result of intensive studies to achieve the above object, the present inventor has, as a result, a colored base coat layer containing at least (1) specific fine particles, and at least one fine particle protruding from the layer, and On the colored base coat layer, (2) if it is a printed matter containing specific resin beads and / or glass beads, and preferably having a transparent protective layer having a thickness of 1 to 5 μm, it has a high-class feeling and low coloring contamination. It was found that both could be satisfied. The present invention has been completed based on such findings.
That is, the present invention
[1] A printed material having at least a colored base coat layer and a transparent protective layer thereon on the substrate, wherein the colored base coat layer and the transparent protective layer each contain fine particles, and at least some of the fine particles in the colored base coat layer Protrudes from the surface of the colored base coat layer, and the fine particles in the transparent protective layer have an average particle size larger than the maximum value of the height of the fine particles protruding from the colored base coat layer surface, and are convex on the surface of the transparent protective layer. Printed matter characterized by forming,
[2] The printed matter according to the above [1], wherein the thickness of the transparent protective layer (not considering convex portions due to fine particles) is 1 to 5 μm,
[3] The printed matter according to the above [1] or [2], wherein the maximum value of the fine particle portion protruding from the surface of the colored base coat layer is 1 to 30 μm.
[4] The average particle diameter of the fine particles in the transparent protective layer is any one of the above [1] to [3], which is 5 to 70 μm larger than the maximum value of the height of the fine particles protruding from the colored base coat layer. Printed matter,
[5] Any of the above [1] to [4], wherein the fine particles in the colored base coat layer and the fine particles in the transparent protective layer are at least one selected from the group consisting of resin beads, glass beads, and a matting agent, respectively. Or printed matter according to claim 1,
[6] The printed material according to any one of the above [1] to [5], which has a primer layer between the printing material and the colored base coat layer,
[7] The printed matter according to any one of the above [1] to [6], which has a pattern print layer between the colored base coat layer and the transparent protective layer,
[8] The printed material according to any one of [1] to [7], in which the substrate is a steel plate, a resin sheet, or a resin film.
[9] The printed material according to any one of [1] to [8], which is used for an entrance door or a partition,
[10] A method for producing a printed material having at least a colored base coat layer and a transparent protective layer thereon on the substrate, wherein the curtain flow coat method or roll is used so that at least some of the fine particles protrude from the surface of the colored base coat layer. A process for producing a colored base coat layer by a coating method, and a gravure printing, gravure offset printing or roll coating method for transparent ink containing fine particles having an average particle size larger than the maximum height of the fine particle portion protruding from the colored base coat layer surface A process for producing a protective layer in which fine particles form protrusions on the surface thereof,
Is to provide.

  According to the present invention, it is possible to provide a printed matter that is visually and tactilely concavo-convex, has a high-class feeling, and does not cause a problem of color contamination due to peeling of a colorant or the like.

As described above, the printed material of the present invention is a printed material having at least a colored base coat layer and a transparent protective layer on the printed material,
The colored base coat layer and the transparent protective layer each contain fine particles, and at least some of the fine particles in the colored base coat layer protrude from the colored base coat layer surface,
The fine particles in the transparent protective layer have an average particle size larger than the maximum value of the height of the fine particles protruding from the surface of the colored base coat layer, and have convex portions formed on the surface of the transparent protective layer.
It is the printed matter characterized by this.
Hereinafter, the printed matter and the manufacturing method thereof will be described in detail.

[Substrate]
Typical materials for printed materials are metallic materials and inorganic non-metallic materials (ceramics, non-ceramic ceramics, etc.), but other materials such as resin-based materials and wood-based materials can also be mixed. Composite materials such as system materials and laminates may be used. Among these, a metal material is preferable.

Examples of the metal-based material include metals such as iron, stainless steel, and aluminum, and a plate shape (metal plate) is preferable.
Examples of the metal plate include plate materials such as mild steel plate, electroformed iron foil, stainless steel plate, aluminum plate, duralumin plate, and steel plate, or one or two types of zinc, tin, aluminum, copper, chromium, nickel, etc. What was plated by the above is mentioned. Examples of the two or more types of plating include an alloy plating of iron and zinc and an alloy plating of aluminum and zinc. Specific examples of the plated metal plate include an electrogalvanized steel sheet, an alloy hot dip galvanized steel sheet, a hot dip galvanized steel sheet, and an aluminum alloy hot dip galvanized steel sheet. Although there is no restriction | limiting in particular in the thickness of these metal plates, Usually, the thickness of 0.3-2 mm can be preferably used, More specifically, thickness, such as 0.4 mm, 0.5 mm, and 0.6 mm Can be preferably used.

  Examples of the resin material include polyolefin resins such as polyethylene, polypropylene, and olefin thermoplastic elastomer, resins such as polyvinyl chloride, acrylic resin, thermoplastic polyester resin, thermoplastic urethane resin, ABS, and polystyrene. These may be commercial products. The resin material is preferably in the form of a sheet or film.

[Primer layer]
The printed material of the present invention has a colored base coat layer on the printed material, but may have a primer layer between the printed material and the colored base coat layer in order to improve their adhesion. The material for the primer layer is not particularly limited as long as it improves the adhesion between the substrate to be printed and the colored base coat layer. For example, polyester resin such as alkyd resin, urethane resin, epoxy resin, melamine resin, phenol resin, A curable coating material in which a crosslinking agent is added to a known resin containing a thermosetting resin such as an acrylic resin can be used. In particular, those obtained by adding a melamine-based crosslinking agent to an unsaturated polyester resin using a sulfonate-based curing catalyst are preferable.
The primer layer can be formed by applying and drying the above-described material on a substrate to be printed by a roll coating method, and further baking and drying at 200 to 250 ° C. in the case of a heat-resistant substrate. Although there is no restriction | limiting in particular in the thickness of the primer layer obtained in this way, Usually, it is preferably 1-10 micrometers, More preferably, it is 1-3 micrometers.
Further, instead of providing the primer layer, for example, surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment may be performed.

[Colored base coat layer]
The colored base coat layer on the printing material or the primer layer is a layer expressing the basic color of the entire design of the obtained printed material.
Such a colored base coat layer comprises at least (a) a binder resin, (b) a colorant, (c) fine particles (5) (numbers correspond to the reference numerals in FIG. 1) [component (a) and component (b), respectively. , May be abbreviated as component (c). ] Is formed. If necessary, extend pigments, weather resistance agents, light resistance agents, surface slipping waxes, and the like may be added to the colored base coat layer.

  (A) As a binder resin, when a to-be-printed material consists of metal type materials, a thermosetting resin is preferable. Examples of the thermosetting resin include polyester resins such as alkyd resins, urethane resins, epoxy resins, melamine resins, phenol resins, acrylic resins, and aminoplast resins. When the obtained printed matter is subjected to bending or the like, a polyester resin having a weight average molecular weight of 8000 or more is suitable.

(B) As the colorant, a known colorant can be used. For example, when the printing material is made of a metal material, carbon black, iron black, titanium white, titanium yellow, yellow iron oxide, antimony white, zinc oxide, Examples include inorganic pigments such as petals, bitumen, and cobalt blue; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments;
These colorants may be used alone or in combination of two or more.
The amount of component (b) used is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the binder resin.

(C) As the fine particles (5), for example, glass beads, matting agents, resin beads and the like are preferably mentioned. These may be used individually by 1 type and may use 2 or more types together.
Preferred examples of the matting agent include silica, talc, calcium carbonate, barium sulfate, and calcium silicate. These may be commercial products.
Examples of resin beads include thermosetting acrylic resin beads, thermosetting urethane resin beads, benzoguanamine / formaldehyde condensate beads, benzoguanamine / melamine / formaldehyde condensate beads, urea resin beads, nylon resin beads, Examples of the plastic resin beads include polyamide beads, acrylic beads, polyolefin beads, polycarbonate beads, and polystyrene beads. Among these, nylon resin beads are preferable. These may be used individually by 1 type, and may mix and use 2 or more types.
The fine particles (5) are preferably fine particles having an average particle diameter of 10 to 30 μm, more preferably fine particles having an average particle diameter of 15 to 25 μm. Furthermore, fine particles having an average particle diameter of 5 μm or less and fine particles having an average particle diameter exceeding 30 μm may be used in combination. In particular, fine particles having a peak indicating two or more particle groups in the particle size distribution are preferable, and it is more preferable to use two types of fine particles having an average particle size of 5 to 13 μm and fine particles having an average particle size of 18 to 25 μm in combination.
The usage-amount of a component (c) becomes like this. Preferably it is 1-10 mass% with respect to all the components which form a colored basecoat layer, More preferably, it is 1-5 mass%.

A base color paint obtained by mixing at least the above components (a) to (c) is applied to a printed material or a primer layer using a curtain flow coat method or a roll coat method, and is not sticky when touched. By drying to the extent, a colored base coat layer can be formed. In the colored base coat layer obtained in this way, a part of the fine particles to which the colorant is attached protrudes randomly from the upper surface. The maximum height of the protruding portion is preferably 1 to 30 μm, more preferably 5 to 20 μm, and the usage amount of component (b) and the usage amount of component (c) are appropriately adjusted. Therefore, it can be within this range. Due to the protrusion of the fine particles (5) from the colored base coat layer, the refraction of light caused by the fine particles, the tactile sensation due to finger touch, etc., it is possible to impart aesthetic and high-quality unevenness to the finally obtained printed matter. .
Although there is no restriction | limiting in particular in the thickness (The protrusion part of the said microparticles | fine-particles is included) of a coloring basecoat layer, Usually, it is preferably 10-50 micrometers, from a viewpoint which makes the protrusion of the microparticles | fine-particles from the coloring basecoat layer surface remarkable. Is more preferably 15 to 30 μm, still more preferably 15 to 25 μm.

[Pattern printing layer]
A pattern printing layer may be provided on the colored base coat layer for the purpose of improving design properties.
As the paint for forming the pattern print layer, one containing the following binder resin and colorant can be used. As the binder resin, for example, a thermosetting resin such as a polyester resin such as an alkyd resin, a urethane resin, an epoxy resin, a melamine resin, a phenol resin, or an acrylic resin is preferable in terms of surface properties. Examples of the colorant include known colorants such as inorganic pigments such as carbon black, iron black, titanium white, titanium yellow, antimony white, zinc oxide, dial, bitumen, cobalt blue; aluminum powder, bronze powder, and the like. Examples thereof include metal powder pigments; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; Commercial products may be used for these binder resins and colorants.
Examples of the design include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, an abstract pattern, and a solid pattern. The thickness of the pattern print layer is preferably 1 to 3 μm, more preferably 1 to 2 μm. In addition, the gravure offset printing method can be used for patterning.

[Transparent protective layer]
Transparent on the colored base coat layer or pattern print layer by a mixture of fine particles (7) (the numbers correspond to the reference numerals in FIG. 1) and a thermosetting resin, thermoplastic resin or ionizing radiation curable resin. A protective layer is formed.
Examples of the thermosetting resin include thermosetting resins such as thermosetting polyester resins, thermosetting urethane resins, epoxy resins, melamine resins, alkyd resins, phenol resins, thermosetting acrylic resins, and printed materials are made of metal. It is preferably used when it is a heat-resistant material such as a system material. These may be commercial products.
Examples of the thermoplastic resin include a polyester resin, an acrylic resin, a polyolefin resin, a vinyl chloride resin, and a fluororesin, and are preferably used when the printed material is a non-heat resistant material. These may be commercial products.
As the ionizing radiation curable resin, a composition in which prepolymers, oligomers, and / or monomers having a polymerizable unsaturated bond or an epoxy group in the molecule are appropriately mixed is used. Examples of these compositions include acrylates such as urethane acrylate, polyester acrylate, and epoxy acrylate, silicon resins such as siloxane, polyester resins, unsaturated polyester resins, epoxy resins, phenol resins, and polyurethane resins. It is preferably used when the substrate is a heat resistant material such as a metal-based material. These may be commercial products.

Examples of the fine particles (7) include glass beads and resin beads. Glass beads and resin beads are preferable, and resin beads are particularly preferable. Moreover, these may be used individually by 1 type and may use 2 or more types together. The fine particles are transparent or translucent.
Examples of the resin beads include acrylic resin beads, urethane resin beads, benzoguanamine / formaldehyde condensate beads, benzoguanamine / melamine / formaldehyde condensate beads, urea resin beads, nylon resin beads, and thermoplastic resin beads such as polyamide. System beads, acrylic beads, polyolefin beads, polycarbonate beads, polystyrene beads and the like. Among these, nylon-based resin beads and urethane-based resin beads are preferable in that they can provide touch feeling by finger touch and visual design. These may be used individually by 1 type, and may mix and use 2 or more types.
The average particle diameter of the fine particles (7) to be contained in the transparent protective layer is preferably 5 to 70 μm, more preferably 10 to 50 μm, and even more preferably the maximum value of the height of the fine particles protruding from the colored base coat layer. Is larger by 10 to 30 μm, usually preferably an average particle size of 10 to 75 μm, more preferably an average particle size of 10 to 50 μm, and still more preferably an average particle size of 15 to 30 μm.
The transparent protective layer contains fine particles (8) having an average particle size smaller than the average particle size of the fine particles (7) (the numbers correspond to the reference numerals in FIG. 1) in order to adjust the gloss. The average particle diameter of the fine particles (8) is most preferably 5 μm or less. By including the fine particles (8), the unevenness of the matting effect that occurs in the portion where the fine particles (7) are present in the transparent protective layer and the portion where they are absent is reduced, and a printed matter having a uniform matt surface is obtained. be able to. As the fine particles (8), conventionally known materials can be used as long as they can impart a matting effect, and preferred examples include silica, talc, calcium carbonate, barium sulfate, and calcium silicate.
The transparent protective layer may contain acrylic resin beads, urethane resin beads, nylon resin beads having an average particle size of 5 μm or less.
The amount of the fine particles (7) used [when the fine particles (8) having different average particle diameters are used in combination, the total amount of them used] is preferably relative to 100 parts by mass of the thermosetting resin or thermoplastic resin. It is 0.5-40 mass%, More preferably, it is 0.5-20 mass%.
By including the fine particles (7) in the transparent protective layer, there is a problem of color contamination due to the colorant present on the surface of the fine particles (5) contained in the colored base coat layer due to wear of the surface of the obtained printed matter. Can be reduced.

A mixture of the fine particles and a thermosetting resin, a thermoplastic resin, or an ionizing radiation curable resin, a known coating method such as a roll coating method, a flow coating method, a spray coating method, a gravure printing method, a gravure offset printing method, When ionizing radiation curable resin is used after coating on a colored base coat layer or pattern print layer by a known printing method such as a silk screen printing method and drying, ultraviolet rays or electron beams are irradiated. On the other hand, in the case of a thermosetting resin or a thermoplastic resin, and the substrate to be printed is a steel plate or a heat-resistant resin plate, the ambient temperature is increased by a known heating method such as hot air heating or far infrared heating. By heat-processing at 180-280 degreeC, Preferably it is 200-250 degreeC, each layer can be hardened completely and the printed matter which has a transparent protective layer on the surface can be obtained.
In the present invention, the thickness of the transparent protective layer (not considering the height of the fine particles) is preferably 1 to 5 μm, more preferably 1 to 4 μm so as not to impair the aesthetic unevenness. More preferably, it is 1 to 3 μm.
The printed matter of the present invention imparts light refraction, tactile sensation by finger touch, etc. by the fine particles (5) in the colored base coat layer, the fine particles (7) in the transparent protective layer, and the fine particles (8) in the transparent protective layer The obtained printed matter has a visually high design and becomes a printed matter having an uneven tactile sensation.

Hereinafter, although the example of a structure of the printed matter of this invention is demonstrated easily using FIG. 1, this invention is not restrict | limited especially by FIG.
FIG. 1 shows that a primer layer (3) is formed on a substrate (2), and a colored base coat layer (4) in which a part of fine particles (5) to which a colorant is attached protrudes from the layer is formed. Furthermore, it is an example of a printed matter (1) on which a transparent protective layer (6) containing fine particles (7) and fine particles (8) is further formed. The fine particles (7) are sufficiently larger than the height (A) of the fine particle portions protruding from the colored base coat layer (4). Thereby, coloring contamination can be prevented simultaneously, maintaining a high-class feeling and high designability.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

<Example 1>
Using a 0.6 mm thick iron-zinc alloy hot-plated steel sheet (silver alloy) as the substrate to be printed, a thermosetting polyester resin primer is applied to the surface of the steel sheet by a roll coating method and dried. After forming a 2 μm primer layer, it was baked and dried at about 230 to 240 ° C. Subsequently, a brown paint [binder resin: colorant = 100: 20 (mass ratio)] composed of a thermosetting polyester resin having a weight average molecular weight of 8000 or more, carbon black, titanium white, a petite, and yellow iron oxide, and fine particles Nylon transparent resin beads having an average particle diameter of 10 μm and nylon transparent resin beads having an average particle diameter of 20 μm [approximately 3: 1 (mass ratio)] were mixed [the brown paint: total resin beads = 100: 4 (mass ratio). The base color paint thus obtained was applied by the curtain flow coat method and dried to the extent that the paint did not adhere to the finger by finger touch to form a colored base coat layer having a thickness of 20 μm. Here, it was confirmed that the maximum height of the fine particle portion protruding from the colored base coat layer was 7 μm. On the colored base coat layer, a pattern printing layer having a grain pattern thickness of 2 μm was formed by a gravure offset printing method using a polyester resin ink. Furthermore, a thermosetting polyester resin [thermosetting polyester resin: resin beads = 10: 15 (mass ratio)] mixed with nylon transparent resin beads having an average particle diameter of 20 μm was applied and dried by a gravure offset printing method, A transparent protective layer of 3 μm (not considering resin beads) was formed. Finally, heat drying was performed at 250 ° C. to completely cure each layer.
The surface (protective layer part) of the printed matter thus obtained does not appear fine particles protruding from the colored base coat layer due to wear in normal use even though the protective layer is thin, and adheres to the fine particles. The colorant is not a problem.

  The printed matter of the present invention is a printed matter that is visually and tactilely concavo-convex, has a high-class feeling and high design properties, and has no color stains, and is laminated as it is as a cosmetic material or on an adherend. It can be suitably used for various applications as a decorative material.

It is an example of the laminated constitution of the printed matter of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Printed material 2 To-be-printed material 3 Primer coat layer 4 Colored base coat layer 5 Fine particle 6 Transparent protective layer 7 Fine particle 8 Fine particle A Height of the fine particle part which protrudes from the colored base coat layer

Claims (10)

  A printed material having at least a colored base coat layer and a transparent protective layer thereon on the substrate, wherein the colored base coat layer and the transparent protective layer each contain fine particles, and at least some of the fine particles in the colored base coat layer are colored base coats. The fine particles in the transparent protective layer protrude from the surface of the layer, and the average particle diameter is larger than the maximum value of the height of the fine particles protruding from the colored base coat layer surface, and convex portions are formed on the surface of the transparent protective layer. Printed matter characterized by that.   The printed matter according to claim 1, wherein the transparent protective layer has a thickness of 1 to 5 μm (not considering convex portions due to fine particles).   The printed matter according to claim 1 or 2, wherein the maximum height of the fine particle portion protruding from the surface of the colored base coat layer is 1 to 30 µm.   The printed matter according to any one of claims 1 to 3, wherein the average particle size of the fine particles in the transparent protective layer is 5 to 70 µm larger than the maximum value of the height of the fine particle portion protruding from the colored base coat layer.   The fine particles in the colored base coat layer and the fine particles in the transparent protective layer are at least one selected from the group consisting of resin beads, glass beads, and a matting agent, respectively. Printed matter.   The printed material according to any one of claims 1 to 5, which has a primer layer between the material to be printed and the colored base coat layer.   The printed matter according to any one of claims 1 to 6, further comprising a pattern print layer between the colored base coat layer and the transparent protective layer.   The printed material according to claim 1, wherein the material to be printed is a steel plate, a resin sheet, or a resin film.   The printed matter according to any one of claims 1 to 8, which is used for an entrance door or a partition. A method for producing a printed material having at least a colored base coat layer and a transparent protective layer thereon on the substrate,
A step of producing a colored base coat layer by a curtain flow coat method or a roll coat method so that at least some of the fine particles protrude from the surface of the colored base coat layer, and a value greater than the maximum height of the fine particle portion protruding from the surface of the colored base coat layer A step of producing a protective layer in which fine particles form convex portions on the surface by applying a transparent ink containing fine particles having an average particle diameter by gravure printing, gravure offset printing or roll coating method;
A method for producing printed matter containing

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