Patent Application
20230364640
The present disclosure relates to a matte article.
Conventionally, so-called decorative materials or sheets have been used as articles to decorate and protect surfaces of, for example, interior members of buildings such as, walls, ceilings, and floors; exterior members such as exterior walls, eaves ceilings, roofs, fences, and rails; fixture or fitting members such as window frames, doors, door frames, railings, baseboards, trims, and moldings; general furniture such as chests, shelves, and desks; kitchen furniture such as dining tables and sinks; surface decorative boards such as cabinets for home appliances and OA equipment; or vehicle interior or exterior members. For example, such decorative members used have a surface layer with a desired function.
In order to improve the design of decorative materials used for these applications, a matte effect (also called “matting effect”) is commonly used as a technique to improve the texture of decorative materials. As a decorative material using the matte effect, for example, PTL1 discloses a decorative sheet having a pattern layer and a concealed layer on one side of a base sheet and a gloss adjustment layer such as a matte layer and a gloss layer on the other side. In the decorative sheet of PTL1, the difference in gloss between the matte layer and the gloss layer of the gloss adjustment layer can cause a design effect so that the pattern layer and the concealed layer stand out. In the Example, the matte layer provided over the entire surfaces is created using a matte ink obtained by adding the total 50 parts by weight of matting agent, namely 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, per 100 parts by weight of resin.
In addition, PTL2 discloses a decorative material including, on a base material, a printing layer and a transparent resin layer in sequence, and an embossed pattern on the top surface of the transparent resin layer.
Representative examples of the method to improve the texture by matte effect include: a method using a matting agent (also called a “matte agent”) to achieve a matte effect by its own light diffusion effect, as in the above-mentioned PTL1; or a method to form an uneven shape on the topmost surface by embossing, as in the above-mentioned PTL2.
Meanwhile, when a matting agent is used as in PTL1, the amount used should be increased to achieve a better matte effect. As the amount of the matting agent used increases, the surface properties tend to deteriorate due to the following reasons: the matting agent drops out of a coating film and damages the coating film, resulting in reduced scratch resistance; scratches are also more visible due to change in gloss caused by lack of matting agent; or contaminants infiltrate a micro-gap at the interface between the matting agent and the resin and in addition, the contaminants are absorbed onto the matting agent itself, resulting in reduced contamination resistance. On the other hand, the matte effect tends to decrease when the amount used is reduced in order to suppress the deterioration of surface properties. There is an antinomic relationship between the surface properties and the matte effect. Therefore, there is a limit to the matting effect while using a matting agent.
When the embossing process is used as in PTL2, preparation of an embossing plate is not easy as it requires a great deal of time and effort, and furthermore, it is necessary to prepare the plate for each desired pattern. Therefore, it cannot be said that this method can sufficiently respond to the diversity of customer demands.
By the way, the diversity of customer demands is large, and not only the visual matte effect as described above, but also tactile expression is required. For example, when using a matting agent as in the above PTL1, increasing the amount used may cause the contours of the matting agent to be exposed on the surface of the decorative sheet, resulting in somewhat rough touch sensation. When embossing is used as in PTL2, tactile sensation may develop due to the uneven shape of the surface formed by the embossing plate. However, in either case, the focus is not on the tactile expression, and it cannot be said that the tactile sensation is sufficient in terms of touch. That is, conventional decorative sheets or materials cannot be said to provide both excellent matte effect and tactile sensation. The present disclosure focuses on a “dry and smooth” touch among the tactile sensations.
The present disclosure addresses the problem of providing a matte article with excellent matte effect visibility and texture and with an excellent dry and smooth touch.
In order to solve the above problems, the present disclosure provides a matte article comprising, on at least a part of a surface thereof, a surface shape with a skewness (Ssk) of 0.00 or more and a kurtosis (Sku) of 3.50 or less as specified in ISO25178-2:2012.
The present disclosure makes it possible to provide a matte article with excellent matte effect visibility and texture and an excellent dry and smooth touch.
[Matte Article]
Hereinbelow, a matte article of the present disclosure will be described. Note that as used herein, the numerical values for “A or more”, “B or less”, and “from A to B” in terms of the numerical value range are numerical values optionally combined; and the numbers in Examples are numbers that can be used for the upper and lower limits of the numerical range.
A matte article of the present disclosure has, on at least a part of a surface thereof, a surface shape with a skewness (Ssk) of 0.00 or more and a kurtosis (Sku) of 3.50 or less as specified in ISO25178-2:2012.
[Surface Shape]
The following describes the surface shape which the matte article of the present disclosure has on at least a part of a surface thereof (hereinafter, simply referred to as “surface shape”).
The surface shape should have a skewness (Ssk) of 0.00 or more and a kurtosis (Sku) of 3.50 or less as specified in ISO25178-2:2012. Such a surface shape causes the matte article of the present disclosure to exhibit excellent matte effect visibility and texture, as well as tactile sensation, namely a particularly “dry and smooth” touch. Here, the “matte effect visibility and texture” is hereinafter sometimes simply referred to as the “matte effect”.
While the “dry and smooth” touch is a sensual expression, the “dry and smooth” herein encompasses all tactile sensations that are generally perceived as “dry and smooth”. Specifically, the term means a touch sensation felt when a non-wet smooth surface is touched with the belly of a finger.
An article with a “dry and smooth” touch cannot be generalized because of, for instance, the surface processing or weaving if the article is a cloth described later. Examples include fine paper which is not coated paper with a coated surface; Fabrics such as oxford fabrics made of fine yarns of 60 to 120 count, which is said to be fine to ultrafine count yarns; and baby skins. Other examples of the article capable of having a “dry and smooth” touch include: Fabrics made of natural fibers such silk or tencel (also called “lyocell”); and metals such as brass, gold, silver, copper, aluminum, steel and stainless steel, in particular, metals with various surface finishes such as hairline, hairline, or silky blast processing. Note that some surface finishes such hairline or silky blast processing on metals may cause a “non-dry-and-smooth” touch sensation depending on, for instance, the degree of processing. Here, it is needless to say that such processed articles are not included. In addition, there are other cloths that do not have a “dry and smooth” touch, depending on the thickness of yarn used, the weaving, and other factors. Here, it is needless to say that such cloths are not included.
Therefore, matte articles of the present disclosure are preferably used for applications where the design of, for instance, surfaces of these cloths or metals is put into practice. In this case, the matte article of the present disclosure preferably have a decorative layer with a surface pattern of each material such as cloth or metal so as to express the desired design. The decorative layer, which may be included in a matte article of the present disclosure, will be described in detail later.
Ssk (skewness) is one of the three-dimensional surface property parameters specified in ISO above, and is an index that indicates the degree of deviation of the height distribution relative to the mean plane. When Ssk is 0, the surface shape is symmetrical with respect to the mean plane. When Ssk exceeds 0, the surface shape is biased toward the lower side of the mean plane, i.e., the height is biased toward the lower side. This measurement value can be understood as a tendency where the convex portion has a pointed narrow top section. Here, the wording “symmetrical with respect to the mean plane” can also be called “normally distributed”.
On the other hand, when Ssk is less than 0, the surface shape is biased toward the upper side of the mean plane, i.e., the height is biased toward the upper side. This measurement value can be understood as a tendency where the convex portion has a blunt and thick top section.
In relation to Sku (kurtosis) described below, Ssk (skewness) is preferably 0.03 or more, more preferably 0.05 or more, and the upper limit is preferably 1.50 or less, preferably 1.00 or less, more preferably 0.75 or less, and still more preferably 0.50 or less. When Ssk (skewness) is within the above range, the matte effect and the dry and smooth touch are improved.
Ssk (skewness) is determined as a measurement value measured using a shape analysis laser microscope on a rectangle (1024 μm×768 μm) of any part of the surface shape of a matte article. The measurement conditions may be adjusted as needed, and for example, the conditions described in Examples can be used for the measurement. In addition, Sku (kurtosis), which will be described later, and RSm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) for contour curves may also be likewise measured.
Sku (kurtosis) is one of the three-dimensional surface property parameters specified in ISO above, and is an index that indicates the degree of kurtosis of the height distribution relative to the mean plane. Sku is a measurement value that provides a tendency in which the surface shape is symmetrical (normally distributed) with respect to the mean plane when Sku is 3, the height distribution has a pointed shape when Sku exceeds 3, and the height distribution has a collapsed shape when Sku is less than 3.
In relation to Ssk (skewness) described previously, Sku (kurtosis) is preferably 2.95 or less, and the lower limit is preferably 1.00 or greater, more preferably 1.50 or greater, still more preferably 2.00 or greater, and still more preferably 2.30 or greater. When Sku (kurtosis) is within the above range, the matte effect and the dry and smooth touch are improved.
The surface shape of a matte article of the present disclosure has a specific Ssk (skewness) and Sku (kurtosis), as already described, and combines the feature that a larger number of convex portions with an elongated cross-sectional shape that have a narrow width with respect to the height in accordance with Ssk (skewness) and have a higher aspect ratio, and are distributed at a certain distance from each other; and the feature that the shape near the top section of each convex portion is rounded in accordance with Sku (kurtosis).
The surface shape of a matte article of the present disclosure is rounded near the top of each convex portion, and there are many elongated convex portions. This allows the user to feel a rounded tip shape when touched with the belly of a finger at a suitable contact frequency. Such a sensation seems to lead to a tactile sensation felt when a non-wet smooth surface is touched, i.e., a “dry and smooth” touch. In addition, the presence of such convex portions is considered to exert a matte effect because of having, in turn, concave portions. The details of how the matte effect is expressed will be described later.
The surface shape of a matte article of the present disclosure should have a micro-wrinkle(s) (creases) visible in the plan view shown in
In order to have Ssk (skewness) and Sku (kurtosis) within the above specific numerical range, and preferably have the RSm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) as described below, in the surface shape of the matte article, it is preferable that, as already mentioned;
By optimizing these parameters, in the surface shape of a matte article of the present disclosure, it is more likely to set the Ssk (skewness) and Sku (kurtosis) within the above specific numerical range, and preferably to set the RSm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) as described below within a given numerical range.
In this disclosure, the surface shape preferably has an RSm (average length of curve elements), which is a parameter of the contour curve in the transverse direction as specified in JIS B0601:2013, of 100.00 μm or less.
The RSm (average length of curve elements) is a transverse parameter of the contour curve and is the average of the lengths of the contour curve elements with a reference length. The smaller the value of RSm (average length of curve elements), the narrower the width of each convex portion, thus the RSm is an indicator that indicates the trend in which the surface shape have convex portions with a narrow width. Thus, the RSm (average length of curve elements) may be 100.00 μm or less for the surface shape satisfying the above Ssk (skewness) and Sku (kurtosis). In this case, the width of each convex portion included in the surface shape becomes narrower and its tip is rounded. This caused the tip shape of each convex portion to be rounded as defined by the previously described Sku (kurtosis). This feature is emphasized, and the dry and smooth touch is improved. In addition, the matte effect can also be enhanced.
The RSm (average length of curve elements) is preferably 90.00 μm or less, more preferably 75.00 μm or less, still more preferably 60.00 μm or less, and still more preferably 40.00 μm or less, and the lower limit is preferably 15.00 μm or greater, more preferably 17.50 μm or greater, and still more preferably 20.00 μm or greater. When the RSm (average length of curve elements) is within the above range, the matte effect and the dry and smooth touch are improved.
Note that when the RSm (average length of curve elements) is measured herein, the cut-off value is 0.8 mm.
In the present disclosure, the surface shape preferably has an Rz (maximum height), which is a parameter of the contour curve in the transverse direction as specified in JIS B0601:2013, of 3.00 μm or more.
The Rz (maximum height) is one of the peak and height parameters of the contour curve and is the sum of the height of the highest peak and the depth of the deepest valley in the contour curve with a reference length. The larger the value of Rz (maximum height), the larger (higher) convex portions exist in terms of the valley, thus the Rz is an indicator that indicates the trend in which such convex portions exist. Thus, when the Rz (maximum height) is 3.00 μm or higher for the surface shape that satisfies the above Ssk (skewness) and Sku (kurtosis), the feature that the tip shape of each convex portion is rounded according to the above-mentioned Sku (kurtosis) is emphasized, and the dry and smooth touch is improved. In addition, the matte effect can also be enhanced.
The Rz (maximum height) is preferably 3.25 μm or higher, more preferably 3.50 μm or higher, and still more preferably 4.00 μm or higher, and the upper limit is preferably 12.50 μm or less, more preferably 11.50 μm or less, and still more preferably 10.50 μm or less. When the Rz (maximum height) is within the above range, the matte effect and the dry and smooth touch are improved.
Note that when the Rz (maximum height) is measured herein, the cut-off value is 0.8 mm.
In the present disclosure, the surface shape preferably has an Ra (arithmetic mean roughness), which is a parameter of the contour curve in the transverse direction as specified in JIS B0601:2013, of 2.00 μm or less.
The Ra (arithmetic mean roughness) is one of the parameters of the contour curve in the height direction, and is the average value of the height difference from the mean plane between the contour curves with a reference length. The smaller the value of Ra (arithmetic mean roughness), the smaller the convex portions in the surface shape and the smaller the concave portions formed accordingly, thus the Ra is an indicator that indicates the trend in which the shape is smoother and more uniform. Thus, when the Ra (arithmetic mean roughness) is 2.00 μm or less for the surface shape that satisfies the above Ssk (skewness) and Sku (kurtosis), there exists a greater number of convex portions having a more uniform and gentler shape in the surface shape, which can suppresses an outlandish tactile sensation, and, in particular, improves a dry and smooth touch. In addition, the matte effect can also be enhanced.
The Ra (arithmetic mean roughness) is preferably 1.90 μm or less, more preferably 1.80 μm or less, and still more preferably 1.75 μm or less, and the lower limit is preferably 0.10 μm or larger, more preferably 0.40 μm or larger, and still more preferably 0.60 μm or larger. When the Ra (arithmetic mean roughness) is within the above range, the matte effect and the dry and smooth touch are improved.
Note that when the Ra (arithmetic mean roughness) is measured herein, the cut-off value is 0.8 mm.
[About Layer Structure]
The matte article of the present disclosure is not limited in terms of a layer structure and any layer structure may be adopted, as long as the surface shape has the shape according to the above parameters. In this case, the layer structure is not limited, and any layer structure may be adopted.
The simplest layer structure that the matte article of the present disclosure has is a single layer structure as shown in
In addition, from the viewpoint of flexibly corresponding to various performance requirements such as the mechanical strength, suitability for post-processing, and design appearance of an article in accordance with various demands, and/or from the viewpoint of, for instance, suitability for manufacturing and suitability for handling, the examples also include an article composed of a laminate produced by laminating multiple layers as shown in
The following describes each layer constituting a matte article of the present disclosure, starting with layers constituting a laminate having a base material and a cured product layer (a matte layer) having the above surface shape on at least a part thereof, which case is one of the preferred embodiments of an article including a laminate.
[Base Material]
The base material for forming a matte article of the present disclosure has no particular restrictions on its form (or shape). It is possible to preferably adopt the base material from various kinds of shapes such as films, sheets, plates, polyhedrons, polygonal columns, cylinders, spheres, or rotary ellipsoids. Here, films, sheets, and plates are referred to as films, sheets, and plates in terms of their relative thinness. However, as used herein, there is no particular significance in making a strict distinction among these three. The differences among films, sheets and plates should not cause any differences in the interpretation of the right of the present disclosure. Therefore, as used herein, film(s), sheet(s), and plate(s) are sometimes collectively referred to as, for example, “sheet(s)” or “sheet-shaped”.
When the matte article of the present disclosure is composed of a laminate, the shape of the base material is preferably a sheet. When the base material is in the form of a sheet, the suitability for manufacturing is improved. In addition, since the base material can be easily integrated with a resin molding by, for instance, adhesion, the suitability for post-processing is improved.
Examples of a material constituting the base material include, but are not limited to, a resin, a metal, a non-metallic inorganic material, a fibrous material, or a woody material. Each material may be selected, if appropriate, depending on its application. A single layer of base material made of these various materials or a combination of two or more layers of base material made of these various materials may be used. In the case of multiple layers, two or more different material layers may be stacked and integrated to complement the functions of the materials in each layer.
When a base material having multiple layers is adopted, the following forms are preferred, where each layer constituting the multi-layer is described as, for example, a layer made of material A and a layer made of material B, and a laminate consisting of these layers is denoted as “A/B”:
In addition, when the base material has multiple layers, the base material may further have, between each of the multiple layers, an adhesive layer, a bonding agent layer, or a primer layer (also called an anchor layer or an easy-to-adhere layer) as a layer to increase adhesion between adjacent layers.
Examples of the resin that can be used for a base material include each synthetic resin or natural resin. Examples of the synthetic resin include a thermoplastic resin or a curable resin. Preferred is a thermoplastic resin in consideration of the suitability for manufacturing, handling, and post-processing of a matte article.
Examples of the thermoplastic resin include: an olefin resin such as polyethylene, polypropylene, polymethylpentene, an ionomer, and each olefin-based thermoplastic elastomer; a vinyl chloride resin such as polyvinyl chloride, polyvinylidene chloride, and a polyvinyl chloride-vinyl acetate copolymer; a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, an ethylene glycol-terephthalic acid-isophthalic acid copolymer, and a polyester-based thermoplastic elastomer; an acrylic resin such as poly(methyl(meth)acrylate), poly(ethyl(meth)acrylate), poly(butyl(meth)acrylate), and a (methyl(meth)acrylate)-(butyl(meth)acrylate) copolymer; a polyamide resin represented by, for instance, nylon 6 or nylon 66; a cellulose resin such as cellulose triacetate, cellophane, and celluloid; a styrene resin such as polystyrene, an acrylonitrile-styrene copolymer, and an acrylonitrile-butadiene-styrene copolymer (ABS resin); or polyvinyl alcohol, an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, a polycarbonate resin, a polyarylate resin, or a polyimide resin.
Examples of the natural resin include natural rubber, pine resin, or amber.
In addition, preferable examples of the curable resin include a thermosetting resin or an ionizing radiation curable resin, which are exemplified as a material constituting a matte layer described below.
Preferable examples of the metal that can be used for the base material include: aluminum or aluminum alloy such as aluminum and duralumin; iron or iron alloy such as iron, carbon steel, and stainless steel; copper or copper alloy such as copper, brass, and bronze; gold, silver, chromium, nickel, cobalt, tin, or titanium. In addition, preferable examples of the base material made of metal include a base material, the surface of which is, for instance, plated using the above metal(s).
Preferable examples of the non-metallic inorganic material that can be used for the base material include: a non-ceramic ceramics-based material such as cement, ALC (lightweight foamed concrete), gypsum, calcium silicate, and wood chip cement; a ceramic ceramics-based material such as porcelain, earthenware, glass, and enamel; or a natural stone such as limestone (including marble), granite, and andesite.
Preferable examples of the fibrous material that can be used for the base material include: paper such as thin paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, sulfate paper, paraffin paper, parchment paper, glassine paper, lining paper for wallpaper, board paper, and plasterboard base paper; or a woven or non-woven fabric made of fiber such as polyester resin fiber, acrylic resin fiber, protein or cellulose-based natural fiber such as silk, cotton, hemp, glass fiber, and carbon fiber. In order to improve the interlaminar strength between the fibers of paper base material made of paper or between the paper based material and other base materials used in combination with the paper based material, and to prevent fluffing, each resin such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin may be added (i.e., the base material may be impregnated or filled with the resin(s) after or during the papermaking process) to these materials. Preferable examples of the resin-added paper include inter-paper reinforced paper or resin-impregnated paper.
Preferable examples of the laminate produced by laminating a layer made of fibrous material and a layer made of resin include wallpaper base paper produced by laminating a resin-made layer such as a vinyl chloride resin layer, an olefin resin layer, and an acrylic resin layer on a surface of wallpaper lining paper, which is widely used in the building materials field.
Preferable examples of a woody material that can be used for the base material include veneer, plywood, laminated wood, particle board, or medium density fiberboard (MDF) made of each wood such ad cedar, cypress, pine, zelkova, oak, walnut, rowan, teak, and rubber wood.
It is possible to use, as the base material, a base material made of the above material(s) without limitation, and the base material may be selected, if appropriate, according to, for instance, the desired properties. From the viewpoints of improving the matte effect and the dry and smooth touch, the base material is preferably made of a resin or made of a fibrous material, and base material made of a resin is more preferable.
Among the resin, an olefin resin, vinyl chloride resin, polyester resin, or acrylic resin is preferable, and an olefin resin, polyvinyl chloride resin, or polyester resin is more preferable. polyethylene or polypropylene is preferable as the olefin resin, and polyvinyl chloride is preferable as the polyvinyl chloride resin. The polyester resin is preferably polyethylene terephthalate. Among fibrous materials, paper is preferred. By using a base material made of these materials, it is particularly easy to obtain the above surface shape and to improve the dry and smooth touch.
The shape and dimensions of the base material including a single layer or laminate are not particularly limited and may be selected, if appropriate, in consideration of the application, desired performance, suitability for post-processing, and others.
When a film, sheet, or plate shape is adopted, the thickness is a typical dimension in the design of a matte article. Such a thickness is not particularly limited, and may be selected from the range of preferably from 10 μm to 10 cm in consideration of, for instance, suitability for manufacturing, handling, or post-processing, mechanical strength, and cost performance. When a film or sheet shape is adopted, the range may be selected preferably from 20 μm to 300 μm, and when a plate shape is adopted, the range may be selected preferably from 1 mm to 2 cm.
From the viewpoint of improving adhesion between the base material and another layer such as a matte layer described below, and adhesion between the base material and an adherend such as a resin molding on which the matte article is stacked, at least one side of the base material can be subjected to surface treatment to improve adhesion, such as physical surface treatment such as an oxidation process and a roughening process, as well as chemical surface treatment.
Examples of the oxidizing process include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, or ozone-UV treatment. Examples of the roughening process include sandblasting or solvent treatment. These surface treatments may each be selected, if appropriate, depending on the type of base material. Corona discharge treatment process is preferred from the viewpoints of, for instance, the effect of surface treatment in improving adhesion and workability.
The base material may be colored or not colored (may be transparent), and if colored, there are no restrictions on the mode of coloring; it may be transparently colored or opaquely colored (concealed coloring), which may be optionally selected.
If the base material is colored, examples of the coloring agent include an inorganic pigment such as a white pigment such as titanium white, iron black, yellow lead, titanium yellow, red oxide, cadmium red, ultramarine blue, and cobalt blue; an organic pigment or dye such as quinacridone red, isoindolinone yellow, phthalocyanine blue, a nickel-azo complex, an azomethine azo-based black pigment, and a perylene-based black pigment; a metal pigment made of aluminum, brass, or other scale-like foil fragments; or a pearl gloss pigment made of titanium dioxide-coated mica, basic lead carbonate, or other scale-like foil fragments. For example, when the surface hue of an adherend such as a resin molding on which a matte article is stacked is uneven, an inorganic pigment such as a white pigment may be used to conceal the surface hue and to improve the stability of the color tone of a decorative layer provided as desired.
In the case of coloring a resin-made base material, any of the following methods can be adopted, including addition of a coloring agent to the resin (kneading, mixing) or formation by coating film application using a coating agent containing a resin and a coloring agent. In the case of coloring a base material made of fibrous material such as paper, woven and non-woven fabric, any of blending with pulp or fiber material or coating film formation may be used, or these processes may be used in combination.
In the case of coloring a base material made of woody material, any of dyeing using a dye or coating film formation may be used, or these processes may be used in combination. In the case of coloring a metal-made base material, an electrolytic coloring process in which a positive electrode oxidation process is used to forma metal oxide film on a surface or other process may be used in addition to coating film formation, In the case of coloring a base material made of non-metallic inorganic material, any of coating film formation or addition into a base material may be used, or these processes may be used in combination.
The base material may be optionally blended with an additive. In the case of a resin as a main component, examples of the additive include an inorganic material such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, an antioxidant, a UV absorber, or a light stabilizer. The amount of additive blended is not particularly limited as long as the amount does not interfere with, for instance, surface properties and processing properties, and can be set, if appropriate, according to the required properties and others.
From the viewpoint of improving the weather resistance of a matte article of the present disclosure, it is preferable to use a weathering agent such as a UV absorber and a light stabilizer among the above additives.
Examples of the UV absorber or light stabilizer include those that can be included in a matte layer described below.
These weathering agents such as a UV absorber and a light stabilizer and/or other various additives may be used singly or a plurality of the kinds may be used in combination.
In this disclosure, the above base materials may be used singly or in combination. Multiple paper base materials may be combined. Also, a paper base material and fiber base material, a paper base material and resin base material, a fiber base material and resin base material, or a paper base material and fiber base material and resin base material may be combined. Here, the resin base material may be structured using a single layer of the above resin base material or multiple layers of the same or different types of resin.
The thickness of the base material is described as above. When the base material is the above resin film or sheet, the thickness is preferably 20 μm or larger, and the upper limit is preferably 300 μm or less. In consideration of, for instance, suitability for manufacturing, handling, or post-processing, mechanical strength, and cost performance, the thickness is more preferably 40 μm or larger, and the upper limit is more preferably 200 μm or less and still more preferably 100 μm or less.
Because of the same reason, when the base material is paper, the typical basis weight is preferably from 20 to 150 g/m2 and more preferably from 30 to 100 g/m2.
[Matte Layer]
A matte layer in a matte article of the present disclosure is provided on at least a part of the above base material and is a layer having the above surface shape, i.e., a surface shape with a skewness (Ssk) of 0.00 or more and a kurtosis (Sku) of 3.50 or less. As shown in
Thus, the matte article of the present disclosure is preferably provided with a matte layer and has a structure in which the above surface shape is formed by the surface of the matte layer. In consideration of, for instance, mechanical strength and suitability for manufacturing, it is preferable that the matte layer is made of a cured resin composition, preferably a cured curable resin composition containing a cured resin.
The above resin composition for forming a matte layer is preferably a resin composition containing a resin and a wrinkle formation stabilizer (hereinafter, sometimes referred to as a “resin composition for forming a matte layer”) in consideration of obtaining a matte article with an excellent matte effect and a dry and smooth touch. That is, the matte layer in the present disclosure is preferably a layer containing a resin and a wrinkle formation stabilizer.
(Wrinkle Formation Stabilizer)
The wrinkle formation stabilizer has the function of stabilizing the formation of wrinkles on at least one surface of the matting layer, thereby providing stable matting effect visibility, wherein the visibility of the matting effect is uniformly expressed over the entire surface of the matting layer having said surface shape, formed at least partially on the surface of the matted article, thereby reducing uneven partial gloss, as well as surface condition uniformity due to stable wrinkle formation over the entire surface of the matting layer. The wrinkles formed in the matte layer also contribute significantly to the development of a dry and smooth touch. As used herein, the wording “stable matte effect visibility” may be used hereafter as “stable matte effect visibility” or other expressions equivalent thereto. In addition, the “surface condition uniformity” is sometimes referred to as a “texture”.
Therefore, even if the so-called “matting agents” in the conventional art and the “wrinkle formation stabilizers” in the present disclosure have the same constituent substances and average particle size, they are different in terms of their matting mechanism (effect), structure for expressing matting, and relationship between the amount used and the degree of gloss (gloss value) on the surface. The wrinkle formation stabilizer also differs from the “matting agent” in development of a dry and smooth touch by forming wrinkles.
In conventional art such as the above-mentioned PTL1, the matting agents used for matte effect expression can elicit their own matte effect visibility due to the light diffusion effect caused by their physical shape. Specifically, what is generally called a matting agent usually has a refractive index difference between the matting agent particles and the surrounding resin and air, and develop the matte effect by the light diffusion effect caused by the light reflection corresponding to the contour shape of the particles and the refractive interface. In contrast, in a matte article of the present disclosure, the wrinkle formation stabilizer does not elicit the matte effect visibility by light diffusion through the light reflection and refraction caused by the particles themselves, but stabilizes the formation of wrinkles on the surface of the matte layer due to the wrinkle formation stabilizer, thereby imparting texture as well as the matte effect visibility to the matte article in a stable manner by the light diffusion effect at a refractive index difference interface between such a surface and air. Therefore, the wrinkle formation stabilizer used in the present disclosure is different from the matting agent that itself expresses matte effect visibility in terms of mechanism and effect of matting, and structure to express matting, even if the constituent substances and average particle size of two are the same.
Further, the “wrinkle formation stabilizer” and the “matting agent” are different in terms of the relationship between the content and the surface gloss (gloss value). The surface 60° gloss value G60°AW(C) of the case where the same substance A is used as a wrinkle formation initiator AW (W: wrinkle) and a specific amount C is included to form wrinkles on a surface is clearly lower than the surface 60° gloss value G60°AM(C) of the case where the same substance A is used as a mere matting agent AM and inclusion of the substance at a specific amount C does not cause wrinkle formation. That is, the following relationship is established:
G60°AW(C)<G60°AM(C).
The matte layer in the matte article of the present disclosure may contain an agent conventionally used as a matting agent. Considering the characteristics of the effect of the present invention, which is to stably obtain extremely excellent matte effect to a degree that cannot be obtained by using a matting agent, and to obtain a dry and smooth touch, the matte layer is preferably free of a matting agent. Thus, it can be said that the matte article of the present disclosure provide extremely excellent matte effect visibility and texture, even though the article is substantially free of a matting agent conventionally used to obtain matte effect visibility. Here, the wording “free of a matting agent” means that, in addition to not containing any matting agent at all, even if it is contained, no matte effect visibility based on their own matting agent effect is elicited. Specifically, the content of matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, and more preferably 3.0 parts by mass or less based on 100 parts by mass of resin.
Note that as used herein, from the viewpoint of forming convex portions by the protrusion effect as already described, specifically, the term “matting agent” means particles with an average particle size, the lower limit of which is more than 100% of the thickness of a layer that can contain the matting agent, namely, the matte layer, or more than 30 μm, whichever is smaller.
In the present disclosure, any of wrinkle formation stabilizer may be used without particular limitation if the stabilizer is not a matting agent and the upper limit of the average particle size is 100% of the thickness of the matte layer or 30 μm or less, whichever is smaller.
Considering the improvement of the matte effect and the dry and smooth touch, it is preferable to use at least one of two types of wrinkle formation stabilizers distinguished by their average particle size for the wrinkle formation stabilizer should have an average particle size, the upper limit of which is 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. The two types of wrinkle formation stabilizers specifically include: a wrinkle formation stabilizer 1 having an average particle size of 1 μm or larger and, as the upper limit, 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller; and a wrinkle formation stabilizer 2 having an average particle size of less than 1 μm.
In the present disclosure, the use of at least one of the two types of wrinkle formation stabilizer stabilizes wrinkle formation and provides a stable and excellent matte effect, as well as a dry and smooth touch. In the present disclosure, the wrinkle formation stabilizer 1 or the wrinkle formation stabilizer 2 may be used singly, or the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 may be used in combination. It is more preferable to use the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 in combination. The combination use can improve the matte effect and the dry and smooth touch.
The wrinkle formation stabilizer used may be, for instance, organic and/or inorganic particles.
Examples of an organic material constituting the organic particles include polymethyl methacrylate, an acrylic-styrene copolymer resin, a melamine resin, polycarbonate, polystyrene, a polyvinyl chloride resin, a benzoguanamine-melamine-formaldehyde condensate, silicone, a fluorine-based resin, or a polyester-based resin.
Examples of an inorganic material constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, or barium sulfate. Among these, silica is preferred because of its excellent transparency.
Examples of the shape of wrinkle formation stabilizer include, but are not particularly limited to, a spherical, polyhedral, scaly, or irregular shape.
The wrinkle formation stabilizer 1 has an average particle size of 1 μm or larger and, as the upper limit, 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. Considering stable enhancement of the matte effect and improvement of the dry and smooth touch, the average particle size of wrinkle formation stabilizer 1 is preferably 1.3 μm or larger, more preferably 1.5 μm or larger, and still more preferably 1.8 μm or larger. The upper limit based on the thickness of the matte layer is preferably 90% or less of the thickness of the matte layer, more preferably 80% or less of the thickness of the matte layer, and still more preferably 70% or less of the thickness of the matte layer. The absolute value is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and still more preferably 7 μm or less. In the case of any combination of the upper limit based on the thickness of the matte layer or the upper limit based on the absolute value, whichever is smaller should be used. For example, either 90% or less of the thickness of the matte layer or 20 μm or less, whichever is smaller, may be used as the upper limit, or either 90% or less of the thickness of the matte layer or 10 μm or less, whichever is smaller, may be used as the upper limit. Note that the thickness of the matte layer is described later.
The average particle size of wrinkle formation stabilizer 2 is less than 1 μm. Considering stable enhancement of the matte effect by the stable wrinkle formation and improvement of the dry and smooth touch, the average particle size of wrinkle formation stabilizer 2 is preferably 1 nm or larger, more preferably 3 nm or larger, and still more preferably 5 nm or larger, and the upper limit is preferably 900 nm or less, more preferably 700 nm or less, and still more preferably 500 nm or less.
As used herein, the average particle size of wrinkle formation stabilizer is measured as the mass-averaged d50 in particle size distribution measurements by laser light diffractometry.
Considering stable enhancement of the matte effect by the stable wrinkle formation and improvement of the dry and smooth touch, the content of wrinkle formation stabilizer (the total content when wrinkle formation stabilizers 1 and 2 are used in combination) is preferably 0.5 parts by mass or larger, more preferably 0.75 parts by mass or larger, still more preferably 1.0 parts by mass or larger, and still more preferably 1.2 parts by mass or larger based on 100 parts by mass of the resin used to form the matte layer. On the other hand, the upper limit is preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, still more preferably 10.0 parts by mass or less, still more preferably 7.5 parts by mass or less, and especially 6.0 parts by mass or less. The upper limit is not particularly limited in terms of improving the stable matte effect and the dry and smooth touch. However, if the upper limit is within the above range, the productivity of decorative material and the matte effect visibility and texture are efficiently improved because of, for instance, coating performance of a resin composition for forming a matte layer.
In the case where the wrinkle formation stabilizers 1 and 2 are used in combination, the content of each wrinkle formation stabilizer 1 or 2 is not particularly limited as long as the total content is within the above-mentioned range. However, the content of wrinkle formation stabilizer 2 based on 100 parts by mass of resin is preferably 0.1 parts by mass or larger, more preferably 0.5 parts by mass or larger, still more preferably 1.0 parts by mass or larger, and the upper limit is preferably 10.0 parts by mass or less, more preferably 7.5 parts by mass or less, still more preferably 5.0 parts by mass or less, and still more preferably 3.5 parts by mass or less. In addition, the blending ratio between the wrinkle formation stabilizers 1 and 2 is set such that the amount of wrinkle formation stabilizer 1 blended when the total content is set to 100 parts by mass is preferably from 0.05 to 0.95 parts by mass, more preferably 0.10 to 0.90 parts by mass, still more preferably from 0.20 to 0.80 parts by mass, and still more preferably from 0.30 to 0.70 parts by mass.
The wrinkle formation stabilizer used may be, for instance, organic and/or inorganic particles as described above. These particle types themselves may include those conventionally used as matting agents. For example, matting agents such as spherical alumina and calcium carbonate is used in the matte layer of the decorative sheet described in PTL1 above. In order that the matting agents, such as spherical alumina and calcium carbonate, develop their own matte effect visibility by the light diffusion effect caused by their physical shape, it is necessary to use the total content of about 50 parts by weight, i.e., 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, per 100 parts by weight of resin as described in PTL1. However, in the present disclosure, even if the content is small as already mentioned, that is, even if the content is smaller than the content required to develop their own matte effect visibility by the light diffusion effect caused by their physical shape, an extremely excellent is obtained, and a drier and smoother touch is also obtained.
Therefore, it can be said that, in the matte article of the present disclosure, wrinkles are stably formed on the surface even though the article contains substantially no matting agents, thereby stably obtaining more excellent matte effect visibility than when a matting agent is used, as well as providing texture, and in addition a dry and smooth touch can be obtained.
(Surface Shape of Matte Layer)
The matte layer in the matte article of the present disclosure is a layer having the above surface shape. This layer is preferably made of a cured resin composition for forming a matte layer, which composition contains a certain content of specific wrinkle formation stabilizer described above. As mentioned above, wrinkles are stably formed on a surface of the matte layer, thereby the matte layer develops stably matte effect by the light diffusion effect caused by the shape of the wrinkles, and also develops a dry and smooth touch.
The wrinkles formed on at least one surface of the matte layer are not particularly limited, as long as the wrinkles have the above surface shape, i.e., a surface shape having a Ssk (skewness) and Sku (kurtosis) within the above specific numerical range, and preferably, in addition, preferably RSm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) within the above specific numerical range. The wrinkles are formed to give the above surface shape, and therefore the wrinkle formation stabilizer stabilizes the formation and causes a stable matte effect and a dry and smooth touch.
With regard to the wrinkles, from the viewpoint of developing the above surface shape, enhancing the matte effect, and improving the dry and smooth touch, at least one surface of the matte layer preferably have an uneven shape composed of irregular wrinkles. The irregular wrinkles are preferably composed of a plurality of convex portions formed by a plurality of protrusions and a plurality of concave portions formed by being surrounded by the plurality of protrusion portions, and the protrusion portions preferably have streak-shaped protrusions. As used herein, the wording “streak-shaped protrusions” (hereinafter also referred to as “streak-shaped protrusions”) means that the ratio (length/width) between the length and the width of each protrusion is 3 or higher, preferably 5 or higher, and more preferably 10 or higher. The method for determining the length and width is described below.
The more preferable irregular wrinkles in the present disclosure are composed of a plurality of convex portions formed by a plurality of streak-shaped protrusions and a plurality of concave portions formed by being surrounded by the plurality of the streak-shaped protrusions.
Examples of these wrinkle-related forms include those shown in
As used herein, the term “curved” means having one or more sections where the direction of extension of each continuous streak-shaped convex portion 3 is inverted from one side to the other side in a plan view. Examples of the section where the direction of extension is inverted from one side to the other side include a form with an inflection point when the width of the shape of each streak-shaped convex portion 3 in a plan view is ignored (when the width of the shape in a plan view is considered to be 0) and the convex portion is approximated by a continuous curve. Other Examples include a form with a section approximated by a V-shaped fold line or two sides flanking one vertex of a triangle when the width of the shape of each streak-shaped convex portion 3 in a plan view is ignored and the convex portion 3 is approximated as a straight line.
The term “meandering” means having at least two sections (hereinafter, also referred to as “inverted sections”) where the extending direction of continuous streak-shaped convex portion 3 is inverted from one side to the other side in a plan view, and having a section where, as the streak-shaped convex portion 3 extends in the extension direction, the extending direction of the streak-shaped convex portion 3 is alternately inverted in the opposite direction at two adjacent sites. Examples include a form with a section approximated by the Roman letter “S” when the streak convex portion 3 is approximated by a continuous curve when the width of the shape is ignored in a plan view. Other examples include a form with a section approximated by the Roman letter “W” when the streak-shaped convex portion 3 is approximated by a straight line when the width of the shape is ignored in a plan view.
As used herein, the term “irregular” means that a shape is not formed by a certain rule or a shape is not arranged by a certain rule, i.e., is not patterned. Typical examples of a non-irregular shape, i.e., a regular shape include a shape periodicity arranged in a certain direction, like a so-called lenticular lens where a plurality of cylindrical unit lenses is arranged adjacent to each other in a direction perpendicular to the longitudinal direction. Thus, irregular wrinkles in the present disclosure encompass embodiments wherein the shape of one protrusion portion itself is not a shape formed according to a certain rule such as periodicity but is irregular; the shape of the plurality of convex portions formed by the plurality of protrusions is not formed and arranged according to a certain rule, and is irregular; or the shape of concave portion surrounded by such a plurality of protrusions is also irregular.
In the matte article of the present disclosure, when any of the shape of one protrusion portion (one convex portion) itself, the shape and arrangement of each of a plurality of protrusion portions (plurality of convex portions), or the shape of concave portion surrounded by a plurality of protrusions is irregular, a matte effect caused by the irregular wrinkles and a dry and smooth touch. Each of the above is preferably irregular. The irregular wrinkles in the matte article of the present disclosure can improve the matt effect visibility and texture, and stably develop an extremely excellent matte effect as well as a dry and smooth touch.
As already mentioned, the matte layer has wrinkles, i.e., an uneven shape, on at least one of its surfaces. The convex and concave portions in the uneven shape are, for example, binarized and distinguished using the difference in brightness of a surface image of a decorative material in the present disclosure such that the darkest part of the density distribution image is set to level 255, the lightest part of the density distribution image is set to level 0, and for levels 0 to 255, levels 0 to 127 should be assigned as a concave portion and levels 128 to 255 should be assigned as a convex portion.
It is preferable that at least a part of the surface of a matte article of the present disclosure has irregular wrinkles, and it is more preferable that irregular wrinkles are formed over the entire surface. There are no restrictions on an area where the wrinkles are formed on a surface of the matte article. For example, if wrinkles are formed not only on the areas corresponding to a pattern described below, i.e., on the pattern, but also on at least a part of the surface, the matte effect by formation of the wrinkles and a dry and smooth touch can be developed. For example, in the case where the below-described decorative layer is provided and part thereof have irregular wrinkles, the wrinkles are formed at an area corresponding to a pattern of the decorative layer, e.g., on a pattern, thereby the design can be improved because the pattern is seen as a more matted area than the surrounding area.
As also shown in
With regard to the shape of the wrinkles formed on at least one surface of the matte layer, the height of the convex portion (the height of the protrusion portion) is preferably 0.5 μm or greater, more preferably 1 μm or greater, and still more preferably 2 μm or greater, and the upper limit is about 10 μm or less. The width of the convex portion is preferably 0.1 μm or larger, more preferably 0.3 μm or larger, and still more preferably 0.5 μm or larger, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, and still more preferably 3 μm or less. When the height and width of the convex portion are within the above ranges, the above surface shape is more likely to appear, and thereby a matte effect can be stably enhanced due to the interaction with the concave portions, and a dry and smooth touch is improved.
Here, the above dimensions of the convex portion are obtained by averaging randomly selected 10 convex portions (protrusion portions) in optionally selected 10 areas (10 areas of 100 μm square regions), i.e., 100 convex portions in total, on a matte product of the present disclosure. As shown in
The depth of the concave portion is preferably 0.5 μm or deeper, more preferably 1 μm or deeper, and still more preferably 2 μm or deeper, and the upper limit is about 10 μm or less. The width of the concave portion is preferably 0.1 μm or larger, more preferably 0.2 μm or larger, and still more preferably 0.3 μm or larger, and the upper limit is preferably 10 μm or less, more preferably 3 μm or less, and still more preferably 2 μm or less. When the depth and width of concave portion are within the above ranges, the above surface shape is more likely to appear, and thereby a matte effect can be stably enhanced due to the interaction with the concave portions, and a dry and smooth touch is improved.
Here, the dimensions of the concave portion are determined in substantially the same way as for the dimensions of the convex portion described above.
The distance from the top of the convex portion to the bottom of the concave portion, i.e., the height difference between the convex and concave portions, is preferably 1 μm or larger, more preferably 2 μm or larger, and still more preferably 4 μm or larger, and the upper limit is preferably 20 μm or less, more preferably 8 μm or less, and still more preferably 7 μm or less. When the distance is within the above range, the above surface shape is more likely to appear, and thereby a matte effect can be stably enhanced and a dry and smooth touch can be improved.
Here, the dimensions of the concave portion are determined in substantially the same way as for the dimensions of the convex portion described above.
The percentage of the convex portion occupied is preferably 15% or larger, more preferably 20% or larger, and still more preferably 30% or larger, and the upper limit is preferably 80% or less, more preferably 70% or less, and still more preferably 60% or less. When the percentage of the convex portion occupied is within the above range, the above surface shape is more likely to appear, and thereby a matte effect can be stably enhanced due to the interaction with the percentage of concave portion occupied by being surrounded by the convex portions and a dry and smooth touch can be improved.
Here, the percentage of the convex portion occupied is obtained by averaging the percentages of the convex portions in randomly selected 10 areas (10 areas of 100 μm square regions) on a matte article of the present disclosure.
The convex and concave portions may have a section extending in substantially the same direction and having substantially the same width. Considering the enhancement of the matte effect and improvement of the drier and smoother touch, their lengths are preferably short. Specifically, the length of each of the continuous convex and concave portions extending in substantially the same direction and having substantially the same width is preferably 95 μm or less, more preferably 80 μm or less, and still more preferably 70 μm or less, and the lower limit is preferably 5 μm or larger, more preferably 10 μm or larger, and still more preferably 15 μm or larger. When the length is within the above range, the wrinkles are more irregular, and thereby a matte effect can be stably enhanced and a dry and smooth touch can be improved.
Here, with regard to any 10 convex and concave portions (i.e., 100 convex and concave portions in total) in any 10 areas (10 areas of 100 μm square regions) on a matte product of the present disclosure, it is preferable that 80% or more of them satisfy the above conditions, it is more preferable that 85% or more of them satisfy the above conditions, it is still more preferable that 90% or more of them satisfy the above conditions, and it is still more preferable that 95% or more of them satisfy the above conditions. As used herein, the term “substantially” of “substantially the same” means that they are generally the same, and means that they are not branched or means a difference within ±3 degrees in terms of direction or a difference within ±5% in terms of width.
The number of the convex portions (the protrusion portions) in a 100 μm square area is preferably 10 or larger, more preferably 20 or larger, and still more preferably 30 or larger, and the upper limit is preferably 200 or less, more preferably 100 or less, and still more preferably 70 or less. When the number of convex portions is within the above range, the matte effect is stably enhanced, and the dry and smooth touch is improved.
The number of the convex portions is obtained by averaging the numbers of the convex portions in 10 areas (10 areas of 100 μm square regions) on a matte article of the present disclosure.
The shape of the concave portion may be, for example, pointed as illustrated in 2a of
On the other hand, the convex portion may be displayed like a semi-circular or semi-elliptical shape, although its width may be narrower or wider, as shown in 3a and 3b of
The thickness of the matte layer is not particularly limited as long as the thickness can cause a stable matte effect and allows for the formation of wrinkles so as to be able to elicit a dry and smooth touch. In view of ease of manufacturing and other factors, the thickness is usually 1 μm or larger, preferably 2 μm or larger, more preferably 3 μm or larger, still more preferably 4 μm or larger, and still more preferably 5 μm or larger, and the upper limit is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less, and still more preferably 100 μm or less.
As used herein, the thickness of the matte layer is determined by measuring the thicknesses at 20 points on a cross section of a matte article from an image taken using a scanning electron microscope (SEM), and averaging the values at the 20 points. Note that the acceleration voltage of the SEM is set to be 3 kV, and the magnification is set according to the thickness. In addition, the same applies to the thicknesses of another layer.
The matte layer is a layer having the above surface shape on its entire surface. Since the matte article of the present disclosure has the above surface shape on at least a part of the surface, the surface shape is only required to be provided on at least a part of the surface of the matte article, or may be provided over the entire surface of the matte article. When the matte article of the present disclosure has the above base material and the matte layer, the surface shape may be provided on at least a part of the surface of the base material, or it may be provided over the entire surface of the base material.
When the matte layer is provided on a section of the matte article that an user can see and touch, that is, when the above surface shape is provided on a section of the matte article that an user can see and touch, the effects of the present invention, namely a matte effect and a dry and smooth touch, can be achieved.
When the base material is in the form of a film, sheet, or plate, the matte layer may be provided on a section of the matte article that an user can see and touch, and the matte layer may be provided on at least a part of the surface or may be provided over its entire surface. From the viewpoint of improving the matting effect and the dry and smooth touch, it is preferable that the matte layer is provided over the entire surface of one of the surfaces, as shown in
(Resin)
As the resin for forming the matte layer, any resin may be used in which a resin composition for forming the matte layer that contains a given amount of the above wrinkle formation stabilizer to constitute a matte layer by producing a cured product though curing. Examples of such a resin include an ionizing radiation curable resin. The matte layer is a layer that can be provided on the top surface of the matte article of the present disclosure, as also shown in
Ionizing radiation curable resins are resins with an ionizing radiation curable functional group. The ionizing radiation curable functional group is a group crosslinked and cured by ionizing radiation irradiation. Preferable examples include an ethylenic double bond-containing functional group such as a (meth)acryloyl group, a vinyl group, and an allyl group. Note that as used herein, the (meth)acryloyl group refers to an acryloyl or methacryloyl group. Note that as used herein, the (meth)acrylate refers to acrylate or methacrylate.
The ionizing radiation means electromagnetic waves or charged particle rays with energy quanta allowing for polymerization and/or cross-linking of molecules. Usually, ultraviolet (UV) light or electron beams (EB) are used. Other examples include electromagnetic waves such as X-rays, and γ-rays and charged particle rays such as α-rays and ion beams).
Examples of the ionizing radiation curable resin include an electron beam curable resin or a UV curable resin. A UV-curable resin is preferred in consideration of stabilizing wrinkle formation by the wrinkle formation stabilizer to enhance the matte effect and to improve the dry and smooth touch.
The ionizing radiation curable resin can be selected for use, if appropriate, from the group consisting of polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.
As each polymerizable monomer, preferred is a (meth)acrylate-based monomer having a radical polymerizable unsaturated group in the molecule. Particularly preferred is a polyfunctional (meth)acrylate monomer. As used herein, the term “(meth)acrylate” means “acrylate or methacrylate”.
Examples of the polyfunctional (meth)acrylate monomer include a (meth)acrylate monomer having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group.
Considering the stabilization of wrinkle formation to enhance stable matte effect and to improve the dry and smooth, and in addition considering improvement of the surface properties such as post-processing properties, scratch resistance, and weather resistance, the number of functional groups in the polyfunctional (meth)acrylate monomer is preferably from 2 to 8 and more preferably from 2 to 6. The above number of functional groups makes it particularly easier to obtain the above surface shape and to improve the dry and smooth touch.
These polyfunctional (meth)acrylates may be used singly or the multiple kinds thereof may be used in combination.
Examples of the polymerizable oligomer include a (meth)acrylate oligomer having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group. Examples include a urethane(meth)acrylate oligomer, an epoxy(meth)acrylate oligomer, a polyester(meth)acrylate oligomer, a polyether(meth)acrylate oligomer, a polycarbonate(meth)acrylate oligomer, or an acrylic(meth)acrylate oligomer.
In addition, other examples of the polymerizable oligomer include: a highly hydrophobic polybutadiene(meth)acrylate-based oligomer with a (meth)acrylate group in the side chain(s); a silicone (meth)acrylate-based oligomer with a polysiloxane linkage in the main chain; an aminoplast resin (meth)acrylate-based oligomer obtained by modifying an aminoplast resin having many reactive groups in a small molecule; or an oligomer with a cationic polymerizable functional group in the molecule such as a novolac epoxy resin, a bisphenol epoxy resin, aliphatic vinylether, and aromatic vinylether.
These polymerizable oligomers may be used singly or the multiple kinds thereof may be used in combination.
Among them, preferable examples of the polymerizable oligomer include a urethane(meth)acrylate oligomer, an epoxy(meth)acrylate oligomer, a polyester(meth)acrylate oligomer, a polyether(meth)acrylate oligomer, a polycarbonate(meth)acrylate oligomer, or an acrylic(meth)acrylate oligomer. More preferred is a urethane(meth)acrylate oligomer or a polycarbonate(meth)acrylate oligomer. Still more preferred is a urethane(meth)acrylate oligomer. Use of each polymerizable oligomer makes it possible to stabilize the wrinkle formation, and thereby the matte effect is stably enhanced, the dry and smooth touch is improved, and further the surface properties such as post-processing properties, scratch resistance and weather resistance are improved.
The number of functional groups in each polymerizable oligomer is preferably from 2 to 8 and the upper limit is more preferably 6 or less and still more preferably 4 or less. If the number of functional groups is within the above range, the wrinkle formation can be stabilized, and therefore the matte effect can be stably enhanced, the dry and smooth touch can be improved, and the surface properties such as post-processing properties, scratch resistance, and weather resistance can be further increased.
For the same reason, the weight average molecular weight of the polymerizable oligomers is preferably from 900 to 7,500, more preferably from 1,000 to 7,000, and still more preferably from 1,200 to 6,000. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and calculated in terms of standard polystyrene.
In the present disclosure, it is preferable to use a combination of the above polymerizable oligomer(s) and polymerizable monomer(s) as the resin for forming a matte layer. In this case, the polymerizable oligomer is preferably a polyfunctional urethane(meth)acrylate oligomer and more preferably a polyfunctional urethane acrylate oligomer; and the polymerizable monomer is preferably a polyfunctional polymerizable monomer, more preferably a polyfunctional (meth)acrylate monomer, and still more preferably a polyfunctional acrylate monomer. By stabilizing wrinkle formation, the matte effect can be stably enhanced, the dry and smooth touch can be improved, and the surface properties such as post-processing properties, scratch resistance, and weather resistance can be further increased.
When used in combination, for the same reason, the content of the polymerizable oligomer per total 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or larger, more preferably 50 parts by mass or larger, still more preferably 55 parts by mass or larger, and still more preferably 60 parts by mass or larger, and the upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass or less. The polymerizable oligomers may also be used in combination. It is preferable to use a combination of two kinds of polymerizable oligomers with different numbers of functional groups. In this case, the content of the polymerizable oligomer with a larger number of functional groups based on the total 100 parts by mass of the polymerizable oligomers is preferably 50 parts by mass or larger, more preferably 55 parts by mass or larger, still more preferably 60 parts by mass or larger, and still more preferably 65 parts by mass or larger.
(Resin Composition)
The matte layer is preferably composed of a cured resin composition containing the above wrinkle formation stabilizer in a predetermined content. The resin composition preferably contains the above resin and the above wrinkle formation stabilizer in a specified content. The resin composition used in the present disclosure may contain, in addition to the above wrinkle formation stabilizer and resin, another component(s) depending on the desired performance and other factors.
The resin composition for forming a matte layer may contain monofunctional (meth)acrylate, for example, to reduce its viscosity. The monofunctional (meth)acrylate may be used singly or the multiple kinds thereof may be used in combination.
Meanwhile, in the case where the above resin is a UV curable resin that can be cured by UV light, it is preferable to include an additive(s) such as a photopolymerization initiator and/or a photopolymerization-promoting agent. By including the additive(s), the resin can be cured with UV light (without ionizing radiation, and as a result, surface properties fit for practical use can be obtained.
Examples of the photopolymerization initiator include at least one compound selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, an α-acyl oxime ester, or thioxanthone.
The photopolymerization-promoting agent reduces the inhibition of polymerization by air during curing and accelerates the curing speed. Examples include at least one compound selected from a p-dimethylaminobenzoic acid isoamyl ester or a p-dimethylaminobenzoic acid ethyl ester.
The matte layer is a layer that can be provided on the top surface of a matte article of the present disclosure. Thus, the layer preferably has weather resistance. For example, it is desirable to include each weathering agent such as a UV absorber or a light stabilizer.
The UV absorber used is not particularly limited and may be a UV absorber commonly used for decorative materials, decorative sheets, and others. Examples include a benzotriazole-based UV absorber, a benzophenone-based UV absorber, a triazine-based UV absorber, or a hydroxyphenyltriazine-based UV absorber. The light stabilizer used is not particularly limited and may be a light stabilizer commonly used for decorative materials, decorative sheets, and others. Examples include a hindered amine-based light stabilizer such as a piperidinyl sebacate-based light stabilizer. Here, the UV absorber or light stabilizer may also have an ethylenic double bond-containing reactive functional group(s) such as a (meth)acryloyl group, a vinyl group, and an allyl group in the molecule.
The weathering agent such as a UV absorber, and a light stabilizer) may be used singly or a plurality of the kinds may be used in combination.
[60° Gloss Value]
The matte article of the present disclosure is an article with excellent matte effect visibility and texture. As used herein, the term “matte” means that gloss is unlikely to be seen. It is difficult to make a general statement because it depends on the color tone and pattern of the article. For example, a 60° gloss value of 20.0 or less and preferably about 10.0 or less is generally considered to be “matte”.
Until now, it has been possible to obtain excellent matte effect visibility with a 60° gloss value of 20.0 or less and preferably 10.0 or less while using a matting agent for black or other dark-colored matte article, for example. Here, the term “dark color” refers to a color with low brightness, for example, an L* value (hereinafter, sometimes simply referred to as “L* value”) of usually about 40 or less and preferably 30 or less in the CIE (International Commission on Illumination) L*a*b* color system as measured in accordance with JIS Z8781-4:2013.
However, a large amount of matting agent may be used. This causes stripes or roughness during layer formation, so that the manufacturing is uneasy and the surface properties deteriorate. For example, for the matte article with a color other than black or other dark colors, there is a lower limit of the 60° gloss value even when a matting agent is used. The same applies to a black-colored matte article. In any case, it has been uneasy to obtain a matte article with excellent surface properties as well as matte effect visibility and texture. This tendency becomes more pronounced as the 60° gloss value decreases.
In the matte article of the present disclosure, two types of wrinkle formation stabilizers each having a given average particle size are used in combination, and their content is small as described above. This results in not only stable and extremely excellent matte effect visibility and texture, but also a dry and smooth touch. In addition, the amount of wrinkle formation stabilizer used may be decreased to a tiny amount to prevent a significant increase in the viscosity of the resin composition, and thereby layer formation becomes easier, and naturally provides excellent surface properties such as stain resistance, scratch resistance, and weather resistance in accordance with the characteristics of resin used for the matte layer.
In the matte article of the present disclosure, the 60° gloss value may change depending on the color tone as previously described, and therefore cannot be uniformly defined. For example, in the case where the matte article has a black or other dark color, the 60° gloss value on the matte layer side can be 10.0 or less, 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, or 2.0 or less, and thus extremely excellent matte effect visibility can be developed.
The above 60° gloss value can also be obtained for a matte article with a color other than black or other dark colors. The 60° gloss value on the matte layer side of the matte article of the present disclosure is substantially the same as the 60° gloss value on the surface of the layer that forms the top surface of the matte article. Unless there is another layer, the value of interest is the 60° gloss value of the surface of the matte layer. When another additional layer is further provided, and this additional layer is provided over the surface side of the matte layer, the 60° gloss value mean the 60° gloss value of the additional layer. The matte article of the present disclosure has a specific 60° gloss value substantially due to the structure of the matte layer.
As used herein, the 60° gloss value on the matte layer side refers to a 60° specular gloss measured in accordance with JIS K 5600-4-7:1999. The value is obtained by averaging values at any 10 points as measured from the matte layer side by using, for instance, a gloss meter.
[Total Light Transmittance]
The matte article of the present disclosure may use, for example, a base material made of a non-transparent material as already described and/or a decorative layer as described below. The matte article is also applicable to exterior and/or interior members. The case of using the above base material or the below-described decorative layer or the case of the above applications are taken into consideration. The total light transmittance of the matte article of the present disclosure as measured in accordance with JIS K7361-1:1997 is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less.
As used herein, the total light transmittance of a matte article is a total light transmittance measured in accordance with JIS K7361-1:1997, and the values measured at any 10 points are averaged.
[Additional Layer]
The matte article of the present disclosure may include, in addition to the above matte layer and base material, an additional layer(s) such as a primer layer, a transparent resin layer, a decorative layer, and/or an adhesive layer as needed.
The matted decorative material 1 shown in
(Primer Layer)
For example, in the case where the matte article of the present disclosure is composed of multiple layers, the matte article may include a primer layer to improve interlayer adhesion between the multiple layers.
In the case where the matte article of the present disclosure has a layer(s) other than the matte layer, for example, in the case where a matte layer and a base material are included, a primer layer may be provided between the matte layer and the base material to improve interlayer adhesion.
The primer layer may consist essentially of a binder resin and may optionally contain an additive(s) such as a UV absorber and/or a light stabilizer.
Preferable examples of the binder resin include a resin such as a urethane resin, an acrylic polyol resin, an acrylic resin, an ester resin, an amide resin, a butyral resin, a styrene resin, a urethane-acrylic copolymer, a polycarbonate-based urethane-acrylic copolymer (a urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate linkage in the polymer main chain and two or more hydroxyl groups at the terminals or the side chains), a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride-vinyl acetate-acrylic copolymer resin, a chlorinated propylene resin, a nitrocellulose resin (nitrocellulose cotton), or a cellulose acetate resin. They may be used singly, or a plurality of the kinds may be used in combination.
The binder resin may also be obtained by adding a curing agent such as an isocyanate-based curing agent and an epoxy-based curing agent to the above resin(s), followed by cross-linking and curing. Among them, the binder resin is preferably obtained by cross-linking and curing a polyol-based resin such as an acrylic polyol resin with an isocyanate-based curing agent. The binder resin is more preferably obtained by cross-linking and curing an acrylic polyol resin with an isocyanate-based curing agent.
The thickness of the primer layer is preferably from 0.1 μm to 10 μm, more preferably from 1 μm to 8 μm, and still more preferably from 2 μm to 6 μm.
In the matte article of the present disclosure, for the purpose of improving adhesion to an adherend such as a resin molding to which the matte article is laminated, a primer layer (also called a “backside primer layer”) may be provided on the opposite side of at least one the surface of the matte layer which has wrinkles, or, in the case with a base material, on the side opposite to the matte layer side of the base material.
(Transparent Resin Layer)
The matte article of the present disclosure may have a transparent resin layer in order to increase its strength, and, in the case where a decorative layer is provided, from the viewpoint of protection of the decorative layer, etc. In the case with a base material, the transparent resin layer may be provided between the base material and the matte layer. In the case with a decorative layer, the transparent resin layer may be provided between the decorative layer and the matte layer to protect the decorative layer.
Examples of a resin constituting the transparent resin layer include a polyolefin-based resin, a polyester resin, a polycarbonate resin, an acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”), an acrylic resin, or a vinyl chloride resin. Among them, a polyolefin-based resin or a vinyl chloride resin is preferred from the viewpoint of, for instance, suitability for post-processing. Two or more kinds of these respective resins may be laminated or mixed and used.
The transparent resin layer may be transparent enough to visually recognize a side closer to the base material relative to the transparent resin layer. In the case with a decorative layer, the transparent resin layer may be transparent enough to visually recognize the decorative layer. The transparent resin layer may be colored and transparent or semi-transparent other than colorless and transparent. In other words, the term “transparent” herein means and includes not only colorless and transparent but also colored and transparent or semi-transparent.
The transparent resin layer may contain a weathering agent such as a UV absorber and a light stabilizer and/or an additive such as a colorant.
When the protection of the decorative layer and the suitability for post-processing, for example, are considered, the thickness of the transparent resin layer is preferably from 20 μm to 150 μm, more preferably from 40 μm to 120 μm, and still more preferably from 60 μm to 100 μm.
(Decorative Layer)
The matte article of the present disclosure may have a decorative layer to improve the design. The decorative layer may be provided on the side opposite to at least one side of the wrinkled surface of the matte layer. In the case with a base material, the decorative layer may be placed between the base material and the matte layer. Also, in the case with a transparent resin layer, the decorative layer, the transparent resin layer, and the matte layer may be provided in this order.
The decorative layer may be, for example, a colored layer covering the entire surface or a patterned layer formed by printing various patterns while using inks and a printing machine. Here, the wording “colored layer covering the entire surface” is also called a “solid colored layer”. The layer is indicated by “6a” in
The pattern (design) of the patterned layer may be any desired pattern without any restrictions. Examples include: a wood grain pattern (e.g., annual rings, conduit grooves) on a wood plate surface; a stone grain pattern on the surface of marble, granite or other stone slabs; a fabric grain pattern on a fabric surface; a skin grain pattern on a leather surface; or a geometric pattern, a letter(s), or a figure(s), or a combination thereof.
In addition, preferable examples include a pattern on a fabric, metal surface, or a baby skin, namely each fabric grain pattern, metal surface processing pattern such as a hairline, or skin grain pattern, which are exemplified as a pattern giving a “dry and smooth” touch. The “dry and smooth” touch of a matte article of the present disclosure may be combined with a pattern of the article with the “dry and smooth” touch to display a more realistic design.
The ink(s) used for the decorative layer may be obtained by mixing the binder resin with, if appropriate, a colorant such as a pigment and a dye, a body pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, a UV absorber, and/or a light stabilizer.
Examples of the binder resin for the decorative layer include, but are not particularly limited to, a resin such as a urethane resin, an acrylic polyol resin, an acrylic resin, an ester resin, an amide resin, a butyral resin, a styrene resin, a urethane-acrylic copolymer, a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride-vinyl acetate-acrylic copolymer resin, a chlorinated propylene resin, a nitrocellulose resin, or a cellulose acetate resin. In addition, it is possible to use each type of resin such as a one-component curable resin or a two-component curable resin with a curing agent such as an isocyanate compound.
A pigment with excellent opacity and weather resistance is preferable as a colorant. The pigment used may be the same as those exemplified as a pigment that can be used for the base material.
The content of the colorant based on 100 parts by mass of the resin constituting the decorative layer is preferably from 5 to 90 parts by mass, more preferably from 15 to 80 parts by mass, and still more preferably from 30 to 70 parts by mass.
The decorative layer may contain a weathering agent such as a UV absorber and a light stabilizer and/or an additive such as a colorant.
The thickness of the decorative layer may be selected, if appropriate, according to the desired pattern. Considering that the base color of the adherend is concealed and the design is improved, the thickness is preferably from 0.5 μm to 20 μm, more preferably from 1 μm to 10 μm, and still more preferably from 2 μm to 5 μm.
(Adhesive)
When the matte article of the present disclosure have a base material and a transparent resin layer, an adhesive layer may be present between the base material and the transparent resin layer to improve adhesion between the two layers.
In the case where a decorative layer is further provided between the base material and the transparent resin layer, the positional relationship between the adhesive layer and the decorative layer is not particularly limited. Specifically, the decorative layer, the adhesive layer, and the transparent resin layer may be provided in this order from the side near the base material. Alternatively, the adhesive layer, the decorative layer, and the transparent resin layer may be provided in this order from the side near the base material.
The adhesive layer may be composed of an adhesive such as a urethane-based adhesive, an acrylic adhesive, an epoxy-based adhesive, a rubber-based adhesive, and the like. Among these adhesives, a urethane adhesive is preferred in terms of adhesion strength.
Examples of the urethane-based adhesive include an adhesive using a two-component curable urethane resin containing each polyol compound such as polyether polyol, polyester polyol, and acrylic polyol, and a curing agent such as an isocyanate compound.
To efficiently achieve a desired adhesion strength, the thickness of the adhesive layer is preferably from 0.1 μm and 30 μm, more preferably from 1 μm to 15 μm, and still more preferably from 2 μm to 10 μm.
[Method for Producing Matte Article]
The first method for producing a matte article according to the present disclosure includes a matte layer formation step of forming a matte layer by irradiating a layer of a resin composition for forming the matte layer that contains the above resin and wrinkle formation stabilizer with light at a wavelength of at least 100 nm or more and 380 nm or less.
The first production method makes it possible to produce a matte article with the structure of such a laminate obtained by laminating a plurality of layers, such as laminates shown in
The method for producing a matte article according to the present disclosure makes it possible to easily obtain the matte article of the present disclosure as already described. Specifically, for the formation of the matte layer, a resin composition for forming a matte layer that contains a wrinkle formation stabilizer for forming a matte layer is irradiated with UV light with a low wavelength of at least 100 nm or more and 380 or less. This allows for the formation of wrinkles on at least one of the surfaces of the matte layer, thereby capable of imparting a matte effect and a dry and smooth touch to the matte article (matte layer).
Although the details of the mechanism by which irradiating the resin composition for forming a matte layer with UV light with such a low wavelength causes the formation of wrinkles on at least one surface of the matte layer, thereby developing a matte effect and a dry and smooth touch are unclear, the following mechanism is assumed.
When a coating layer coated with a resin composition for forming a matte layer at a given thickness is irradiated with UV light with a low wavelength, the energy of the UV light to penetrate only the surface area, and no energy reaches a layer(s) lower than the area. Accordingly, only the surface area containing the resin composition starts to cure. Therefore, it is considered that only the surface is cured and shrinks, resulting in the formation of wrinkles. In this way, the formation of wrinkles is considered to occur in a state where the surface of the resin composition for forming a matte layer is cured only in a certain thickness direction by irradiation with UV light at a low wavelength.
From the comparison with the below-described Examples and Comparative Examples, the wrinkle formation becomes unstable when no wrinkle formation stabilizer is included, and the matte effect visibility and texture are thus unstable and insufficient over the entire surface of the matte layer, thereby the dry and smooth touch is not adequately exhibited. Therefore, the stable appearance of the matte effect and the dry and smooth touch cannot be explained only by the curing of only the surface area by low-wavelength UV light. In other words, it is essential to include a wrinkle formation stabilizer in order to develop a matte effect and a dry and smooth touch caused by wrinkles stably provided on the matte article of the present disclosure.
Considering that neither a stable matte effect nor a dry and smooth touch caused by the wrinkle formation is obtained in the case without any wrinkle formation stabilizer, the wrinkle formation stabilizer functions like a wrinkle formation-triggering nucleus. Centered on the nucleus, the resin of the surface area containing the above resin composition gathers to form wrinkle convex portions (protrusion portions) and concave portions along with the formation of the convex portions (protrusion portions). It is considered that this result in stable formation of wrinkles, thereby stably eliciting a matte effect and a dry and smooth touch.
The wrinkle formation stabilizer used in the production method of the present disclosure and the resin composition for forming a matte layer that contains the wrinkle formation stabilizer are the same as those described above as the resin composition for forming a matte layer and the wrinkle formation stabilizer that may be used in the above matte decorative materials in the present disclosure.
In the production method of the present disclosure, the resin composition for forming a matte layer is irradiated with light at a wavelength of at least 100 nm or more and 380 nm or less. This irradiation can cause the energy of the UV light to penetrate only the surface area as already described. Since the energy does not reach the lower layers, only the surface area containing the resin composition starts curing. Therefore, only the surface is cured and shrinks, thus the formation of wrinkles is stabilized. As a result, the surface of the resin composition layer becomes a cured product and constitutes the matte layer. After that, curing progresses from the near surface area to deep inner area, where curing is slower, in the depth direction, and thereby the resin composition layer becomes a cured product. Accordingly, the resin composition is cured over its entire thickness, and this causes the resin composition layer to constitute a matte layer with wrinkles where a light diffusion effect is expressed on the surface and a dry and smooth touch is developed. To accelerate the progress of curing to the deep inner area, it is preferable to perform irradiation with light at a wavelength of 100 nm or more and 380 nm or less, followed by additional other irradiation treatment as described below.
Examples of the light at a wavelength of at least 100 nm or more and 380 nm or less include “excimer light,” which includes light in the ultraviolet wavelength range from a dimer in an excided state, i.e., excimer, formed by the discharge of rare gas such as Ar, Kr, Xe, and Ne, halides of rare gas by halogen such as F, Cl, I and Br, or a mixture of these gases. Examples of the wavelength of excimer light and excimer as a light source include light at a wavelength of 126 nm as emitted from an excimer Ar2 (hereinafter, referred to as “126 nm (Ar2)). Wavelength light such as 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), or 351 nm (XeF) can be preferably employed. As excimer light, either spontaneous emission light or laser light with high coherence (interference) due to induced emission can be used. However, natural emission light is usually sufficient. Note that a light (UV light)-emitting discharge lamp is also called an “excimer lamp”.
Excimer light has a single wavelength peak and is characterized by a narrower half-width of wavelength than ordinary UV light (e.g., UV light emitted from a metal halide lamp, a mercury lamp, etc.). The use of such excimer light stabilizes the formation of wrinkles, and thereby a matte effect is stably enhanced and a dry and smooth touch is also improved.
In order to stabilize the wrinkle formation to stably enhance the matte effect and to improve the dry and smooth touch, the wavelength is preferably 120 nm or longer, more preferably 140 nm or longer, still more preferably 150 nm or longer, and still more preferably 155 nm or longer, and the upper limit is preferably 320 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, still more preferably 200 nm or less, and most preferably 172 nm (Xe2). As such, in the present disclosure, in order to stably enhance the matte effect and to improve the dry and smooth touch, it is preferable to use light with a shorter wavelength. More preferred is UV light with an intermediate wavelength (wavelength: 280 to 320 nm) or UV light with a short wavelength (wavelength: 280 nm or less). Still more preferred is UV light with a short wavelength.
From the viewpoints of stabilizing the wrinkle formation to stably enhance the matte effect and to improve the dry and smooth touch, the cumulative light amount of light with the above wavelength is preferably 1 mJ/cm2 or larger, more preferably 10 mJ/cm2 or larger, still more preferably 30 mJ/cm2 or larger, and still more preferably 50 mJ/cm2 or larger. In addition, the upper limit is not particularly limited. Considering that the number of lamps required for emitting wavelength light is reduced and the productivity such as production efficiency is increased, the cumulative light amount is more preferably 1,000 mJ/cm2 or less, more preferably 500 mJ/cm2 or less, and still more preferably 300 mJ/cm2 or less. For the same reason, the UV power density is preferably 0.001 W/cm or higher, more preferably 0.01 W/cm or higher, still more preferably 0.03 W/cm, and the upper limit is preferably 10 W/cm or lower, more preferably 5 W/cm or lower, and still more preferably 3 W/cm or lower.
It is preferable that the oxygen level at the time of irradiation with the above wavelength light is lower. The oxygen level is preferably 1,000 ppm or less, more preferably 750 ppm or less, still more preferably 500 ppm or less, and still more preferably 300 ppm or less.
At the matte layer formation step in the method for producing a matte article according to the present disclosure, in addition to the irradiation with light at a wavelength of at least 100 nm or more and 380 nm less as described above, additional treatment may be performed that contributes to curing of the resin composition for forming a matte layer.
For example, in other to stabilize the formation of wrinkles caused by the difference in the degree of progression of curing between the surface area and the deep inner area away from the surface in the depth direction, and to accelerate the progression of curing at the deep inner area, the resin composition for forming a matte layer may be pre-cured overall by pre-irradiation with light at a wavelength of more than 380 nm, preferably light at a wavelength of about 385 nm or more and 400 nm or less, and then irradiated with light at a wavelength of 100 nm or more and 380 or less, or alternatively may be irradiated with light at a wavelength of 100 nm or more and 380 nm or less, and then post-cured to further cure the resin composition. The presence or absence of pre-curing and/or post-curing may be suitably decided according to the desired properties required for the matte layer, such as processing characteristics and surface properties including stain resistance. The above wavelength light belongs to UV light, but is not limited to UV light. It is also possible to use other ionizing radiation such as an electron beam. For example, during post curing, an electron beam may be preferably used from the viewpoint of improving the surface properties of the matte layer.
In the production method of the present disclosure, the matte layer may be formed by irradiating, with light at a wavelength of at least 100 nm or more and 380 or less, a coating layer (uncured resin layer), which is coated with the resin composition for forming a matte layer by a known technique such as gravure printing, bar coating, roll coating, reverse roll coating, and comma coating.
The matte article obtained by the production method of the present disclosure may include another layer(s), such as a transparent resin layer, in addition to the base material, as described above as a layer(s) that can be employed in the matte article of the present disclosure.
For example, the decorative layer, adhesive layer, or primer layer may be formed by applying a coating liquid containing a composition for forming each layer by the above known technique and, if necessary, drying and curing. In the case of forming a transparent resin layer, a resin film for forming the transparent resin layer may be formed by, for instance, dry lamination.
Among the matte articles of the present disclosure, an article structured by a single layer as shown in
The second production method includes the steps of; applying a resin composition for forming a matte article that contains a resin and a wrinkle formation stabilizer on a release layer of a support sheet having the release layer to form a coating layer; irradiating the coating layer with light at a wavelength of at least 100 nm or more and 380 nm or less; and peeling off the support sheet.
The support sheet may be suitably selected from those exemplified as optionally used as the above base material. For example, a base material made of a fibrous material, preferably paper such as high-quality paper may be used. It is easy to peel off the support sheet from the matte article after the resin composition is made into a matte article, the handling is easy as well as cost-effective.
The release layer is a layer provided to facilitate the removal of the support sheet from a matte article after the resin composition is made into the matte article. The release layer excels in releasability. Examples include those containing an acrylic resin, vinyl chloride-vinyl acetate, an olefin resin, a silicone resin, a fluorine resin, or each silicone or fluorine-modified resin. The release layer may be optionally admixed with wax.
Preferable examples of the wax include each wax such as microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, each low-molecular-weight polyethylene, wood wax, beeswax, whale wax, insect wax, wool wax, shellac wax, candelilla wax, petrolatum, partially modified wax, a fatty acid ester, or a fatty acid amide.
The resin composition for forming a matte article that contains a resin and a wrinkle formation stabilizer may be adopted from the resins and wrinkle formation stabilizers exemplified as those that can be used for the resin composition for forming a matte layer. In addition, the content of wrinkle formation stabilizer, for instance, is also the same as that of the resin composition for forming a matte layer.
The resin composition for forming a matte article may be applied like the application of the resin composition for forming a matte layer as described above. The method of irradiating the coating layer with light at a wavelength of at least 100 nm or more and 380 nm or less is like the irradiation of a layer containing the resin composition for forming a matte layer.
The thickness of the coating layer is the thickness of the matte article as it is. The thickness of the coating layer should be determined according to the desired thickness and is not particularly limited. The thickness may be selected from a range from 1 μm to 10 cm, which is the widest thickness of the above base material. In view of, for instance, the suitability for manufacturing and handling, the thickness of the coating layer is preferably 3 μm or larger and more preferably 5 μm or larger, and the upper limit is preferably 300 μm or less and more preferably 200 μm or less.
A decorative layer may be provided to improve the design before formation of the coating layer containing a resin composition for forming a matte article. Thus, in the case of a single layer structure as shown in
By irradiating the coating layer of the resin composition for forming a matted article with light at the above wavelength, the surface is cured and shrinks in the same manner as the above matte layer. Thereby, the formation of wrinkles is stabilized, and the resin composition surface layer becomes a cured product with the above surface shape. Furthermore, curing progresses from the surface to the deep inner area, where curing is slower, in the depth direction, and the resin composition is totally overall. Accordingly, a matte article having the above surface shape on at least a part of the surface is produced.
In addition, regarding irradiation, post-curing or pre-curing may be performed to accelerate curing in the deep inner area.
By irradiating light at the above predetermined wavelength to cure a coating layer of the resin composition for forming a matte article, and the peeling off the support sheet, a matte article having the above surface shape on at least a part of the surface can be obtained.
Among the matte articles of the present disclosure, an article structured by a single layer as shown in
The third production method includes the step of embossing at least a part of the surface of a resin molding by using, for instance, an embossing plate or shaped sheet to give the above surface shape.
The embossing plate or shaped sheet may be used without any particular restriction so as to be able to impart the above surface shape. The surface shape of embossing plate or shaped sheet is a shape opposite to the surface shape having been imparted. Specifically, the shape is such that Ssk (skewness) and Sku (kurtosis) are numerical value that are symmetric across a normal distribution of 0 and 3, respectively, with Ssk (skewness) and Ssk (skewness) of the shaped sheet. Accordingly, with regard to the shaped sheet used to obtain a matte article of the present disclosure, an embossing sheet or a shaped sheet having a surface shape with a Ssk (skewness) of 0 or less and a Sku (Kurtosis) of 3 or more may be used. For example, when an embossing plate or shaped sheet with a Ssk (skewness) of −0.50 and a Sku (kurtosis) of 3.75 is used, a matte article having a surface shape with a Ssk (skewness) of 0.50 and a Sku (kurtosis) of 2.25 can be obtained. Note that the numerical values about the surface shape of the shaped sheet or the matte article are, in principle, theoretical numbers. Of course, some errors are included.
Meanwhile, examples of the matte article of the present disclosure include a thermosetting resin decorative sheet such as a high-pressure melamine resin decorative sheet, a low-pressure melamine resin decorative sheet, a diallyl phthalate (DAP) resin decorative sheet, a polyester decorative sheet, a guanamine resin decorative sheet, or a phenolic resin decorative sheet. The thermosetting resin decorative sheet is a decorative sheet obtained by impregnating a fibrous material, for example, paper, a woven or non-woven fabric made of fiber described as a base material that can be employed as the above base material for a matte article, with a liquid uncured thermosetting resin; and by pressure molding or heat-pressure molding the resulting material at, for example, a heating temperature of 100 to 200° C., a pressure of 0.1 to 9.8 MPa, and a molding time of 10 seconds to 120 minutes to give a decorative sheet. When the pressure molding or heat-pressure molding is performed, the base material and the above-mentioned embossing plate or shaped sheet are arranged so that they are laminated, and then molded. Thereby, a decorative sheet as a matte article having the above surface shape.
In this case, preferable examples of the thermosetting resin impregnated in the base material include a melamine resin, a urea resin, a melamine-urea resin, a guanamine resin, a diallyl phthalate resin, a polyester resin, a phenol resin, an epoxy resin, an amino alkyd resin, a silicon resin, or a polysiloxane resin. Preferred is a thermosetting resin such as a melamine resin, a urea resin, a melamine-urea resin, a guanamine resin, or a sulfonamide resin. Among them, preferred is a melamine resin, a melamine-urea resin, or a phenolic resin. Particularly preferred is a melamine resin.
<Application>
The matte article of the present disclosure is applicable as a decorative member as described below.
In addition, the matte article of the present disclosure may also be used as a shaped sheet. When used as a shaped sheet, the matte article can be used as, for instance, an embossing plate or a shaped sheet used for embossing in the second and/or third production method described above. This can produce the above article structured by a single layer or a thermosetting resin decorative sheet.
The surface shape of the shaped target material (e.g., an article structured by a single layer, a thermosetting resin decorative sheet) should have a shape opposite to the surface shape of the shaped sheet, which is a matte article of the present disclosure, as described above. Therefore, the target material such as an article structured by a single layer, or a thermosetting resin decorative sheet has a Ssk (skewness) of 0.00 or less and a Sku (kurtosis) of 2.50 or more, and thereby has a moist touch and a matte effect.
[Decorative Member]
The matte article of the present disclosure may be used as a decorative member as it is, or may be used as a decorative member obtained by laminating, compositing, or combining an adherend therewith. Which case should be adopted may be determined as desired. When the matte article of the present disclosure is used for a decorative member, the matte article preferably has a decorative layer.
In the case with an adherend, the decorative member has the adherend and the matte article of the present disclosure as described above. Specifically, the surface of the adherend requiring decoration and the surface of the matte layer of the matte article opposite to the one side where wrinkles are formed to develop a matte effect and a dry and smooth touch are laminated facing each other. In the case with an adherend, it is also preferable that the matte article of the present disclosure is in a film form or a sheet form in consideration of efficient lamination performance.
On the other hand, the article of the present disclosure is suitable when an article with a single layer structure, as illustrated in
Of the articles structured by a single layer as shown in
(Adherend)
Examples of the adherend include a plate member such as a flat plate, a curved plate a three-dimensional object like a cylinder and a polygonal column, or a sheet (or film), which are made of various raw material. Examples include: a wood member used as, for instance, a plate member or a three-dimensional object like a wood fiberboard such as a wood veneer, a wood plywood, a laminated wood, a particleboard, and a MDF (medium density fiberboard) made of each type of wood such as cedar, cypress, pine, and lauan; a metal member used as, for instance, a plate member, three-dimensional object, or sheet made of metal such as iron, aluminum, copper, and alloy containing one or more of these metals; a ceramic member used as, for instance, a plate member or three-dimensional object made of non-ceramic ceramic system material such as glass, ceramic like pottery, gypsum, cement, ALC (lightweight foamed concrete), and calcium silicate series; or a resin member used as, for instance, a plate member, three-dimensional object, or sheet made of resin such as an acrylic resin, polyester resin, polystyrene resin, polyolefin resin like polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, polyvinyl chloride resin, cellulose resin, and rubber. These members may be used singly, or a plurality of the kinds may be used in combination.
The adherend may be selected, if appropriate, from the above according to its application. When the application involve: an interior member for buildings such as a wall, ceiling, and floor; an exterior member such as an exterior wall, roof, eaves ceiling, fence, and gate; or a fixture or fitting member such as a window frame, door, handrail, baseboard, trim, and molding, the adherend is preferably made of at least one member selected from the wood member, the metal member, and the resin member. When the application involve an exterior member such as an entrance door, a window frame, or a fixture such as a door, the adherend is preferably made of at least one member selected from the metal member and the resin member.
The thickness of the adherend may be selected, if appropriate, according to the application and material, and is preferably from 0.1 mm to 100 mm, more preferably from 0.3 mm to 5 mm, and still more preferably from 0.5 mm to 3 mm.
(Adhesive Layer)
It is preferable that the adherend and the matte article are attached via an adhesive layer to obtain excellent adhesion.
The adhesive used for the adhesive layer is not particularly limited, and any known adhesive can be used and may be suitably selected depending on its usage. Preferable examples of the adhesive include a moisture-curing adhesive, an anaerobic curing adhesive, a dry-curing adhesive, a UV-curing adhesive, a thermally sensitive adhesive (e.g., a hot melt adhesive), or a pressure-sensitive adhesive.
Examples of a resin used for each adhesive include an acrylic resin, a urethane resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, a styrene-acrylic copolymer, a polyester resin, an amide resin, a cyanoacrylate resin, or an epoxy resin. They may be used singly, or a plurality of the kinds may be used in combination. In addition, it is possible to use an ester-based adhesive or a two-component urethane-based curable adhesive using, for instance, an isocyanate compound as a curing agent.
Further, a bonding agent may also be used for the adhesive layer. The bonding agent used may be selected, if appropriate, from each bonding agent such as an acrylic, urethane-based, silicone-based, and rubber-based bonding agent.
The thickness of the adhesive layer is not particularly limited. In order to obtain excellent adhesion, the thickness is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and still more preferably from 10 μm to 30 μm.
[Total Light Transmittance]
The decorative member using the matte article of the present disclosure may be equipped with, for instance, a base material, a decorative layer or the like made of non-transparent material, or may employ an adherend made of non-transparent material, as already described above. The decorative member is also applicable to, for instance, exterior member, interior member, and the like. In consideration of the above, the total light transmittance of the decorative member using the matte article of the present disclosure as measured in accordance with JIS K7361-1:1997 is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less.
(Method for Producing Decorative Member)
The decorative member may be produced through the step of laminating a matte article of the present disclosure and an adherend.
This step is a step of laminating an adherend and a matte article of the present disclosure. The surface of the adherend requiring decoration and the surface of the matte layer of the matte article opposite to the one side where wrinkles are formed to develop a matte effect and a dry and smooth touch, or the side of the base material if a matte article of the present disclosure has the base material, are laminated facing each other. If the matte article of this disclosure has a base material, the decoration-requiring surface faces and is layered on the surface on the base material side. Examples of the method of laminating an adherend and a matte article includes a lamination method in which a matte article is laminated, via an adhesive layer, onto a plate-shaped adherend by applying pressure with a pressurizing roller.
In the case where a hot melt adhesive (also called a “heat-sensitive adhesive”) is used as an adhesive, the heating temperature depends on the type of resin included in the adhesive, and is preferably from 160° C. to 200° C. For a reactive hot melt adhesive, the heating temperature is preferably from 100° C. to 130° C. In addition, vacuum forming may be generally performed while heating. This temperature is preferably from 80° C. to 130° C. and more preferably from 90° C. to 120° C.
The decorative member obtained in the above manner may be cut as desired, and then the surface and the wood end portion may be decorated with grooves, chamfers, etc., by using a router, a cutter, or another cutting machine. The decorative member is suitable for various applications, for example, interior members of buildings such as walls, ceilings, and floors; exterior members such as exterior walls, eaves ceilings, roofs, fences, and rails; fixture or fitting members such as window frames, doors, door frames, railings, baseboards, trims, and moldings; general furniture such as chests, shelves, and desks; kitchen furniture such as dining tables, and sinks; surface decorative boards such as cabinets for home appliances and OA equipment; vehicle interior or exterior members; and so on.
In addition to the above decorative members used for buildings and the like, the matte article of the present disclosure may be used for packaging materials, whiteboards or blackboards, credit cards, cash cards, telephone cards, various types of cards such as various certificates, keyboards of various keyboards, windows, doors, transparent boards (e.g., window glass) for partitions, artificial leather, etc., as a single form, or in a laminated, composite, or combined form with another material(s) (e.g., an adherend). In these applications, it is preferable that the matte article of the present disclosure developing a matte effect and a dry and smooth touch is usually placed on the topmost surface. Other forms of use are of course possible, depending on, for instance, the application and usage.
Next, the present disclosure will be further described in detail with reference to Examples. The present discloser, however, is no way limited to these Examples.
(Measurement Method of Surface Shape)
The Ssk (skewness), Sku (kurtosis), RSm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) of the article obtained in each of Examples and Comparative Examples were measured on each rectangle (1024 μm×768 μm) of any part of the surface shape of the article while using a shape analysis laser microscope (“VK X150 (control unit)/VK-X160 (measurement unit); manufactured by Keyence Corporation) with a 50× objective lens under conditions at a laser wavelength: 658 nm, a measurement mode: surface shape mode, a measurement pitch: 0.13 μm, and measurement quality: high-speed mode.
The cutoff values for RSm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) were each set to 0.8 mm.
(Evaluation Method: 60° Gloss Value)
A gloss meter (“Micro-Gloss (model name)”; manufactured by BYK Gardner, Inc.) was used to measure the 60° specular gloss of the article obtained in each of Examples and Comparative Examples in accordance with K 5600-4-7:1999.
(Evaluation of Texture (Evenness of Surface Condition))
Given 20 adults were instructed to evaluate the surface texture (evenness of surface condition) of the article obtained in each of Examples and Comparative Examples under the following criteria.
(Evaluation of Dry and Smooth Touch)
While an oxford fabric with 80-count cotton yarn was used as a touch reference, which is a reference for a dry and smooth touch, given 20 adults were instructed to evaluate the surface touch of the article obtained in each of Examples and Comparative Examples under the following criteria.
A polypropylene sheet (thickness: 100 μm) treated with corona discharge was used as a base material. On one side of the base material, a colored layer (thickness: 3 μm) was provided by applying printing ink (binder resin: two-component curable acrylic-urethane resin) by gravure printing. On the colored layer, a primer layer (thickness: 2 μm) was provided by applying a resin composition containing an acrylic resin and a urethane resin as a binder resin. A matte layer was provided on the base material in a manner that: applying a resin composition for forming a matte layer (polyfunctional urethane acrylate oligomer 1 (tetrafunctional; average molecular weight: 1800): 65 parts by mass; a polyfunctional acrylate monomer (bifunctional; molecular weight: 400): 35 parts by mass; wrinkle formation stabilizer 1 (silica particles; average particle size: 3 μm): 3.0 parts by mass; wrinkle formation stabilizer 2 (silica particles; average particle size: 5 nm): 3.0 parts by mass; a photopolymerization initiator (benzophenone): 0.8 parts by mass) on the primer layer by gravure printing (coating amount: 5 g/m2 (when dried)); then, irradiating with UV light (wavelength: 395 nm; UV dose: 6 W/cm2) using a UV irradiation device including an LED; then, irradiating with UV light (wavelength: 172 nm (Xe2); UV power density: 1 W/cm; cumulative light amount: 10 to 100 mJ/cm2; nitrogen atmosphere (oxygen level: 200 ppm or less)) using an excimer light irradiation device; and further irradiating using a high-pressure mercury lamp (UV power density: 200 W/cm). Thereby, a matte article having the base material and the matte layer was obtained. The 60° gloss value of the obtained matte article was measured from the matte layer side and was 1.4. In addition, the surface shape was measured, and the texture and the touch were evaluated by the above protocols. Table 1 shows the results.
Each of a matte articles was obtained in the same manner as in Example 1 except that the amount of each wrinkle formation stabilizer used in the resin composition for forming a matte layer, the resin composition used for forming the matte layer, and the base material were as designated in Table 1. The polyfunctional urethane acrylate oligomer 2 used in Examples 5 and 6 is an oligomer with three functional groups. Table 1 shows the 60° gloss value and texture evaluation of each of the resulting matte articles on the matte layer side. In addition, the surface shape was measured, and the texture and the touch were evaluated by the above methods. Table 1 shows the results.
An article was obtained in the same manner as in Example 1 except that the amount of each wrinkle formation stabilizer used in the resin composition for forming a matte layer was set to 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value on the matte layer side of the resulting article was determined. In addition, the surface shape was measured, and the texture and the touch were evaluated by the above methods. Table 1 shows the results.
An article was obtained in the same manner as in Example 1 except that the amount of each wrinkle formation stabilizer used in the resin composition for forming a matte layer was set to 0 parts by mass, instead 15.0 parts by mass of matting agent (average particle size: 8.0 μm) was used instead, and only electron beams (acceleration voltage: 75 kV; irradiation dose: 30 kGy (3 Mrad)) were used for irradiation. The 60° gloss value on the matte layer side of the resulting article was determined. In addition, the surface shape was measured and the texture and the touch were evaluated by the above methods. Table 1 shows the results.
A polypropylene sheet (thickness: 100 μm) treated with corona discharge was used as a base material. On one side of the base material, a colored layer (thickness: 3 μm) was provided by applying printing ink (binder resin: two-component curable acrylic-urethane resin) by gravure printing. On the colored layer, a primer layer (thickness: 2 μm) was provided by applying a resin composition containing an acrylic resin and a urethane resin as a binder resin. A matte layer was provided on the base material in a manner that: applying a resin composition for forming a matte layer (polyfunctional urethane acrylate oligomer 1 (tetrafunctional; average molecular weight: 1800): 65 parts by mass; a polyfunctional acrylate monomer (bifunctional; molecular weight: 400): 35 parts by mass; wrinkle formation stabilizer 1 (silica particles; average particle size: 3 μm): 3.0 parts by mass; wrinkle formation stabilizer 2 (silica particles; average particle size: 5 nm): 3.0 parts by mass; a photopolymerization initiator (benzophenone): 0.8 parts by mass) on the primer layer by gravure printing (coating amount: 5 g/m2 (when dried)); then, irradiating with UV light (wavelength: 172 nm (Xe2); UV power density: 1 W/cm; cumulative light amount: 10 to 100 mJ/cm2; nitrogen atmosphere (oxygen level: 200 ppm or less)) using an excimer light irradiation device; and further irradiating using a high-pressure mercury lamp (UV power density: 200 W/cm). Thereby, a matte article having the base material and the matte layer was obtained. The 60° gloss value of the obtained matte article was measured from the matte layer side and was 1.6. In addition, the surface shape was measured, and the texture and the touch were evaluated by the above protocols. Table 2 shows the results.
A matte articles was obtained in the same manner as in Comparative Example 3 except that a paper base material (thickness: 30 μm) was used as a base material. Table 2 shows the 60° gloss value and texture evaluation of the resulting matte article on the matte layer side. In addition, the surface shape was measured, and the texture and the touch were evaluated by the above protocols. Table 2 shows the results.
A matte articles was obtained in the same manner as in Comparative Example 3 except that only a polyfunctional (bifunctional) acrylate monomer was used as the resin in the resin composition for forming a matte layer. Table 2 shows the 60° gloss value and texture evaluation of the resulting matte article on the matte layer side. In addition, the surface shape was measured, and the texture and the touch were evaluated by the above protocols. Table 2 shows the results.
A polypropylene sheet (thickness: 100 μm) treated with corona discharge was used as a base material. On one side of the base material, a colored layer (thickness: 3 μm) was provided by applying printing ink (binder resin: two-component curable acrylic-urethane resin) by gravure printing. On the colored layer, a primer layer (thickness: 2 μm) was provided by applying a resin composition containing an acrylic resin and a urethane resin as a binder resin. A matte layer was provided on the base material in a manner that: applying a resin composition for forming a matte layer (polyfunctional urethane acrylate oligomer 1 (tetrafunctional; average molecular weight: 1800): 65 parts by mass; a polyfunctional acrylate monomer (bifunctional; molecular weight: 400): 35 parts by mass; wrinkle formation stabilizer 1 (silica particles; average particle size: 3 μm): 3.0 parts by mass; wrinkle formation stabilizer 2 (silica particles; average particle size: 5 nm): 3.0 parts by mass; a photopolymerization initiator (benzophenone): 0.8 parts by mass) on the primer layer by gravure printing (coating amount: 5 g/m2 (when dried)); then, irradiating with UV light (wavelength: 395 nm; UV dose: 6 W/cm2) using a UV irradiation device including an LED; then, irradiating with UV light (wavelength: 172 nm (Xe2); UV power density: 1 W/cm; cumulative light amount: 10 to 100 mJ/cm2; nitrogen atmosphere (oxygen level: 200 ppm or less)) using an excimer light irradiation device; and further irradiating using a high-pressure mercury lamp (UV power density: 200 W/cm). Thereby, a shaped sheet having the base material and the matte layer was obtained.
Next, phenolic impregnated kraft paper (made by impregnating 200 g/m2 kraft paper with 30 mass % phenolic resin; manufactured by Ohta Industry, Inc.), black titanium paper (80 g/m2) as the decorative layer, and overlay paper (made by impregnating 22 g/m2 paper (manufactured by Mead corporation) with 300 mass % methylol-melamine resin (manufactured by Cymel, Inc.)) were prepared. The phenolic impregnated kraft paper, the black titanium paper, and the overlay paper were laminated in this order. Further, the overlay paper and the side with a surface shape of the above-mentioned shaped sheet were overlapped so that they are in contact with each other. The resulting material was held between mirror plates, and heat-formed for 30 minutes at a pressure of 7.8 MPa (80 kg/cm2) and a temperature of 145° C., thereby the resin was impregnated and cured to be integrated. Accordingly, a thermosetting resin decorative sheet (high-pressure melamine decorative sheet) as a matte article was obtained.
The 60° gloss value of the obtained matte article was measured from the matte layer side and was 1.5. In addition, the surface shape was measured and the texture and the touch were evaluated by the above protocols. Table 3 shows the results.
A shaped sheet was obtained in the same manner as in Comparative Example 6 except that the resin contained in the resin composition for forming a matte layer in Comparative Example 6 was 90 parts by mass of a polyfunctional urethane acrylate oligomer and 10 parts by mass of a mono-functional acrylate monomer. The resulting shaped sheet itself was used as the matte article in Comparative Example 7. The 60° gloss value of the obtained matte article was measured from the matte layer side and was 1.6. In addition, the surface shape was measured, and the texture and the touch were evaluated by the above protocols. Table 3 shows the results.
The results in Table 1 have demonstrated that the matte articles of the present disclosure each have a 60° gloss value of 1.4 on the matted layer side, and the articles have extremely excellent matte effect visibility as well as excellent texture. The articles have also been found to give an excellent dry and smooth touch.
In contrast, in the wrinkle formation stabilizer-free article of Comparative Example 1, wrinkles somewhat occurred on the surface as shown in
The articles in Comparative Examples 3 to 5 had 60° gloss values of 1.4 to 1.6 on the matte layer side. The articles have extremely matte effect visibility and excel in the texture. However, the touch was neither dry nor smooth, and the touch was rather rough.
The articles in Comparative Examples 6 and 7 had 60° gloss values of 1.5 and 1.6, respectively, on the matte layer side. The articles have extremely excellent matte effect visibility and excel in the texture. However, the touch was neither dry nor smooth, and the touch was rather moist.
The matte article of the present disclosure gives excellent matte effect visibility and texture and excels in a dry and smooth touch. Thus, the decorative member is suitable for various applications, for example, interior members of buildings such as walls, ceilings, and floors; exterior members such as exterior walls, eaves ceilings, roofs, fences, and rails; fixture or fitting members such as window frames, doors, door frames, railings, baseboards, trims, and moldings; general furniture such as chests, shelves, and desks; kitchen furniture such as dining tables, and sinks; surface decorative boards such as cabinets for home appliances and OA equipment; or vehicle interior or exterior members.
In addition to the above decorative members used for buildings and the like, the matte article of the present disclosure can be used for packaging materials, whiteboards or blackboards, credit cards, cash cards, telephone cards, various types of cards such as various certificates, keyboards of various keyboards, windows, doors, transparent boards (e.g., window glass) for partitions, artificial leather, etc., as a single form, or in a laminated, composite, or combined form with another material(s) (e.g., an adherend).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-154137 | Sep 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/031945 | 8/31/2021 | WO |
