WO2022054644A1 - Article rendu mat - Google Patents

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Publication number
WO2022054644A1
WO2022054644A1 PCT/JP2021/031944 JP2021031944W WO2022054644A1 WO 2022054644 A1 WO2022054644 A1 WO 2022054644A1 JP 2021031944 W JP2021031944 W JP 2021031944W WO 2022054644 A1 WO2022054644 A1 WO 2022054644A1
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Prior art keywords
matte
layer
resin
less
article
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PCT/JP2021/031944
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English (en)
Japanese (ja)
Inventor
康宏 松川
祥太 西根
玲子 桜井
亮介 西垣
健 小笠原
美幸 飯原
敦 桑子
健史 西園
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大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Publication of WO2022054644A1 publication Critical patent/WO2022054644A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating

Definitions

  • the scratch resistance is reduced by falling off from the coating film and damaging the coating film, and the scratches become more noticeable due to the change in gloss due to the lack of the matting agent, or the minute gaps at the interface between the matting agent and the resin are contaminated.
  • the surface characteristics tend to be deteriorated due to the permeation of the substance and the deterioration of the stain resistance due to the adsorption of the contaminated substance on the matting agent itself.
  • the amount used is reduced in order to suppress the deterioration of the surface characteristics, the matting effect tends to decrease, and the surface characteristics and the matting effect have a bilateral relationship. Therefore, there is a limit to the matte effect using a matting agent.
  • Coarse cotton cloth such as Oxford cloth using thick thread, or linen cloth using thick thread of about 10 to 50 counts can be mentioned.
  • stone materials such as concrete, marble, terrazo, granite, sandstone; ceramic materials such as pottery, terracotta; wood-based materials such as natural wood, bamboo, cork; corrosive metals, and brass, gold, silver, copper, aluminum, etc.
  • Metals such as steel and stainless steel, especially those having various surface treatments such as hairline processing and silky blasting; coarse paper materials such as thin leaf paper and Japanese paper; and the like can also be mentioned as having a "rough” feel.
  • surface treatments such as hairline processing and silky blast processing on metal there are some that do not have a "rough” feel depending on the degree of processing, but it does not include those that have undergone such processing. Not to mention.
  • some other ceramic materials and wood materials do not have a "rough” feel depending on the surface processing, but it goes without saying that such processed materials are not included. .. Therefore, the matte article of the present disclosure is preferably used for applications such as expressing the design of the surface of these fabrics, stones, ceramic materials, metals, paper materials and the like.
  • the Sk (Kurtosis) is preferably 3.60 or more, more preferably 3.70 or more, still more preferably 3.80 or more.
  • the upper limit is not particularly limited, but is about 10.00 or less, preferably 9.00 or less, and more preferably 8.00 or less from the viewpoint of ease of manufacture and the like.
  • the Sk (Kurtosis) is within the above range, the matte effect and the rough texture are improved.
  • the surface shape of the matte article of the present disclosure has a specific Sk (skune) and Sk (Kurtsis), and the width with respect to the height is narrow according to the provisions of Sk (skune).
  • Sk sekune
  • Sk Korean
  • the surface shape of the matte article of the present disclosure has a pointed tip shape, and many elongated convex portions are scattered, so that the tip shape is sharpened with an appropriate contact frequency when touched with the pad of a finger. Can be felt.
  • the Rz (maximum height) is preferably 8.50 ⁇ m or more, more preferably 9.00 ⁇ m or more, still more preferably 9.50 ⁇ m or more, and the upper limit is preferably 30.00 ⁇ m or less, more preferably 26.00 ⁇ m or less. More preferably, it is 22.00 ⁇ m or less.
  • the cutoff value is 0.8 mm.
  • the layer structure is not particularly limited, and any layer structure may be adopted.
  • the simplest layer structure of the matte article of the present disclosure includes a single layer structure as shown in FIG.
  • the article shown in FIG. 3 is, for example, a cured product layer of a resin composition, preferably a cured product layer of a curable resin composition containing a curable resin such as an ionizing radiation curable resin described later, on one side thereof.
  • Examples thereof include an article having the above-mentioned surface shape on the surface, and an article composed of a single layer such as an article in which the surface of a resin molded product is subjected to processing such as embossing to shape the surface shape.
  • Wood-based materials that can be used as the base material include veneer, plywood, and laminated wood made of various types of wood such as cedar, cypress, pine, zelkova, ⁇ , oak, walnut, lauan, teak, and rubber wood. Particle board, medium density fiberboard (MDF) and the like are preferably mentioned.
  • MDF medium density fiberboard
  • the base material is used from the viewpoint of improving the adhesion to other layers such as the matte layer, which will be described later, which constitutes the matte article, and the adhesion to the adherend such as the resin molded product in which the matte article is laminated.
  • At least one surface thereof can be subjected to physical surface treatment such as acid value method and unevenness method, and surface treatment for improving easy adhesion such as chemical surface treatment.
  • the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method and the like
  • examples of the unevenness method include sandblasting method and solvent treatment method.
  • an adherend such as a resin molded product on which matte articles are laminated
  • May use an inorganic pigment such as a white pigment.
  • the above-mentioned base materials may be used alone or in combination of two or more. It may be a combination of a plurality of paper base materials, a paper base material and a fiber base material, a paper base material and a resin base material, a fiber base material and a resin base material, and a paper base material and a fiber base material and a resin base material. It may be a combination with a material. Further, the resin base material may be composed of either a single layer of the above resin base material or a multi-layer of the same type or different types of resin.
  • the "does not contain a matting agent” means that, in addition to not containing the matting agent at all, even if it is contained, it does not have the visibility of the matting effect based on the action effect of the matting agent itself. Specifically, it means that the content of the 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 with respect to 100 parts by mass of the resin. ..
  • the "matte agent” is specifically a layer in which the matte agent can be contained, that is, the thickness of the matte layer, from the viewpoint of forming a convex portion by the effect of cueing as described above. It means a particle having an average particle diameter whose lower limit is the smaller of more than 100% and more than 30 ⁇ m.
  • the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used alone, or the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used in combination. It is more preferable to use the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 in combination. When used in combination, the matte effect and the rough texture are improved.
  • the upper limit is not particularly limited in terms of improving the stable matte effect and improving the rough texture, but if the upper limit is within the above range, for example, the applicability of the resin composition for forming a matte layer The productivity of the decorative material is improved, and the visibility and texture of the matte effect are efficiently improved.
  • the blending ratio of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is preferably 0.05 to 0.95 as the blending amount of the wrinkle-forming stabilizer 1 when the total amount thereof is 100 parts by mass. It is by mass, more preferably 0.10 to 0.90 parts by mass, still more preferably 0.20 to 0.80 parts by mass, and even more preferably 0.30 to 0.70 parts by mass.
  • organic particles and inorganic particles can be used as described above, but the types of these particles themselves can be said to include those conventionally used as a matting agent, for example, the above-mentioned patent documents.
  • a matting agent such as spherical alumina or calcium carbonate is used in the matte layer of the decorative sheet according to 1.
  • a matting agent such as spherical alumina or calcium carbonate to exhibit the visibility of the matting effect by itself due to the light diffusion effect caused by the physical shape, as described in Patent Document 1.
  • the matte layer in the matte article of the present disclosure is a layer having the above-mentioned surface shape, and is preferably a cured product of a resin composition for forming a matte layer containing the above-mentioned specific wrinkle-forming stabilizer in a specific content. It is a layer composed of. As described above, by stabilizing the formation of wrinkles on the surface of the matte layer, the layer has a stable matte effect due to the light diffusion effect caused by the shape of the wrinkles, and also has a rough texture. ..
  • FIG. 6 is a schematic view showing an embodiment of the matte article of the present disclosure in a plan view, and is a schematic image of the surface of the matte article obtained in the examples.
  • planar view means to see the surface of the matte article from the positive direction of the Z axis in the XYZ coordinate system shown in FIGS. 3 to 6.
  • the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions, and the protrusions are linear. It is preferable to have a protrusion.
  • the “streak protrusion” (hereinafter, also referred to as “streak protrusion”) means that the ratio (length / width) of the length and width of the protrusion is 3 or more, preferably 5. As described above, it means that it is more preferably 10 or more, and the method for determining the length and width is as described later.
  • a more preferable irregular wrinkle is one composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions.
  • curvature means having one or more portions in which the extending direction of the convex portion 3 of the continuous line is reversed from one side to the other side in a plan view.
  • portion where the extending direction is reversed from one side to the other side for example, when the width of the convex portion 3 of the line is ignored (when the width of the plan view shape is regarded as 0).
  • the width of the convex portion 3 of the streak is ignored and the width is approximated by a straight line, the shape has a V-shaped polygonal line or a portion approximated by two sides sandwiching one vertex of the triangle. And so on.
  • the matte layer has wrinkles, that is, uneven shapes on at least one surface thereof.
  • the darkest part in the density distribution image is set to gradation 255, and the lightest part in the density distribution image is gradation.
  • the gradations 0 to 255 may be classified by binarizing the gradations 0 to 127 into concave portions and the gradations 128 to 255 into convex portions.
  • the height of the convex portion is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 2 ⁇ m or more.
  • the upper limit is about 10 ⁇ m or less.
  • the width of the convex portion is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, still more preferably 0.5 ⁇ m or more, and the upper limit is preferably 10 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3 ⁇ m. It is as follows.
  • FIG. 3 is a cross-sectional view showing an embodiment of the matte article of the present disclosure, and is a cross-sectional view of the matte article 1 cut along a plane parallel to the thickness direction thereof.
  • the thickness direction of the matte article 1 is the Z direction in FIG.
  • the shape of the concave portion may be, for example, an acute-angled shape as shown in 2a of FIG. 3, a semicircular or semi-elliptical shape as shown in 2b, or a combination thereof. Further, the shape as shown in 2c of FIG. 3 may be obtained, in which one convex portion has a concave portion in a part thereof.
  • the shape of the convex portion although the width is wide and narrow as shown in 3a and 3b of FIG. 3, it exhibits a semicircular or semi-elliptical shape.
  • the matte layer may be provided at a place where the consumer can see and touch the matte article, and at least one of the surfaces thereof. It may be provided on a part of the surface, or may be provided on the entire surface thereof. From the viewpoint of improving the matte effect and the rough texture, it is provided over the entire surface of one surface as shown in FIGS. 4 to 6. It is preferable that the film is used.
  • the number of functional groups of the polyfunctional (meth) acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, further preferably 2 or more and 4 or less, and further preferably 2 or more and 3 or less. Further, when the number of functional groups is the above, the above-mentioned surface shape is particularly easy to be obtained, and it is easy to improve the rough tactile sensation.
  • These polyfunctional (meth) acrylates may be used alone or in combination of two or more.
  • polymerizable oligomer a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond in the main chain.
  • aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resin having many reactive groups in small molecules, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether and the like.
  • oligomers and the like having cationically polymerizable functional groups.
  • dark color means a CIE (International Commission on Illumination) L * a * b * L * value in a color system (hereinafter referred to as "dark color”), which has a low brightness and is measured according to, for example, JIS Z8781-4: 2013. It may be simply referred to as "L * value”), which means that it is usually about 40 or less, preferably 30 or less.
  • the matte article of the present disclosure may employ a base material made of a non-transparent material, a decorative layer described later, and the like, and may be used for exterior members, interior members, and the like. It is possible. Considering the case where the above-mentioned base material, the decorative layer described later, etc. are adopted, and the case where it is used for the above-mentioned application, the total light transmittance of the matte article of the present disclosure is measured in accordance with JIS K7361-1: 1997. The rate is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less. In the present specification, the total light transmittance of the matte article is the total light transmittance measured in accordance with JIS K7361-1: 1997, and is an average value of measurements at any 10 points.
  • the matte article of the present disclosure may have, for example, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer and the like as other layers in addition to the matte layer and the base material.
  • 4 and 5 show cross-sectional views showing an embodiment of the matte article of the present disclosure having these layers.
  • 4 and 5 are cross-sectional views showing an embodiment of the matte article of the present disclosure, which is a cross-sectional view of the matte article 1 cut along a plane parallel to the thickness direction thereof.
  • the "thickness direction” means the Z direction in FIGS. 4 and 5.
  • the matte decorative material 1 shown in FIG. 4 has a base material 5 and a matte layer 4 in this order
  • the matte article 1 shown in FIG. 5 has a base material 5, a decorative layer 6, and an adhesive layer 7. It has a transparent resin layer 8, a primer layer 9, and a matte layer 4 in this order.
  • the matte article of the present disclosure When the matte article of the present disclosure is composed of, for example, a plurality of layers, it may have a primer layer in order to improve the interlayer adhesion of the plurality of layers.
  • a primer layer is used between the matte layer and the base material in order to improve the interlayer adhesion. Can be provided.
  • the thickness of the primer layer is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 1 ⁇ m or more and 8 ⁇ m or less, and further preferably 2 ⁇ m or more and 6 ⁇ m or less.
  • the matte article of the present disclosure may have a transparent resin layer in order to increase its strength and, in the case of having a decorative layer described later, from the viewpoint of protecting the decorative layer and the like.
  • the transparent resin layer has a base material
  • it may be provided between the base material and the matte layer, and when it has a decorative layer, the decorative layer and the matte layer are provided in order to protect the decorative layer. It may be provided in between.
  • the resin constituting the transparent resin layer examples include a polyolefin resin, a polyester resin, a polycarbonate resin, an acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”), an acrylic resin, and a vinyl chloride resin.
  • ABS resin acrylonitrile-butadiene-styrene resin
  • acrylic resin acrylic resin
  • vinyl chloride resin a polyolefin resin and a vinyl chloride resin are preferable from the viewpoint of post-processing suitability and the like. Further, two or more kinds of these various resins may be laminated or mixed and used.
  • the transparent resin layer may be transparent to the extent that the substrate side can be visually recognized from the transparent resin layer, and if it has a decorative layer, it may be transparent to the extent that the decorative layer can be visually recognized.
  • Colored transparent and translucent That is, in the present disclosure, "transparency" means not only colorless and transparent but also colored transparent and translucent.
  • the matte article of the present disclosure described above can be easily obtained.
  • a resin composition for matte formation containing a wrinkle-forming stabilizer for forming the matte layer with ultraviolet rays having a low wavelength of at least 100 nm or more and 380 nm or less. Wrinkles can be formed on at least one surface of the matte layer, and it is possible to impart a matte effect and a rough texture to the matte article (matte layer).
  • thermosetting such as high pressure melamine resin decorative board, low pressure melamine resin decorative board, diallyl phthalate (DAP) resin decorative board, polyester decorative board, guanamine resin decorative board, phenol resin decorative board and the like.
  • a resin resin veneer can also be mentioned.
  • the thermosetting resin decorative board is a liquid state of a thermosetting resin on a fibrous material, for example, a woven fabric or a non-woven fabric made of paper, which has been described as a base material that can be adopted as a base material for the above-mentioned matte article.
  • the matte article of the present disclosure can also be used as a shaping sheet.
  • a shaping sheet When used as a shaping sheet, it can be used as an embossing plate used for embossing in the second manufacturing method, the third manufacturing method, a shaping sheet, or the like, whereby the article composed of the above-mentioned single layer.
  • a thermosetting resin decorative board can be obtained.
  • the surface shape of the shaped object (article composed of a single layer, thermosetting resin decorative board, etc.) is the surface shape of the shaped sheet which is the matte article of the present disclosure. The shape is the opposite.
  • the matte article of the present disclosure can be used as a decorative member as it is, or can be used as a decorative member by laminating, compounding, or combining with an adherend. Which one to use may be determined as desired.
  • the matte article of the present disclosure is used for a decorative member, it is preferable that the matte article has a decorative layer.
  • the matte article composed of the cured product of the resin composition for forming the matte article obtained by the above-mentioned second production method is made up as it is. It can be used as a member, or it can be used in combination with an adherend depending on the thickness.
  • the decorative member using the matte article of the present disclosure includes a base material, a decorative layer, etc. made of a non-transparent material, and a cover made of a non-transparent material. There are cases where a landing material is used, and it can also be used for applications such as exterior members and interior members.
  • the total light transmittance of the decorative member using the matte article of the present disclosure measured in accordance with JIS K7361-1: 1997 is preferably 20% or less, more preferably 15% or less, and further. It is preferably 10% or less.
  • the matte article of the present disclosure is used as it is, or the matte article is laminated, composited, or combined with another material (adhesive material).
  • another material adheresive material.
  • the matte article of the present disclosure is arranged on the outermost surface, which exhibits a matte effect and a rough texture, but other uses are used depending on the use, purpose of use, etc. Of course, it is also possible to make it into a form.
  • Example 1 A polypropylene sheet (thickness: 100 ⁇ m) that has been subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by the gravure method to color it.
  • a layer (thickness: 3 ⁇ m) is provided, a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 ⁇ m), and the primer layer is matted.
  • Example 2 A matte article was obtained in the same manner as in Example 1 except that a paper base material (thickness: 30 ⁇ m) was used as the base material in Example 1.
  • Table 1 shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 1.
  • Example 1 the amount of the wrinkle forming stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, and 15.0 parts by mass of the matting agent (average particle size: 8.0 ⁇ m) was used instead. Then, an article was obtained in the same manner as in Example 1 except that only an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) was irradiated. The 60 ° gloss value on the matte layer side of the obtained article, the surface shape was measured by the above method, and the texture and tactile sensation were evaluated. These results are shown in Table 1.
  • Resin composition for layer formation polyfunctional urethane acrylate oligomer 1 (tetrafunctional, average molecular weight: 1800): 65 parts by mass, polyfunctional acrylate monomer (bifunctional, molecular weight: 400): 35 parts by mass, wrinkle formation stabilizer 1 (Silica particles, average particle size: 3 ⁇ m): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.
  • UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet amount: 6 W). / Cm 2 ), then irradiate with ultraviolet rays using an excima light irradiation device (wavelength: 172 nm (Xe 2 ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm 2 , nitrogen atmosphere (oxygen concentration 200 ppm).
  • Comparative Examples 3 to 7 In Comparative Example 2, the wrinkle formation stabilizer in the resin composition for forming the matte layer was compared except that the amount used as shown in Table 2, the resin composition for forming the matte layer to be used, and the base material were used. A matte article was obtained in the same manner as in Example 2.
  • the polyfunctional urethane acrylate oligomer 2 used in Comparative Examples 6 and 7 is an oligomer having 3 functional groups.
  • Table 2 shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 2.
  • a PET sheet (thickness: 100 ⁇ m) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method to color it.
  • a layer (thickness: 3 ⁇ m) is provided, a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 ⁇ m), and the primer layer is matted.
  • Resin composition for layer formation polyfunctional urethane (meth) acrylate oligomer (tetrafunctional, average molecular weight: 1800): 65 parts by mass, polyfunctional acrylate monomer (bifunctional, molecular weight: 400): 35 parts by mass, wrinkle formation stable Agent 1 (silica particles, average particle size: 3 ⁇ m): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): (0.8 parts by mass) is applied by the gravure method (application amount: 5 g / m 2 (when dried)), and then ultraviolet rays are irradiated using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet amount).
  • a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet amount).
  • the paper and the overlay paper are stacked in this order, and the overlay paper and the surface having the surface shape of the shaping sheet are overlapped so as to be in contact with each other, and then sandwiched between the end plates, and the pressure is 7.8 MPa (80 kg / cm 2 ). It was heat-processed and molded at a temperature of 145 ° C. for 30 minutes, and the resin was permeated, cured, and integrated to obtain a thermosetting resin decorative board (high-pressure melamine decorative board) as a matte article. The gloss value of the obtained matte article was measured at 60 ° from the matte layer side and found to be 1.5. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 3.
  • Comparative Example 9 In Comparative Example 8, the resin contained in the resin composition for forming the matte layer was applied in the same manner as in Comparative Example 8 except that the polyfunctional urethane acrylate oligomer: 90 parts by mass and the monofunctional acrylate monomer: 10 parts by mass. Obtained a mold sheet. The obtained shaped sheet itself was used as a matte article of Comparative Example 9. When the 60 ° gloss value of the obtained matte article was measured from the matte layer side, it was 1.6. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 3.
  • the matte articles disclosed in the present disclosure have 60 ° gloss values of 1.4 and 1.6 on the matte layer side, and are extremely excellent in visibility of the matte effect. It was confirmed that the texture was excellent. It was also confirmed that the texture was excellent.
  • the article of Comparative Example 1 containing a matting agent contained 15.0 parts by mass, which is larger than the content of the wrinkle forming stabilizer in the examples, but wrinkles were formed on the surface layer corresponding to the matte layer. It was confirmed that there was no formation, the 60 ° gloss value was 8.3, which was inferior to the gloss value of the matte article of the example, and the texture was also inferior.
  • FIGS. 7 to 9 are optical microscope images of the matte articles of Examples 1 to 3, respectively (the width of each image corresponds to 272.0 ⁇ m). According to the optical microscope images of Examples 1 to 3 (FIGS. 7 to 9 respectively), it can be confirmed that the matte decorative materials of these Examples have irregular wrinkles on the surface thereof. On the other hand, according to the optical microscope image (FIG. 10) of Comparative Example 1, wrinkles like the matte decorative material of the example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. The surface condition was unstable (not uniform), and the texture was not excellent. From this result, the matte article of the present disclosure exhibits a specific surface shape due to wrinkles on the surface thereof, and due to the surface shape, the matte article has an extremely excellent matte effect visibility and texture. It was confirmed that the moist texture was excellent.
  • the articles of Comparative Examples 2 to 7 have a 60 ° gloss value of 1.4 on the matte layer side, are extremely excellent in visibility of the matte effect, and are also excellent in texture. Was confirmed. However, there was no rough texture, but rather a silky texture.
  • the articles of Comparative Examples 8 and 9 have 60 ° gloss values of 1.5 and 1.6 on the matte layer side, are extremely excellent in visibility of the matte effect, and are also excellent in texture. It was confirmed that it was a thing. However, there was no rough texture, but rather a moist texture.
  • the matte article of the present disclosure is used as it is, or the matte article is laminated, composited, or combined with another material (adhesive material).
  • another material adheresive material.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un article rendu mat présentant d'excellentes visibilité et texture d'effet de matage et une excellente texture tactile rugueuse, l'article ayant une surface conçue de telle sorte qu'au moins une partie de la surface a une asymétrie (Ssk) supérieure ou égale à 0,00 et un aplatissement (Sku) supérieur à 3,50, définis par la norme ISO 25178-2:2012.
PCT/JP2021/031944 2020-09-14 2021-08-31 Article rendu mat WO2022054644A1 (fr)

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JP2020154135 2020-09-14

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JP7201123B1 (ja) 2022-03-17 2023-01-10 大日本印刷株式会社 化粧シート及び化粧材
JP7294482B1 (ja) 2022-03-11 2023-06-20 大日本印刷株式会社 積層体
WO2023191052A1 (fr) * 2022-03-31 2023-10-05 凸版印刷株式会社 Feuille décorative et procédé de fabrication d'une feuille décorative
JP7440709B1 (ja) 2022-09-15 2024-02-28 バンドー化学株式会社 木目調加飾フィルム及び木目調加飾フィルムの製造方法
WO2024058079A1 (fr) * 2022-09-16 2024-03-21 Ｄｏｗａエレクトロニクス株式会社 Procédé de production d'élément semi-conducteur optique

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JP7294482B1 (ja) 2022-03-11 2023-06-20 大日本印刷株式会社 積層体
JP2023133013A (ja) * 2022-03-11 2023-09-22 大日本印刷株式会社 積層体
JP7201123B1 (ja) 2022-03-17 2023-01-10 大日本印刷株式会社 化粧シート及び化粧材
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WO2023191052A1 (fr) * 2022-03-31 2023-10-05 凸版印刷株式会社 Feuille décorative et procédé de fabrication d'une feuille décorative
JP7440709B1 (ja) 2022-09-15 2024-02-28 バンドー化学株式会社 木目調加飾フィルム及び木目調加飾フィルムの製造方法
WO2024058079A1 (fr) * 2022-09-16 2024-03-21 Ｄｏｗａエレクトロニクス株式会社 Procédé de production d'élément semi-conducteur optique
JP7464667B2 (ja) 2022-09-16 2024-04-09 Ｄｏｗａエレクトロニクス株式会社 光半導体素子の製造方法

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