JP2014024318A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an aqueous pigment dispersion of C. I. Pigment Yellow 74 capable of obtaining, in a high manufacturing efficiency, an aqueous pigment dispersion dispersed at extremely fine particle diameters in such a way that an ink composition for ink jet recording prepared by using the dispersion as a main component can yield images excellent in terms of glossiness and coloration.SOLUTION: The method for manufacturing an aqueous pigment dispersion for ink jet recording comprises a kneading step of preparing a colored kneaded admixture solid at normal temperature by kneading an admixture including a pigment, a styrene-acrylic acid copolymer, a humectant, and a basic compound and a mixing step of agitating a mixture obtained by adding an aqueous medium to the resulting colored kneaded admixture; in this method for manufacturing an aqueous pigment dispersion for ink jet recording, the pigment is C. I. Pigment Yellow 74, and 15-50 mass% of water is added to the pigment in the kneading step.

Description

  INDUSTRIAL APPLICABILITY The present invention is used as an interior material for covering a wall surface, a floor surface, etc. in a building such as a house, or a covering material for a surface of a building fixture, furniture, housing equipment, etc. in a living room. The present invention relates to a decorative sheet capable of imparting high design properties such as a pattern.

Conventionally, various methods for imparting a three-dimensional appearance such as irregularities to a decorative sheet and enhancing design properties have been used. For example, in a decorative sheet in which a pattern such as a wood grain is formed, a more natural wood texture can be given by giving a stereoscopic effect corresponding to the grain.
As a method of imparting a natural three-dimensional effect, for example, a printed layer with a grain pattern is laminated on a base sheet, and irregularities are actually formed by pressing or the like on a transparent film sheet laminated as the outermost surface. A method of changing the appearance of the wood grain pattern according to the direction in which it is performed. However, it is impossible to form irregularities corresponding to a fine grain pattern by pressing a film sheet, and there is a limit to improving the wood texture by the irregular pattern that does not necessarily correspond exactly to the grain pattern.

On the other hand, a pattern with a glossy pattern that changes the gloss state corresponding to the pattern of wood grain, etc. is formed, and a difference in level feeling due to partial gloss and luster corresponding to the pattern of wood grain etc. is formed to give a natural three-dimensional feeling Since the method of applying can form a glossy or glossy pattern by gravure printing, for example, when a wood grain pattern is formed, a more natural wood texture corresponding to a fine wood grain pattern can be realized. For this reason, the method is used for the production of a decorative sheet, mainly using a paper base sheet having excellent fine gravure printability and adhesiveness during construction as a base material. The sheet has been applied on a wooden substrate and applied to the production of a decorative board having a natural wood design, for example (see Patent Document 1).
However, although the paper base sheet is excellent in dimensional stability, the “elongation” is insufficient, so that the followability to the surface of the object to be coated at the time of construction is lacking. For this reason, there is no problem at the time of construction on a flat surface such as a wall surface. However, when the object to be coated has a three-dimensional shape, for example, it is necessary to wind up decorative paper to the end face or the back face, a good covering state is realized. It was difficult. Especially when performing construction and processing by wrapping through a process using a wrapping machine or V-cut machine, the decorative sheet stretches or breaks due to local tensile or bending stress at corners and ridges. However, a good finished state such as corners could not be realized.

For the above decorative sheets, plastic films are also used as base sheets, and base sheets containing polyolefin resins, polyester resins, acrylic resins, acrylonitrile butadiene styrene resins, vinyl chloride resins, etc. are studied and used. Has been.
Among them, in particular, the vinyl chloride resin is easy to control the mechanical performance by adjusting the blending or using a plasticizer. For example, when a decorative sheet is wound while covering the corner portion of the boundary between the surface and the end surface of the material to be coated, the decorative sheet can be stretched easily, so that it does not easily wrinkle, and even if the boundary portion has a large curvature, The material sheet is less likely to whiten and deteriorate the mechanical properties of the decorative sheet. In addition, coloring is basically easy, and it is easy to use a base sheet having a color tone that is optimal for the pattern of the assumed decorative sheet. In addition, it is easier to adhere to the material to be coated than a polyolefin resin or the like, and no primer treatment is required. On the other hand, it has been found that dioxins during combustion, which has been a concern in the past, can be eliminated by incineration at a high temperature of 800 ° C. or higher. There are many advantages as a base sheet, such as low consumption and flame retardancy. For this reason, for example, a wallpaper composed mainly of a polyvinyl chloride resin layer has been studied, and the surface layer portion is not necessarily good in adhesion, but a urethane resin layer having good mechanical strength can exert a gloss matte effect. (Patent Document 2).

However, in spite of having the above-mentioned various advantages and being inexpensive, in the decorative sheet having a high design such as a grain pattern having a natural three-dimensional effect, the base sheet containing the vinyl chloride resin Is not actually used and commercialized, and despite the drawbacks in construction and processing, the conversion from the conventional paper base sheet has not progressed. This is because when the top coat formed on the outermost surface of the decorative sheet is cured and aged, the base sheet containing a vinyl chloride resin that is relatively weak against heating may be thermally damaged, causing deformation and wrinkles. It is thought that it is easy.
On the other hand, if the temperature during curing and aging is lowered, the top coat layer will be insufficiently cured, so that the wear resistance and the like are likely to be lowered, and sufficient durability of the decorative sheet surface after construction may not be realized. There is. In particular, in the case of a decorative sheet, further durability and wear resistance are required at the corner when the covering material is wound. Such parts may have reduced mechanical properties due to deformation of the base sheet, and must receive external loads not by the surface but by lines and points, and the large unit area This is because it is a part that receives external force, and on the other hand, it is a part that is more likely to come into contact with people and things and is subject to friction. Considering the situation in which the top coat layer is not a uniform film formed on the outermost surface, but forms a specific pattern itself and forms irregularities on the surface, it is assumed that the concentration of external force will further progress, Abrasion resistance is even more important.

As means for improving the abrasion resistance of the topcoat layer, methods of adding inorganic fine particles, spherical glass beads and silicone-based release agents have been studied (see Patent Documents 3 and 4), and further non-reactive. Silicone oil is also added (see Patent Document 5). However, in patent document 3, although the abrasion-resistant resin layer containing an abrasive | polishing agent is formed, the whole cosmetics layer exhibits the rough appearance and designability may fall. On the other hand, the gloss improving resin layer forming the outermost layer is not subjected to treatment for improving wear resistance. In Patent Document 4, wear resistance is ensured by beads made of SiO ₂ inorganic substance having an average particle diameter of 2 to 5 μm and olefin wax, but lack of lubricity due to olefin wax at corners and ridges. There is a concern that beads may fall off due to lack of lubricity. Further, in Patent Document 5, the silicone release agent added for imparting lubricity to the outermost layer and improving wear resistance is reversed when the raw sheet of the decorative sheet is wound, so that the decorative sheet is coated. There is a possibility that the adhesion to the material may be lowered, and there is a concern that the abrasion resistance of the outermost layer itself may deteriorate with time due to such a transition. None of these means for improving wear resistance is necessarily sufficient to compensate for the decrease in wear resistance when a thermosetting resin is used and a production process with low curing temperature and low aging temperature is used. In particular, it was difficult to achieve wear resistance at the corners. It is conceivable to use a UV curable resin or the like for the topcoat layer, but it contains an inexpensive vinyl chloride resin in consideration of a significant change in manufacturing equipment used for paper and an increase in raw material costs. Using the base sheet, it is impossible to achieve the original manufacturing cost reduction purpose of achieving the same or better quality while keeping the price low. In addition, the non-flammability and flameproofness of vinyl chloride resin cannot be realized at low cost.

JP-A-5-092537 JP-A-5-278189 JP-A-2004-090319 JP 2004-136478 A JP2001-129929

The object of the present invention is a decorative sheet in which a high-design pattern such as a three-dimensional pattern is formed on a base sheet containing a vinyl chloride resin, and a paper base sheet is used. While forming a fine design equivalent to the above, it has excellent workability at the time of entrainment to the coated object, excellent surface wear resistance, particularly wear resistance at the corner where it is entrained, and preferably made of paper It is to provide a decorative sheet that does not cause a large price increase compared to the case of using the base material sheet.
Further, the object of the present invention is to cover articles having a flat part, a ridge part, and a corner part such as joinery, furniture, and dwelling equipment by covering the surface with a single decorative sheet and covering the article. A method of manufacturing an article, which can be coated using a single decorative sheet having a high design such as a three-dimensional wood grain pattern, and moreover, the surface of furniture, fittings, etc. after the coating process, in particular An object of the present invention is to provide a method for manufacturing an article having good wear resistance at ridges and corners.
Furthermore, an object of the present invention is a fitting, furniture, housing equipment, etc. that has been subjected to a wrapping coating process using a single decorative sheet having a high design such as a three-dimensional wood grain pattern, and is covered with a decorative sheet An object of the present invention is to provide a joinery or the like which has no wrinkles or seams on the surface and has excellent wear resistance on the decorative sheet surface, particularly on the ridge.

The inventors basically changed the paper base sheet to a base sheet containing a vinyl chloride resin, based on the configuration of the decorative sheet using the conventional paper base sheet, Even if the aging temperature during the production of the decorative sheet is lowered by adding a specific lubricant to the topcoat layer and preferably increasing the Tg of the resin in the matte layer, the surface layer of the decorative sheet has sufficient friction resistance. We have found that it can be given and have arrived at the present invention.
That is, the present invention is a decorative sheet having a topcoat layer for forming a pattern print layer, a matte layer, and a gloss pattern on a base sheet, the base sheet containing a vinyl chloride resin, The top coat layer includes a thermosetting resin and a reactive silicone oil.
Furthermore, this invention is a manufacturing method of the articles | goods which have a ridge part between adjacent planes, and this adjacent both plane and this ridge part are coat | covered with the decorative sheet, Comprising: The makeup | decoration of Claims 1-6 Provided is a method for producing an article, characterized in that the sheet is produced through a process using a wrapping machine or a V-cut machine.

  The decorative sheet of the present invention has a pattern print layer, a matte layer, and a top coat layer that forms a gloss difference pattern on a base sheet, and uses a gloss matte effect corresponding to the pattern pattern. Since visual unevenness can be formed on the pattern, high designability can be imparted. Furthermore, since a base sheet containing a vinyl chloride resin that can easily adjust the mechanical properties such as elongation is used, it has a three-dimensional shape and has a ridge and corner. In addition, when the wrapping process is performed at the time of construction and the process is performed and the ridges and the corners are wound with one decorative sheet, the decorative sheet may be broken even if the curvature of the ridges is large. The base sheet is not whitened at the ridges or the like. In addition, a base sheet containing an inexpensive vinyl chloride resin is used, and a thermosetting resin is used for the topcoat layer to reduce manufacturing costs, and a reactive silicone oil improves surface slipperiness. Therefore, a decorative sheet having good wear resistance can be manufactured at low cost, particularly at the corners and ridges where the entrainment process has been performed. Furthermore, during the aging after winding the original fabric after printing, the silicone oil is less likely to move to the back surface of the vinyl chloride resin sheet, so that the adhesion failure of the decorative sheet to the coated member is less likely to occur.

A method for manufacturing an article covered with a decorative sheet according to the present invention is a method for manufacturing an article having a ridge between adjacent planes, and the ridge is covered with the decorative sheet. Manufacturing method using a wrapping machine from one surface to the other surface via the ridge, or a flat decorative plate coated with a decorative sheet in advance, and V groove on the back of this It is a manufacturing method that is manufactured through the process of bending the decorative sheet together with the core material with the V-groove part inside, but as a decorative sheet, a pattern printed layer, a matte layer, and a gloss difference are formed on the substrate. A top coat layer for forming a pattern, the base material contains a vinyl chloride resin, and the top coat layer uses a decorative sheet containing a thermosetting resin and a reactive silicone. The part corresponding to the ridge The decorative sheet does not break or stretch, and the decorative sheet can be produced without impairing the high design properties.
And articles such as joinery, furniture, and housing equipment coated using such a coating method have an excellent design with a detailed design of the decorative sheet and a stereoscopic effect of the design. Is granted.

  The decorative sheet of the present invention has a fine pattern having a three-dimensional effect, and has good processability when a wrapping process is performed via a process using a wrapping machine or a V-cut machine, and the decorative sheet surface Excellent wear resistance. In particular, the surface of the decorative sheet covering the ridge portion is excellent in durability and wear resistance with respect to the object having the ridge portion between adjacent planes.

1 is a schematic cross-sectional view showing a configuration of a decorative sheet according to a first embodiment of the present invention. It is a cross-sectional schematic diagram which shows the structure of the decorative sheet which is the 2nd embodiment of this invention. It is the cross-sectional schematic which shows the structure of the decorative sheet which used the glass woven fabric for the base | substrate and improved nonflammability performance.

The basic structure of the decorative sheet of the present invention is shown in FIGS. The decorative sheet of the present invention has a pattern coating printing layer, a mat layer, and a top coat layer for forming a gloss pattern on a base sheet containing a vinyl chloride resin. You may form the colored layer which printed the background color of the pattern pattern in a pattern pattern printing layer between a base material sheet and a pattern pattern printing layer.
Hereinafter, each structure in the decorative sheet of this invention is demonstrated in detail.

The base material sheet used for the decorative sheet of the present invention contains a vinyl chloride resin. The vinyl chloride resin may be a mixture of polyvinyl chloride and other resins, but preferably contains polyvinyl chloride as a main component having the largest mass ratio as a component of the mixture. Is more preferably polyvinyl chloride.
As the base sheet for the decorative sheet of the present invention, vinyl chloride is used so that the workability is improved when the wrapping process is performed on the object having the ridges and corners using a lapping machine. It is preferable to contain a soft vinyl chloride resin containing 5 to 40 parts by mass, more preferably 10 to 35 parts by mass, and further preferably 15 to 30 parts by mass of a plasticizer with respect to 100 parts by mass of the resin. More preferably, it is made of a vinyl resin.

The base sheet containing the vinyl chloride resin used in the present invention is a surface of a material to be coated having a ridge portion and a corner portion on the boundary between two adjacent planes, via the ridge portion and the corner portion. When covering from one side to the other with a wrapping machine etc., the follow-up property of the decorative sheet is good at the entrainment part, and the part in contact with the ridge part etc. of the decorative sheet with the tension when winding the ridge part and corner part is It is preferable not to extend excessively. Appropriate stretching of the decorative sheet during the lapping process is, for example, when the decorative sheet is coated without being whitened and wrinkled along a large curvature change when the ridges or the like are entangled, or after being coated along the V-cut portion. This is an essential characteristic when the sheet is bent without whitening or breaking. However, when the decorative sheet is excessively elongated, the dimensional accuracy is lowered, the shape and dimensions after coating become unstable, the printed layer is peeled off, and the decorative sheet is easily broken.
When considering the entrainment process through the process of the decorative sheet wrapping machine or the V-cut machine as described above, a preferable mechanical property of the base sheet made of the vinyl chloride resin of the decorative sheet is TD of the base sheet. It is preferable that the elongation rate when the substrate sheet cut to be 100 mm in the direction and 25 mm in the MD direction is a test piece and pulled at 1 kg in the measurement length in the TD direction is 3.0% or less. It is more preferably 0.0% or less, even more preferably 1.0% or less, even more preferably 0.5% or less, and even more preferably 0.3% or less. These can be measured from strain-stress characteristics when the test piece is fixed between chucks of a tensile tester and a tensile test is performed at a test speed of 0.1 to 2 mm / min.
Further, the thickness of the base sheet is preferably 50 μm to 250 μm in consideration of workability and durability, and it is preferable to select the base sheet so that the range of the elongation rate according to the measurement conditions is within this range.

  When the base material sheet made of vinyl chloride resin is colored, it is preferable because it can be used as it is as the background color of the pattern print layer formed thereon. Colored vinyl chloride resin sheet can be selected from among a wide variety of color variations, with the color most suitable for the background color of the assumed pattern, for example, it can be matched to the background color of the wood grain pattern .

  The pattern print layer is formed directly on the base sheet of the decorative sheet of the present invention or through a colored layer formed on the base sheet. The pattern print layer is printed on the base sheet with the color tone of the base sheet as the background color, and when printed on the colored layer, the color layer is set with the color tone of the background color. Patterns, texture patterns, crest patterns, geometric patterns, characters, symbols, line drawings, various abstract pattern patterns, and the like are formed. When visual irregularities are formed by the gloss mat method corresponding to the pattern pattern by the matte layer formed on the pattern print layer and the top coat layer, especially when the pattern pattern is a wood grain pattern, A more natural stereoscopic effect is imparted and the design is high.

The pattern is formed on the surface of the base sheet by a printing method using ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. can do.
Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

As binder resin, polyester-based urethane resin treated with hydrophilic treatment, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative Alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, and the like can also be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above natural rubber, etc. Resin can also be used. The said binder resin can be used individually or in combination of 2 or more types. You may add a crosslinking agent, a polymerization initiator, or a polymerization accelerator to the said resin as needed. Among the above resins, it is preferable to use an acrylic resin.
The pattern can be created by using a known printing method such as a gravure printing method, an offset printing method, and a silk screen printing method using the ink having the above composition.
The thickness of the print layer of the pattern is preferably 0.2 μm to 10.0 μm.

When the background color of the pattern pattern printing is the color tone of the colored layer formed by solid printing on the base sheet, the colored layer formed before the pattern pattern printed layer is laminated on the base sheet is the hue of the base sheet. May be completely hidden to set a new background color, but the hue of the base sheet may be used to adjust the hue with a colored layer to form a background color.
The coloring layer can be formed by applying a coloring layer coating material containing a coloring agent and a resin, and the coloring agent and the resin can be selected from known materials used for coloring the substrate. Examples of resins include polyurethane resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, vinyl chloride / vinyl acetate copolymer resins, and chloride resins. Any one selected from vinyl / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins and the like may be used alone or in admixture of two or more. Or you may use it selecting suitably from the colorant which can be used for the ink for pattern pattern printing layers, and the colorant and resin which were already illustrated as resin.
If necessary, a curing agent such as a crosslinking agent, a polymerization initiator, or a polymerization accelerator may be added to the resin.
The colored layer is the above-described paint for the colored layer, for example, gravure coating method, micro gravure coating method, roll coating method, knife coating method, air knife coating method, kiss coating method, rod coating method, die coating method, lip coating method, comma coating method. It can be formed by using a coating method such as a flow coating method or a dip coating method.
The thickness of the colored layer is preferably 0.2 μm to 8.0 μm, and the coating amount is preferably 0.3 to 10 g / m 2.

A matte layer is formed on the pattern print layer. The formation of the matte layer gives the design pattern a high-quality design, and when the pattern is a wood grain pattern, the matte layer is formed to give a high-quality wood texture and corresponds to the design. This is performed to form a basic mat portion for forming a three-dimensional effect as gloss mat printing in which a gloss difference is formed.
As the resin used for the matte layer, a transparent or transparent colored resin having excellent wear resistance and stain resistance is used, and a matte agent is strongly dispersed and retained, and a film with good film strength is preferable, and thermosetting Resin, ionizing radiation curable resin, etc. are typical, but melamine resin, alkyd resin, epoxy resin, unsaturated polyester resin can be used to form a coating film with existing equipment and control manufacturing costs. A thermosetting resin such as a resin, an acrylic resin, or a urethane resin is preferable. In particular, it is preferable to use a two-component curable resin such as a two-component curable urethane resin, a polyol such as an acrylic polyol, a polyester polyol, or a polyether polyol is used as a main agent, and an aliphatic or alicyclic polyisocyanate is used as a crosslinking agent. Is preferred. Among them, those using acrylic polyol as the main agent are preferable.

Examples of the matting agent to be used include inorganic matting agents composed of particles such as amorphous silica, spherical silica, alumina, kaolinite, calcium carbonate, barium sulfate, and glass, polycarbonate resin, acrylic resin, and polyamide (nylon). Organic matting agents such as resins, urea resins and silicon resins can be used. The particle shape of the matting agent is spherical, polyhedral, scale-like or the like. The particle size of the matting agent is about 1 to 10 μm. The addition amount of the matting agent may be such that the difference in gloss between the high gloss portion and the low gloss portion can be visually discerned. Further, as the matting agent, it is preferable to select a matting agent that is excellent in wear resistance because there is a portion where the matting layer becomes the outermost surface layer. Examples are matting agents such as amorphous silica, spherical silica, and alumina. Further, the glass transition point Tg of the resin used for ensuring the abrasion resistance of the basic coating film is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and further 100 ° C. or higher. preferable. The matte layer is formed by applying a paint for matte layer containing the above resin and matting agent from the top of the pattern print layer by spray coating, comma coating, flow coating, roll coating, gravure coating, etc. Can be done.
The thickness of the matte layer can be appropriately adjusted in consideration of the state of gloss mat printing, but is preferably 3.0 μm to 10 μm, and more preferably 2.0 μm to 6.0 μm. The gloss of the matte layer is preferably 15 or less in terms of gloss value.

On the matte layer, a topcoat layer for forming a gloss pattern is formed. The topcoat layer contains a thermosetting resin as a resin component, and is preferably a thermosetting resin excellent in wear resistance, stain resistance and transparency. As thermosetting resins, unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-ureas Examples thereof include a cocondensation resin, a silicon resin, and a polysiloxane resin. A curing agent such as a crosslinking agent, a polymerization initiator, or a polymerization accelerator can be added to the resin. For example, as a curing agent, isocyanate or organic sulfonate is added to unsaturated polyester resin or polyurethane resin, organic amine is added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. The radical initiator is added to the unsaturated polyester resin.
Among the above, a two-component polyurethane resin is preferable because it easily improves the wear resistance, impact resistance, stain resistance, scratch resistance, weather resistance, and the like of the decorative sheet. The two-component curable urethane resin is not particularly limited. Among them, a polyol component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) having an OH group as a main component and an isocyanate component (tolylene diene) which is a curing agent component. Isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate and the like) can be used. In particular, a two-component curable polyurethane resin using an acrylic polyol and an isocyanate curing agent is preferable.

A reactive silicone oil is added to the topcoat layer in the present invention. The reactive silicone oil is firmly held in the top coat layer, and it is difficult for the back surface to migrate during winding after application during production, so that the adhesiveness of the produced decorative sheet to the coating material is not impaired. Also, it functions as a good lubricant on the surface, and as a result, improves the wear resistance of the decorative sheet surface, especially when the ridges and corners are frequently in contact with people and objects when entrained. Excellent resistance to contamination.
As the reactive silicone oil that can be used, various addition polymerization type silicone oils and condensation polymerization type silicone oils can be used, but the condensation polymerization type silicone oil that can be selected according to the reactive functional group of the resin used together. Oil is preferred. Amino-modified silicone oil, carbinol-modified silicone oil, carboxyl-modified silicone oil, phenol-modified silicone oil, and the like can be used. Of these, amino-modified silicone oil and carboxyl-modified silicone oil are preferable because they have good reactivity. Oil is most preferred. By using these in combination with the two-component polyurethane resin, a top coat layer having excellent wear resistance can be formed.
The content of reactive silicone oil is preferably 0.1 to 20 parts, more preferably 0.2 to 18 parts, and 0.3 parts with respect to 100 parts of resin in the topcoat layer excluding the curing agent. -15 parts are more preferred, 0.5 parts to 12 parts are more preferred, and 1 part to 10 parts are even more preferred.
Further, by adding a matting agent with good wear resistance added to the matte layer, the gloss and gloss of the topcoat layer can be adjusted, and the wear resistance can be further improved. Here, the abrasion resistance of the topcoat layer is basically maintained by the excellent lubricity of the reactive silicone oil, so the matting agent is used mainly to adjust the gloss and gloss of the topcoat layer. It is possible to adjust the gloss and gloss.
As a method of forming the surface protective layer with the thermosetting resin, for example, the above-described thermosetting resin is made into a solution, and a top coat layer coating material to which a reactive silicone oil is added is applied to a roll coating method, a gravure coating method, or the like. It is formed by coating by a known coating method, or using these as inks, printing using a known printing method such as a gravure printing method, an offset printing method, a screen printing method, etc., drying and curing. be able to.

  In the decorative sheet of the present invention, a gloss pattern is formed by the top coat layer formed on the mat layer. The gloss pattern is a pattern in which the difference in gloss and gloss between the matte layer and the top coat layer is visually recognized, and is used independently to improve the design of the decorative sheet. Good gloss matte printing can be performed by forming in synchronization with the pattern of the layer. The gloss and gloss of the top coat layer set with a difference to the matte layer can be set high or low for the matte layer, but the gloss and gloss of the entire decorative sheet Since the top coat layer is set with a matte layer, the topcoat layer has a higher gloss and gloss than the matte layer, so that the contrast of the gloss difference that can be expressed by the gloss pattern can be further expanded. It is preferable. Further, at this time, the top coat layer can be laminated so as to form a tuning pattern such as a negative pattern or a positive pattern with respect to the pattern of the pattern printing layer.

In the gloss mat printing of the present invention produced with the top coat layer as the outermost surface, the high glossy and glossy parts are raised, and the low glossy part recedes in a matte state. A design pattern is formed. For example, by changing the gloss and glossy state between the conduit part and the non-conduit part of the wood grain pattern, a wood grain pattern having a more natural three-dimensional effect is formed in synchronization with the wood grain pattern formed on the picture pattern printing layer. . Here, whether to select a stereoscopic effect so that the conduit or non-conduit portion can be seen in the foreground is related to the overall pattern pattern that is assumed, the type of material to be coated, the installation location of the article after coating, etc. Can be selected.
For example, as in the examples described later, the glossy state of the non-conduit part compared to the non-laminate part of the topcoat layer where the matte layer is the outermost surface by making the laminated part of the topcoat layer a non-conduit part, The gloss value is improved, and the gloss value can be raised and visually recognized. In other words, the non-conduit portion corresponds to the gross portion, the conduit portion corresponds to the mat portion, and the dark brown and black portions, which are wood-grained conduit portions, recede toward the back compared to other non-conduit portions. The Such a visual three-dimensional effect is in agreement with the actual unevenness of the coating surface although the level difference is very small, and is considered a preferable method for forming a more natural visual three-dimensional effect.

However, although the topcoat layer has a higher gloss than the matte layer, the overall gloss is often designed to be low, such as when expressing a high-class feeling due to the wood, so external loads must be applied. When receiving or rubbing different materials, the luster changes in the direction of increasing, or in some cases, the coat layer is peeled off. Therefore, it is conceivable to add inorganic fine particles such as an antifriction material, but in the case of the gloss mat printing of the present application that receives a load from an external force at the convex portion of the topcoat layer, the load is concentrated on the convex portion. The added inorganic fine particles are easily detached from the surface of the top coat layer. In the present application, the top coat layer forms a gloss pattern, and the fact that these inorganic fine particles are not held by the uniformly formed top coat layer is even more so. In particular, in the corners and ridges after coating, a slight elongation of the decorative sheet occurs, and considering the fact that contact pressure with a person or article must be received by a line rather than a plane, the above situation is further increased. It tends to occur. In order to prevent this, it is necessary to improve the slipperiness of the topcoat layer. For this purpose, the addition of reactive silicone oil is extremely important for improving the wear resistance.
On the other hand, it is difficult to add the reactive silicone oil in the matte layer that is partially the outermost layer at a location where the topcoat layer is not formed. This is because the silicone oil added to the matte layer is retained on the surface layer, which may hinder the adhesion of the topcoat layer formed thereon. Therefore, it is necessary for the resin for the matte layer to improve the glass transition point and to provide abrasion resistance in addition to the matte effect. The surface of the matte layer is subject to direct frictional force, which may change the surface shape and increase gloss and gloss. However, the external force is mainly retained by the convex surface of the topcoat layer and blended. When the reactive silicone oil used exhibits a good effect of improving lubricity, the frictional force received by the matte layer is reduced and is not damaged.

  The decorative sheet of the present invention contains a vinyl chloride resin, preferably on a base sheet containing as a main component, or on a colored layer formed on the base sheet, a pattern printed layer, a matte layer, and The top coat layer can be applied and dried sequentially, and each layer or several layers can be formed together by applying a coating forming process such as curing and aging.

The covering material is coated using the decorative sheet formed as described above. Examples of the material to be coated include wood-based materials such as plywood, MDF, particle board and medium-density fiberboard, synthetic resin-based materials such as injection-molded products and extrusion-molded products, and metal-based materials such as iron, stainless steel and aluminum. is there. When the material to be coated is planar, an adhesive is often applied to the material to be coated for coating, and after the adhesive layer is formed, it is stuck with a laminator or the like. As the adhesive layer, a heat-sensitive, pressure-sensitive or moisture-curable resin suitable for the material of the material to be coated can be appropriately used. When the material to be coated is a synthetic resin-based material, it is preferable to use a resin having an affinity for these materials. When the material of the material to be coated is wood or ceramic, chlorinated polyolefin resin, chlorinated ethylene-acetic acid Vinyl copolymers, polyamide resins, urethane adhesives and the like can be used.
When the material to be coated is three-dimensional, even if the shape is mainly planar, and has ridges and corners at the boundary between adjacent planes, the adhesive is usually applied to the back surface of the decorative sheet, and the adhesive layer The covering sheet is coated by subjecting the decorative sheet to a covering material by a wrapping machine or the like.

The decorative sheet of the present invention uses a reactive silicone oil in the top coat layer that forms a gloss pattern, particularly at the corners and ridges when the corners and ridges of the material to be coated are covered. The wear resistance is improved by improving the slipperiness. At corners and ridges where tensile and lash stresses tend to concentrate, the contact pressure and external force per unit area that acts when in contact with people and objects are large. Easy to drop off. Furthermore, the pattern of a specific pattern is formed, and the top coat layer itself that does not form a uniform film is easily peeled off by an external force, and it is essential to provide stable lubricity.
The method of the present invention uses a vinyl chloride resin containing a thermosetting resin for the topcoat layer and it is difficult to set a sufficiently high curing temperature or aging temperature for the topcoat layer. A decorative sheet that is extremely effective when a material sheet is used, has a high design with good wear resistance, and has good incombustibility and flame resistance, can be produced with inexpensive raw materials and low manufacturing costs.
On the other hand, it is necessary for the top coat layer to have good wear resistance at the corners and ridges, because the resin sheet has better heat resistance than the base sheet containing the vinyl chloride resin used in the present invention. The same applies to the case of using an ionizing radiation curable resin other than the thermosetting resin used in the present invention. Therefore, the method for improving the wear resistance of the present invention is generally applied to a decorative sheet having a top coat layer widely formed in a pattern, and particularly to a decorative sheet subjected to gloss mat printing. The present invention can be widely applied as a technique for improving the wear resistance of corners and ridges of articles covered by using.

In addition, the decorative sheet produced as described above is laminated on a base sheet having other various functions as a decorative layer having high design and excellent wear resistance, and the function of the base sheet In addition to the above, it is possible to obtain a new decorative sheet further imparted with good high designability and wear resistance. As the other base sheet, the function can be further improved by using those having various functions that the decorative sheet of the present invention does not have or is not sufficient even if it has.
The decorative sheet of the present invention has many constituent parts made of vinyl chloride resin, which itself has good non-flammability and flameproofness. However, the decorative sheet as a whole has a high design and wear resistance as a decorative layer. By laminating the base material sheet with extremely good nonflammability and flameproofness, a decorative sheet with further improved nonflammability and flameproofness can be obtained.
As such a base material sheet, a glass woven fabric that is extremely excellent in incombustibility and heat insulation can be used. That is, in the decorative sheet of the present invention, a glass woven fabric is laminated on the surface of the base sheet opposite to the pattern print layer to obtain a new decorative sheet. Because the glass woven fabric is extremely thin and lightweight, the formation of such a backing layer does not significantly increase the film thickness and weight of the entire decorative sheet. It is possible to provide an incombustible decorative sheet with good characteristics. Furthermore, the formation of the backing layer further suppresses deformation of the entire decorative sheet and further increases the dimensional stability, so that whitening during bending is less likely to occur (see FIG. 3).
The surface of the glass woven fabric has irregularities on the texture, but when the entire decorative sheet of the present invention is used as a decorative layer and laminated with the glass woven fabric, the unevenness is the image quality of the pattern printing layer of the decorative sheet. Almost no effect is observed. This is because the surface of the base sheet of the decorative sheet of the present invention that has flexibility absorbs the irregularities of the glass woven fabric, and the colored layer, matte layer, and overcoat formed on the base sheet. In the layer, and also in the pattern print layer, the film-forming resin that constitutes the layer has undergone a curing treatment using a crosslinking agent, and the rigidity near the decorative sheet surface is high, so that the appearance of the decorative sheet It is thought that the unevenness does not affect.
Furthermore, it is considered that the presence of the matte layer formed on the pattern print layer makes the uneven pattern more difficult to see.

  The glass woven fabric used as the other substrate is woven from warps and wefts using a bundle of glass fibers as a thread. Prior to weaving, a bundle of two or more glass fibers may be pre-twisted. In particular, glass filaments having a monofilament diameter of 3 to 9 μm are 50 to 800 monofilaments, 2.8 to 135 tex (g / 1000 m) of glass fiber bundles are used as warps and wefts, and the weaving density of warps is 20 to 75. / 25 mm, and weaved with a plain weave so that the weave density of the weft is 20 to 75/25 mm.

Adhesion of the decorative sheet of the present invention to the glass woven fabric as the other base material is performed on the surface of the decorative sheet opposite to the pattern printed layer of the base sheet (of the decorative sheet of the present invention) and the glass woven fabric. May be performed by thermocompression as it is. Alternatively, the base sheet (of the decorative sheet of the present invention) and the glass woven fabric can be thermocompression bonded via an adhesive. The adhesive may be applied in advance to the adhesive surface of the base sheet, or the glass woven fabric may be impregnated with the adhesive and adhered to the base sheet (of the decorative sheet of the present invention). At this time, a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer, or the like can be used as an adhesive used for bonding the base sheet (of the decorative sheet of the present invention) and the glass woven fabric.
The glass woven fabric (other base material) is obtained by previously bonding an auxiliary resin film on the surface opposite to the side to be bonded to the base material sheet (of the decorative sheet of the present invention) as a new other base material. May be. By using a glass woven fabric pre-bonded with such an auxiliary resin film, the strength of the glass woven fabric is reinforced, and the glass woven fabric is prevented from being damaged in the step of bonding the base sheet of the decorative sheet of the present invention. it can. Further, when the adhesive is applied and bonded to the base sheet side, the adhesive does not pass through the gaps of the glass woven fabric and can be bonded more reliably.
Further, when the glass woven fabric is impregnated into the adhesive and bonded to the base material sheet (of the decorative sheet of the present invention), the surface of the glass woven fabric opposite to the base material sheet (of the decorative sheet of the present invention) Other auxiliary resin films can be brought into contact with each other and thermocompression-bonded to both sides so as to sandwich the glass woven fabric.
As described above, in the step of bonding the base sheet (of the decorative sheet of the present invention) to the glass woven fabric, the resin film seems to exist on the opposite side of the base sheet (of the decorative sheet of the present invention) of the glass woven fabric. By doing so, the stress applied to the base sheet from the irregularities on the surface opposite to the base sheet (of the decorative sheet of the present invention) of the glass woven fabric during the bonding process is alleviated by the deformation of the resin film, and the pattern print layer This is preferable because the influence of image quality on the image quality is further reduced.

The decorative sheet produced as described above using a glass woven fabric with good non-combustible performance as a part of the base material has excellent design properties, shape stability, and workability when coating a coating material. In addition to the good wear resistance of articles such as decorative plates and frame materials produced by coating a material to be coated, it has a function of improving the non-combustibility and flameproof performance of these articles.
Furthermore, since the decorative sheet itself has good non-flammability and flameproof performance while being thin and lightweight, the film-like form mainly composed of glass woven fabric is maintained and collapses even in a fire. There is nothing. Therefore, the decorative sheet alone can be suitably used as a membrane ceiling or curtain having good incombustibility and high design.

The example of the decorative sheet having the configuration defined in the present invention is shown below, and the effect is confirmed.
Example 1
[Base material sheet]
As a colored base sheet for a decorative sheet, a vinyl chloride resin sheet colored with a light brown color (Tatsuno Chemical Co., Ltd., thickness 120 μm, plasticizer compounding amount 11 parts by mass with respect to 100 parts by mass of resin) was prepared.
(Measurement of elongation at constant load (1 kg) in tensile test)
The vinyl chloride resin sheet was cut to be 100 mm in the TD direction and 25 mm in the MD direction to obtain a measurement sample of a colored vinyl chloride resin sheet for measuring elongation. This was set between the chucks in a tensile tester using a Tensilon RTC-1250A manufactured by Orientec so that the measurement length in the TD direction was 50 mm. This is subjected to a tensile test in the TD direction at a test speed of 0.3 mm / min in an environment of 26 ° C., and the elongation when pulled at 1 kg is 0.29% from the strain at the tensile stress of 1 kg. I understood.

[Colored layer, pattern printing layer, matte layer]
Using the above-mentioned colored vinyl chloride resin sheet, an acrylic polyol-based ink (4 parts of polyisocyanate as a curing agent is blended with 100 parts of acrylic polyol manufactured by DIC) as a solid color layer by gravure printing. The coating layer for the colored layer) was applied so that the coating amount at the time of drying was 2.0 g / m 2, and the colored layer serving as the background color was printed.
Next, as a pattern pattern printing layer, an acrylic resin-containing ink (manufactured by DIC) was printed with a wood grain pattern conduit portion so that the coating amount when dried was 1.5 g / m 2. Next, acrylic matte coating agent (containing 100 parts of acrylic polyol manufactured by DIC, containing amorphous silica as a matting agent, and 20 parts of polyisocyanate as a curing agent is used as a matting layer. , A matting paint having a glass transition point of 100 ° C. at the time of curing) was printed so that the coating amount upon drying was 6.0 g / m 2.

[Topcoat layer]
Next, an acrylic polyol-based coating agent (coating agent used by mixing 20 parts of polyisocyanate as a curing agent with 100 parts of acrylic polyol manufactured by DIC) as a top coat layer, and an amino-modified reactive as an additive The top coat layer paint containing 6 parts of a reactive silicone oil (made by DIC) containing silicone oil as the main component is tuned to the part other than the pattern pattern so that the coating amount when dried is 5.0 g / m2. Printed. Thereafter, aging was performed for 72 hours in an environment of 40 ° C. to obtain a decorative sheet 1 in which a wood grain conduit pattern was gloss mat printed on a vinyl chloride resin base material sheet.
[Coating with decorative sheet]
Next, a medium density fiber board having a thickness of 18 mm, a width of 100 mm, and a length of 1800 mm is prepared, and a solvent-based urethane adhesive (5275 manufactured by No-Tape Kogyo Co., Ltd.) is applied to the back surface of the decorative sheet 1. Coating was performed with a knife coater so as to be m2, and lapping was performed using a Marnaka wrapping machine PL-300CM. At this time, lapping was performed so as to involve the upper surface portion, both side surface portions, and a part of the rear surface with respect to the longitudinal direction of the medium density fiberboard. Thus, a decorative sheet wrapping frame material 1 in which a wood grain pattern was gloss mat printed on a vinyl chloride resin base material sheet was obtained.

<< Example 2 >>
It is a vinyl chloride resin sheet manufactured by Nanya Plastics Co., Ltd. with a thickness of 70 μm and a plasticizer compounding amount of 16 parts by mass with respect to 100 parts by mass of the resin, and a constant load (1 kg) of the tensile test in the same measurement as in Example 1. A decorative sheet 2 and a decorative sheet wrapping frame material 2 were obtained in the same manner as in Example 1 except that a colored vinyl chloride resin sheet having an elongation percentage of 0.9% was used.
Example 3
This is a vinyl chloride resin sheet manufactured by Riken Technos with a thickness of 120 μm and a plasticizer content of 7 parts by mass with respect to 100 parts by mass of the resin, and the elongation at a constant load (1 kg) in the tensile test in the same measurement as in Example 1. A decorative sheet 3 and a decorative sheet wrapping frame material 3 were obtained in the same manner as in Example 1 except that a 0.2% colored vinyl chloride resin sheet was used.
Example 4
Makeup in the same manner as in Example 1 except that the amount of the reactive silicone oil blended in the topcoat layer in Example 1 was 0.5 part with respect to 100 parts of the acrylic polyol in the topcoat layer coating material. Sheet 4 and decorative sheet wrapping frame material 4 were obtained.

Example 5
A decorative sheet 5 in the same manner as in Example 1 except that the amount of the reactive silicone oil blended in the topcoat layer in Example 1 was 12 parts with respect to 100 parts of the acrylic polyol in the topcoat layer coating material. And the decorative sheet wrapping frame material 5 was obtained.
Example 6
A decorative sheet 6 and a decorative sheet wrapping frame material 6 were obtained in the same manner as in Example 1, except that the main component of the release agent in Example 1 was changed to a carboxyl-modified reactive silicone oil.
Example 7
A decorative sheet 7 and a decorative sheet wrapping frame material 7 were obtained in the same manner as in Example 1 except that the Tg of the acrylic coating agent for the topcoat layer in Example 1 was set to 70 ° C.

≪Comparative example 1≫
A decorative sheet 8 and a decorative sheet wrapping frame material 8 were obtained in the same manner as in Example 1 except that no reactive silicone oil was used for the topcoat layer in Example 1.
≪Comparative example 2≫
The decorative sheet 9 and the makeup are the same as in Example 1 except that non-reactive silicone oil (KF96-50CS manufactured by Shin-Etsu Chemical Co., Ltd.) is used for the topcoat layer in Example 1 instead of reactive silicone oil. A sheet wrapping frame material 9 was obtained.
≪Reference Example 1≫
The decorative sheet wrapping frame material 10 was produced by setting the aging temperature of the topcoat layer in Comparative Example 1 to 60 ° C. Alcohol resistance, abrasion resistance of the corners of the flat part were good, but the vinyl chloride resin film as the base film was deformed, the decorative sheet was wrinkled and the design was greatly impaired, and the wrapping machine Although it is possible to perform coating by the above method, the workability is poor due to wrinkles and deformation, and it has not been possible to perform a good entrainment process on the material to be coated.

  A list is shown below about the manufacturing conditions of the decorative sheet in the said Example and a comparative example.

About the test sample of length 150mm cut out from each center part of the decorative sheet wrapping frame materials 1-10 produced in Examples 1-7, Comparative Example 1, and Comparative Example 2, the following test items and evaluation Evaluation was performed according to criteria.
≪Test items and evaluation criteria≫
1. Alcohol resistance While applying a load of 500 g / cm ² with a waste cloth impregnated with ethanol (Kim towel wiper manufactured by Nippon Paper Crecia Co., Ltd.), the surface of the decorative sheet of the test sample is rubbed strongly 10 times, and the degree of gloss change is observed.
◎: Almost no gloss change
○: Minor but gloss change occurs
Δ: Easily recognize the occurrence of gloss change ×: Significant gloss change occurs

2. Gloss Matte Property The decorative sheet surface of the test sample is visually evaluated for the design property by the gloss contrast between the matte transparent coat layer and the top coat layer.
◎: Three-dimensional effect is obtained and high designability is obtained. ○: Contrast is clear and good designability is obtained. △: Contrast is not clear and designability is insufficient.
×: The contour itself lacks clarity and has low design properties

3. Drying resistance 3-1 Flat part The decorative sheet surface of the test sample cut out from the decorative sheet wrapping frame material was reciprocated 10 times while applying a load of 200 g / cm ² with a waste cloth (Kim Towel Wiper, Nippon Paper Crecia Co., Ltd.) The surface condition at that time is visually evaluated.
A: Almost no gloss change is observed. O: A slight gloss change occurs. Δ: A gloss change can be easily recognized. X: Top coat or ink can be taken. 3-2 Corner (sheet entrainment part)
The test sample cut out from the decorative sheet wrapping frame material is equally divided with respect to the corner portion covered with the decorative sheet and having the vertical angle of the vertical cross section formed from the upper surface portion and the side surface portion. In the direction, a cotton towel (EA929HG-3 manufactured by Esco Corporation) is applied with a load of 100 g / cm ² and reciprocated 5000 times, and the surface condition at that time is visually evaluated.
◎: Almost no gloss change is observed ○: Minor but gloss change occurs △: Gloss change can be easily recognized ×: Top coat or ink can be removed

4). Base Material Adhesion The test sample cut out from the decorative sheet wrapping frame material is cooled to 5 ° C., and the base material breakage rate is evaluated when the decorative sheet is cut and forcibly removed.
A: Material breakage rate is 80% or more
○: Material breakage rate is 60% or more and less than 80% △: Material breakage rate is 30% or more and less than 60% ×: Material breakage rate is less than 30%

5. Bending processability The state of elongation of the decorative sheet at the corner (sheet entraining part) of the test sample cut out from the decorative sheet wrapping frame material was confirmed.
A: Sheet elongation is hardly seen
○: Minor but sheet elongation occurs Δ: Sheet elongation occurs and whitening is observed at the corners ×: Sheet breakage or significant whitening of the corners occurs

  Below, the result of having evaluated by the said evaluation item about the decorative sheet wrapping frame materials 1-10 produced in Examples 1-7 and Comparative Examples 1 and 2 is shown.

  As shown in Table 2, the gloss mat decorative sheets shown in Examples 1 to 7 showed good results in all evaluation items. However, in Example 2 in which the elongation percentage of the base sheet was increased, the bending workability was not affected, but the wear resistance at the corners was slightly lowered. On the other hand, in Example 3 in which the elongation percentage of the base sheet was decreased, only the bending workability was improved without affecting other characteristics. In Example 4 in which the addition amount of the reactive silicone acrylate was reduced from 6 parts to 0.5 parts, the evaluation in Table 2 was the same as in Example 1, but the adhesion of the base material was Example 1. It was further improved slightly, and the wear resistance of the flat and corner portions was slightly reduced. On the other hand, in Example 5 in which the addition amount of the reactive silicone acrylate was increased to 12 parts, the abrasion resistance of the flat part and the corner part was slightly improved, but the adhesion to the substrate was slightly lowered. Moreover, in Example 6 using the reactive silicone acrylate containing carboxyl group instead of the amino group-containing reactive silicone acrylate, the characteristics were almost the same as in Example 1. However, although it does not appear as a difference in Table 2, the wear resistance at the corners slightly decreased. In Example 7 in which the Tg of the acrylic coating agent of the topcoat layer was lowered, the alcohol resistance and the abrasion resistance of the flat and corner portions were slightly lower than in Example 1. On the other hand, in Comparative Example 1 in which no reactive silicone oil was added, the alcohol resistance was greatly reduced, and in particular, the wear resistance at the flat and corner portions was significantly reduced. In Comparative Example 2 using a non-reactive silicone oil instead of a reactive silicone oil, the alcohol resistance and the wear resistance of the flat portion were slightly lowered, but the wear resistance of the corner portion was lowered. However, when the decorative sheet was wound into a roll after laminating each layer with respect to the raw material of the base material sheet, the back-off of the silicone oil was affected, and the adhesion to the base material was remarkably lowered.

Furthermore, the decorative sheets 1 to 7 prepared in Examples 1 to 7 are used as a decorative layer, and a glass woven fabric is used as a new base material. On the base material sheet of the decorative sheet, a pattern forming layer is formed on the base material. The opposite side surfaces were laminated so as to face each other.
As the glass woven fabric, a fabric obtained by bundling about 250 glass filaments having a monofilament type of 6 μm into a glass yarn and plain woven with a density of 32 warps / 25 mm and 32 wefts / 25 mm was used.
A vinyl chloride resin film having a thickness of 85 μm is bonded to the glass woven fabric through an adhesive to produce a composite sheet of the vinyl woven resin film on the glass woven fabric side. The base sheet in the decorative sheets 1 to 7 produced in Examples 1 to 7 is made to face the surface opposite to the pattern print layer, and a vinyl chloride-vinyl acetate copolymer is used as an adhesive. And laminated (see FIG. 3).
A 10 cm × 10 cm evaluation sheet was cut out from the new decorative sheets 1 to 7 with glass woven fabric thus produced, and the appearance of the pattern was evaluated according to the following evaluation criteria.
[Appearance evaluation of decorative sheet with glass woven fabric]
A: Printing with a uniform background color and fine printing with a pattern are formed.
Even if a magnifying glass (3x) is used, there is no disorder in printing.
○: Although the presence of the woven fabric pattern is confirmed when observed with a magnifying glass (3 times), it is hardly discernable visually.
△ ・ ・ ・ Glass woven fabric pattern is slightly visible in the background color, and the outline of the pattern lacks smoothness × ・ ・ There is uneven printing due to the woven fabric pattern of the glass woven fabric in the background color, and the pattern Chipping occurs.
The evaluation results of the new decorative sheets 1 to 7 with glass woven fabric prepared by laminating the decorative sheets prepared in Examples 1 to 7 on the glass woven fabric as a new decorative layer were as follows.

  As is clear from Table 3, all newly produced decorative sheets maintained an appearance having high design properties. However, in Example 2 where the elongation percentage of the base sheet is large, the influence of the unevenness of the glass woven fabric is recognized although it is very slight, and Example 7 in which the Tg of the acrylic coating agent for the matte layer is slightly low is also observed after lamination. A slight influence on the surface of the glass woven fabric due to winding was observed.

  The decorative sheet of the present invention can be used as a highly-designed decorative sheet having a fine pattern with a three-dimensional effect to cover the surface of furniture, furniture, housing equipment, and the like. These decorative sheets are inexpensive, can be coated by a simple method using a wrapping machine, and have good wear resistance.

DESCRIPTION OF SYMBOLS 1 Cosmetic sheet 2 Base film 3 Colored layer 4 Picture pattern printing layer 5 Matte layer 6 Top coat layer 7 Glass woven fabric 8 Vinyl chloride resin film 9 Cosmetic sheet with glass woven fabric

Claims (9)

  A decorative sheet having a topcoat layer for forming a pattern print layer, a matte layer, and a glossy pattern on a base sheet, wherein the base sheet contains a vinyl chloride resin, and the top coat layer is A decorative sheet comprising a thermosetting resin and a reactive silicone oil. The decorative sheet according to claim 1, wherein the gloss pattern formed by the top coat layer is formed in synchronization with the pattern of the pattern pattern printing layer. The decorative sheet according to claim 1, wherein the top coat layer has a gloss higher than that of the matte layer and forms a negative pattern with respect to the pattern of the pattern print layer.   The decorative sheet according to any one of claims 1 to 3, wherein the matting layer contains a matting agent and a resin having a glass transition point of 60 ° C or higher.   The film base material has an elongation percentage of 3.0% or less when a sample cut to 100 mm in the TD direction and 25 mm in the MD direction is subjected to a load of 1 kg in the TD direction. The decorative sheet according to item 1.   The decorative sheet according to any one of claims 1 to 5, wherein the reactive silicone is an amino-modified silicone oil or a carboxyl-modified silicone oil.   It is a manufacturing method of the article | item which has a ridge part between adjacent planes, and this both adjacent planes and this ridge part are coat | covered with the decorative sheet, Comprising: The decorative sheet of Claims 1-6 is used. An article manufacturing method, wherein the article is manufactured through a process using a wrapping machine or a V-cut machine. The article manufactured using the manufacturing method according to claim 7 is one selected from the group consisting of joinery, furniture, and housing equipment. The decorative sheet according to any one of claims 1 to 6, wherein a glass woven fabric is laminated on the surface of the base sheet opposite to the pattern print layer.

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