JP3641946B2 - Decorative sheet - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet for use in interior and exterior materials of buildings such as houses, building materials such as construction materials and fittings, furniture fixtures, surface equipment such as housing equipment and home appliances, etc. More particularly, the present invention relates to an environmentally friendly decorative sheet that is suitable for three-dimensional molding applications such as wrapping laminate or vacuum molding laminate, and preferably does not generate toxic gas during combustion.
[0002]
[Prior art]
Conventionally, as a decorative sheet used in such a field, for example, there has been a paper-based decorative sheet obtained by printing a desired pattern such as wood grain on the surface of paper. In addition, low-strength paper is used, so surface properties such as surface hardness, abrasion resistance, water resistance and solvent resistance are poor, and the surface of the paper is essentially porous and rough. Since printing is performed, the sharpness of the printed pattern is low and the design is inferior, so there are problems such as limited usable applications and unsuitable for applications that require a high-class feeling. It was.
[0003]
On the other hand, there is also a resin-type decorative sheet in which a film or sheet made of a thermoplastic resin is used as a base sheet instead of paper, and an appropriate desired pattern such as wood grain is printed on the front or back surface. It was. This is a decorative sheet that solves the problems of the physical properties and design of the paper-based decorative sheet described above, and was used in a wide range of applications, including applications that demand strict physical properties and applications that require a high-class feel. .
[0004]
As such a resin-based decorative sheet, a decorative sheet having a single-layer configuration in which a pattern is printed on the front surface side or the back surface side of the thermoplastic resin base sheet, and a thermoplastic resin base sheet on the back surface side of the pattern layer. There is a decorative sheet having a multilayer structure sandwiched between the transparent resin layer on the surface side. The former has the advantage that it can be manufactured easily and cheaply because of its simple structure, while the latter is somewhat disadvantageous from the manufacturing and price points, but the pattern is protected from both the front and back sides, so the wear resistance of the pattern It combines surface properties such as solvent resistance and weather resistance, and resistance to the adhesive used when adhering to the substrate to be adhered, and also from the design side, it is highly concealed by coloring the base sheet and transparent There are many advantages in terms of performance, such as being able to achieve both high design by embossing the resin layer. Due to this relationship, both are properly used according to the performance and price required by the application.
[0005]
Conventionally, polyvinyl chloride resin, which is inexpensive and excellent in processability and physical properties, has been used most frequently as a constituent material for the base sheet and transparent resin layer of various resin-based decorative sheets described above. In response to the growing social interest in the problem, decorative sheets using resins other than polyvinyl chloride resin, such as polyolefin-based thermoplastic resins, that have less adverse effects on the environment have been developed and put into practical use (Japanese Patent Application Laid-Open No. Hei 11 (1998)). No. 6-166159).
[0006]
A decorative sheet using the above-mentioned polyolefin-based thermoplastic resin has been conventionally used in terms of flexibility and whitening resistance required for secondary processing such as laminating of a decorative sheet to a substrate to be adhered and V-cut processing. Since the performance almost equivalent to that of polyvinyl chloride resin can be obtained relatively easily, it is currently considered most promising among various alternative materials for polyvinyl chloride resin. On the other hand, however, the thermoplastic polyolefin-based thermoplastic resin has a lower surface hardness than the polyvinyl chloride resin having the same flexibility, and tends to have poor scratch resistance on the surface.
[0007]
On the other hand, various decorative sheets using a polyester-based thermoplastic resin have been proposed. Polyethylene terephthalate resin, the most common polyester-based thermoplastic resin, has a tensile modulus of 400 kgf / mm. ² Before and after, and because it is poor in flexibility for a decorative sheet, the processability is inferior, so modification for softening by adding various copolymerization components has been attempted, such as cold crystallization temperature and glass transition temperature. The difference in temperature is made of a copolyester having a temperature of 60 ° C. or less, has a quasicrystal melting peak temperature not lower than the cold crystallization temperature and not higher than the melting point, and has a tensile modulus of 0.1 to 50 kgf / mm. ² A decorative sheet using a flexible polyester film is proposed (see JP-A-6-166159, JP-A-7-17005, JP-A-7-137205, etc.).
[0008]
However, although the above-mentioned flexible polyester film has solved the problems such as whitening and breakage caused by bending such as V-cut, it has low surface hardness due to its flexibility and is inferior in scratch resistance. In addition, the base material to which the decorative sheet is attached is not necessarily a flat plate, and base materials having various three-dimensional shapes are increasing in various uses such as for bathroom wall surfaces. When affixing to a shaped substrate by a lapping method, a vacuum forming method, or the like, the above-described flexible polyester film is too soft and has a problem that wrinkles, scratches and the like are likely to occur.
[0009]
[Problems to be solved by the invention]
The present invention has been made in order to solve the above-described problems in the prior art, and the object of the present invention is not only to laminate on a planar substrate but also to a three-dimensional substrate. An object of the present invention is to provide a decorative sheet that can withstand three-dimensional molding such as lapping and vacuum forming, and has excellent surface properties such as scratch resistance.
[0010]
[Means for Solving the Problems]
In order to solve the above problems, the present invention has a glass transition point of 60 ° C. or higher and 85 ° C. or lower and a tensile elastic modulus of 100 kgf / cm. ² 300 kgf / cm ² Provided is a decorative sheet comprising at least a polyester-based thermoplastic resin layer as described below.
[0011]
The present invention further provides a decorative sheet comprising the decorative sheet, wherein the pattern layer and the transparent polyester-based thermoplastic resin layer are sequentially laminated on the thermoplastic resin base sheet. .
[0012]
The present invention further provides the decorative sheet, wherein the thermoplastic resin base sheet is made of a polyolefin-based thermoplastic resin.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a laminated structure of an example of the decorative sheet of the present invention.
[0014]
In the example shown in FIG. 1, the decorative sheet of the present invention is configured by sequentially laminating a pattern layer 2 and a transparent polyester-based thermoplastic resin layer 1 on a thermoplastic resin base sheet 3, Particularly in the invention, the polyester-based thermoplastic resin layer 1 has a glass transition point of 60 ° C. or higher and 85 ° C. or lower, and a tensile elastic modulus of 100 kgf / cm. ² 300 kgf / cm ² It is the layer which consists of a polyester-type thermoplastic resin which is the following.
[0015]
The reason for limiting the glass transition point and tensile elastic modulus of the polyester-based thermoplastic resin layer 1 to the above numerical ranges is that sufficient three-dimensional moldability at a heating temperature (about 60 to 85 ° C.) in three-dimensional forming such as normal vacuum forming. As a result, there is little residual internal stress, and it has moderate flexibility and moderate waist and surface hardness, so it does not cause wrinkles or drawdown during three-dimensional molding, such as surface scratch resistance This is because the surface physical properties of a sufficient level as a decorative sheet can be obtained. If the glass transition point is less than 60 ° C, it becomes too soft due to molding heat at the time of three-dimensional molding and causes wrinkles, scratches, drawdown, etc. On the other hand, if it exceeds 80 ° C, the softening at the time of three-dimensional molding is insufficient, This may cause molding defects, residual internal stress, cracking, whitening, and the like. Tensile modulus is 100 kgf / c m ² If it is less than 3, the resin is too flexible and the surface has insufficient scratch resistance, and causes wrinkles and scratches during drawing, drawdown, etc. c m ² If it exceeds 1, the flexibility of the resin is inadequate, resulting in poor processability, causing molding defects, residual internal stress, cracking, whitening, and the like.
[0016]
The polyester-based thermoplastic resin layer 1 being “transparent” is not necessarily limited to being transparent in a strict sense, and may be translucent or colored transparent. Further, the present invention is not limited to the decorative sheet having the multilayer structure as described above. For example, it does not have the thermoplastic resin base sheet 3 in FIG. 1 and the surface of the polyester-based thermoplastic resin layer 1 or This includes a decorative sheet having a single layer structure with a pattern layer 2 provided on the back side. When the pattern layer 2 is provided on the surface of the polyester thermoplastic resin layer 1, the polyester thermoplastic resin layer 1 is used. May be opaque. In addition, one or more transparent thermoplastic resin layers of the same or different type as the polyester thermoplastic resin layer 1 may be provided between the polyester thermoplastic resin layer 1 and the pattern layer 2. One or more other pattern layers may be provided between the layers.
[0017]
The specific chemical composition of the polyester-based thermoplastic resin constituting the polyester-based thermoplastic resin layer 1 is not particularly limited as long as the glass transition point and the tensile elastic modulus are in the above numerical ranges. For example, dicarboxylic acid or dicarboxylic acid In the condensation polymerization reaction between an acid ester and a diol, an aromatic dicarboxylic acid such as terephthalic acid or naphthalenedicarboxylic acid and / or an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid and a fat such as ethylene glycol or 1,4-butanediol A hard structural unit using an alicyclic diol such as an aliphatic diol and / or a cyclohexanediol, and a polyether diol having hydroxyl groups at both ends, such as polyethylene glycol and polytetramethylene glycol, as the diol, and / Or as dicarboxylic acid -(AB) -n type block copolymer with soft structural unit using aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid such as succinic acid, eicoic acid, dodecanedioic acid and dimer acid It is possible to suitably use a copolyester resin or the like that exhibits the properties of a thermoplastic elastomer.
[0018]
In addition, the polyester-based thermoplastic resin may include, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a difficulty, depending on the intended use of the decorative sheet. One or more conventionally known various additives such as a fuel and a filler may be added.
[0019]
Examples of antioxidants include phenols, sulfurs, phosphoruss, etc., ultraviolet absorbers such as benzophenones, benzotriazoles, salicylates, cyanoacrylates, formamidines, oxanilides, etc. Hindered amines, nickel complexes, etc., heat stabilizers such as hindered phenols, sulfurs, hydrazines, etc., plasticizers depending on the type of resin, but phthalates, phosphates, fatty acids, etc. Type, aliphatic dibasic acid ester type, oxybenzoic acid ester type, epoxy type, polyester type, etc., as the lubricant, for example, fatty acid ester type, fatty acid type, metal soap type, fatty acid amide type, higher alcohol type, paraffin type, etc. Antistatic agents include, for example, cationic, anionic, and nonio Examples of flame retardants such as bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium, boron, and zirconium, and fillers such as calcium carbonate, talc, It can be used in one or a mixture of two or more selected from wax, kaolin and the like.
[0020]
There is no restriction | limiting in particular in the thickness of the polyester-type thermoplastic resin layer 1, It can set equivalent to the case of the conventional common decorative sheet. Specifically, when it is used as a transparent resin layer of a decorative sheet having a multilayer structure as shown in FIG. 1, it is often in the range of about 20 to 150 μm. In many cases, the range is about 300 μm.
[0021]
The pattern layer 2 is provided for the purpose of imparting the desired decorative design of the desired decorative sheet to the target decorative sheet, and the type of the pattern is not particularly limited. For example, the grain pattern, the stone pattern, Various patterns similar to the case of a conventional decorative sheet, such as an abstract pattern and a solid plain color, can be employed. There is no particular limitation on the constituent material and the forming method of the pattern layer 2, and for example, a colorant such as an organic or inorganic dye or pigment is dissolved or dispersed in an appropriate solvent together with an appropriate binder resin. Printing ink or a coating agent or the like can be provided by printing or coating by an appropriate printing method or coating method.
[0022]
Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, cadmium red, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments, and the like. Metallic pigments such as organic pigments, gold powder, silver powder, copper powder, aluminum powder, bronze powder, pearl luster pigments such as fish scale powder, basic lead carbonate, bismuth oxide oxide, titanium oxide-coated mica, fluorescent pigments, nocturnal pigments, etc. Alternatively, a mixture of two or more selected from these can be used.
[0023]
Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, polyvinyl resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, and melamine resins. , Various synthetic resins such as fluorine-based resins, silicone-based resins, fiber derivatives, and rubber-based resins, or a mixture or copolymer of two or more thereof can be used.
[0024]
Examples of the solvent include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, methylcyclohexane, ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyacetate. Ester-based organic solvents such as ethyl, alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, and ketone-based organics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Solvents, ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; salts such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene It can be used various organic solvents such systems an organic solvent, an inorganic solvent such as water, or two or more mixed solvents thereof.
[0025]
In addition, various additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion assistants, desiccants, stabilizers, curing agents, curing accelerators, or curing retarders as necessary. Can also be added as appropriate.
[0026]
The method for forming the pattern layer 2 is not particularly limited, and various conventionally known printing methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method are used. be able to. In addition, for example, in the case of a solid surface, in addition to the above-described various printing methods, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method Various coating methods such as a dip coating method can also be used. In addition, for example, a hand-drawn method, ink-sink method, photographic method, laser beam or electron beam drawing method, partial vapor deposition method or etching method of metal or the like, or a combination of these methods can of course be performed.
[0027]
In the decorative sheet having a multilayer structure as shown in FIG. 1, the pattern layer 2 is placed on the polyester-based thermoplastic resin layer 1 side before the thermoplastic resin base sheet 1 and the polyester-based thermoplastic resin layer 2 are laminated. Although you may provide, you may provide in the thermoplastic resin base material sheet 3 side. Further, prior to the formation of the pattern layer 2, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, heavy chromium are applied to the printing surface of the polyester-based thermoplastic resin layer 1 or the thermoplastic resin base sheet 3. By performing surface treatment such as acid treatment, anchor treatment or primer treatment, the adhesion between the polyester-based thermoplastic resin layer 1 or the thermoplastic resin substrate sheet 3 and the pattern layer 2 can be improved.
[0028]
There is no restriction | limiting in particular in the kind of thermoplastic resin which comprises the thermoplastic resin base material sheet 3, The various thermoplastic resins conventionally used as the base material sheet of the decorative sheet which concerns can be used. Specifically, for example, polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, polyolefin resins such as ethylene-vinyl acetate copolymer or a saponified product thereof, and ethylene- (meth) acrylic acid (ester) copolymer. Copolymer, Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, Polyarylate, Polyester resin such as polycarbonate, Acrylic resin such as polymethyl methacrylate, 6-Nylon, 6,6-Nylon, 6,10-Nylon Polyamide resin such as polystyrene resin, AS resin, ABS resin, styrene resin such as cellulose acetate, cellulose derivatives such as nitrocellulose, chlorinated resin such as polyvinyl chloride and polyvinylidene chloride, polyvinyl fluoride, poly Fluorine resins such as vinylidene chloride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc., or two or more types of copolymers or mixtures selected from these, mixtures, composites, laminates, etc. are used. be able to.
[0029]
However, considering the adaptation to the environmental problems described above, among the above-mentioned various thermoplastic resins, the use of a chlorine-based resin or a fluorine-based resin is not very preferable, and contains a halogen element such as chlorine or fluorine. It is preferable to use a non-halogen thermoplastic resin. Among these, a polyolefin-based thermoplastic resin is most preferable in view of various balances such as a balance between appropriate flexibility and strength, processability such as bending, cutting and cutting, and weather resistance.
[0030]
Various homopolymers and copolymers such as those listed above are known as the above-mentioned polyolefin-based thermoplastic resins. Among them, the most suitable as a material for a base sheet for a decorative sheet is a polypropylene-based resin, that is, polypropylene. A single or copolymer as a main component, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and an α having 2 to 20 carbon atoms other than propylene Examples thereof include propylene-α-olefin copolymers containing 15 mol% or more of an olefin, preferably ethylene, butene-1,4-methylpentene-1, hexene-1 or octene-1. . Further, modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, which are usually used for softening polypropylene resins can be added. .
[0031]
The thermoplastic resin constituting the thermoplastic resin base sheet 3 includes, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, depending on the intended use of the decorative sheet. One or more conventionally known various additives such as an antistatic agent, a flame retardant, and a filler may be added. Specific examples of these additives include those already exemplified as additives for polyester-based thermoplastic resins.
[0032]
In addition to the above, the thermoplastic resin substrate sheet 3 may be colored by adding a colorant such as an appropriate organic or inorganic dye or pigment to the thermoplastic resin constituting the thermoplastic resin substrate sheet 3. it can. In particular, when the decorative sheet needs to be concealed depending on the application, it is preferable to make the thermoplastic resin base sheet 3 concealable by using a concealing pigment. The concealing pigment is a pigment having a high refractive index as compared with the thermoplastic resin as a dispersion medium. From the viewpoint of high refractive index, weather resistance, chemical resistance, etc., for example, a titanium oxide pigment or an iron oxide pigment. It is preferable to use at least an inorganic pigment such as Of course, instead of making the thermoplastic resin base sheet 3 itself concealing, a concealing solid layer 4 made of a printing ink or a coating agent containing a concealing pigment or the like may be provided, or both may be used in combination. it can.
[0033]
There is no restriction | limiting in particular in the thickness of the thermoplastic resin base material sheet 3, The thing of the same thickness as the base material sheet of the conventional general decorative sheet can be used. Specifically, although it depends on the use of the decorative sheet and the type of resin, it is generally selected from a range of about 50 to 200 μm.
[0034]
In the case of three-dimensional molding, the thermoplastic resin base sheet 3 also generally has a glass transition point or softening point of 85 ° C. or less and a tensile elastic modulus of 300 kgf / cm. ² It is desirable to comprise the following thermoplastic resin. However, especially when the thermoplastic resin base sheet 1 is thinner than the polyester-based thermoplastic resin layer 4, the upper limit is not necessarily limited as long as the former can sufficiently follow the latter thermal deformation. In some cases. The lower limit is not particularly limited as long as it is in a range that does not cause general inconveniences as a base sheet for a decorative sheet, for example, is adhesive.
[0035]
In the present invention, the method for laminating the polyester-based thermoplastic resin layer 1 and the thermoplastic resin base sheet 3 is not particularly limited, and any conventionally known method can be appropriately applied. Specifically, for example, an appropriate adhesive such as a dry laminate adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, or an ionizing radiation curable adhesive is applied to the polyester-based thermoplastic resin layer 1 previously formed into a film or sheet. The method of adhering to the surface of the thermoplastic resin substrate sheet 3 through 5 or the method of directly adhering by means such as thermocompression bonding or ultrasonic welding without using an adhesive, or heat-melting a polyester-based thermoplastic resin From among various conventionally known methods, such as a method of extruding into a film or sheet and simultaneously laminating and adhering to the surface of the thermoplastic resin base sheet 3, a method that matches the characteristics of the resin is appropriately selected. Can be used.
[0036]
In addition, of course, the pattern layer 2, the masking layer 4, etc. may be given to the polyester-type thermoplastic resin layer 1 and / or the thermoplastic resin substrate sheet 3 prior to the above-mentioned lamination. For the purpose of improving the property, an appropriate surface activation treatment such as corona treatment or ozone treatment or an appropriate adhesive resin composition is applied to the adhesive surface of the polyester-based thermoplastic resin layer 1 and / or the thermoplastic resin substrate sheet 3. An anchor layer 6 or 6 'made of a material can also be applied. In the case of the extrusion laminating method, the adhesiveness can be improved by co-extrusion lamination so that the adhesive resin is sandwiched between the thermoplastic resin base sheet 3 together with the polyester-based thermoplastic resin. .
[0037]
The surface of the polyester-based thermoplastic resin layer 1 may be provided with an emboss 7 having an appropriate pattern as required as conventionally known. There is no particular limitation on the type of embossed 7 pattern, and it may be various patterns such as, for example, wood grain (especially a conduit pattern), stone texture, Japanese paper, fabric texture, geometric pattern, or the like. For example, it may be a simple matte shape, a grain shape, a hairline shape, a suede tone or the like. Further, it is possible to further improve the design by synchronizing the pattern of the emboss 7 with the pattern of the pattern layer 2, but if it is not necessary, it may be non-synchronized. An emboss 7 having a pattern including both a pattern synchronized with the pattern and a pattern not synchronized can be provided.
[0038]
A method for forming the embossing 7 is not particularly limited, but a mechanical embossing method using a metal embossing plate is the most common. There is no particular limitation on the formation time of the emboss 7, and any time can be selected before, simultaneously with or after the lamination with the thermoplastic resin substrate sheet 2. The emboss 7 having the same or different pattern can be applied a plurality of times at a plurality of times. In addition, the concave part of the emboss 7 may be filled with the colorant 8 by a method such as a wiping method, if necessary, whereby a decorative sheet having a color pattern synchronized with the uneven pattern on the surface is excellent. Can be obtained.
[0039]
Moreover, the topcoat layer 9 can also be provided on the surface of the polyester-based thermoplastic resin layer 1 for the purpose of imparting more excellent surface properties to the surface of the decorative sheet. As a constituent material of the top coat layer 9, any one selected from various known top coat agents conventionally used as a constituent material of the top coat layer of the decorative sheet can be used. In general, it is necessary to have at least transparency that allows the base to be seen through, and it has surface properties such as abrasion resistance, scratch resistance, solvent resistance, and contamination resistance required for decorative sheet applications. In order to achieve this, it is preferable to use a material mainly composed of a curable resin. However, in the case of three-dimensional molding, it is necessary to consider flexibility in order to follow the elongation of the decorative sheet.
[0040]
Specific examples of the constituent material of the top coat layer 9 include heat such as melamine resin, phenol resin, urea resin, epoxy resin, aminoalkyd resin, urethane resin, polyester resin, and silicone resin. A curable resin, an ionizing radiation curable resin such as an acrylic resin, or the like can be preferably used. If necessary, various additives such as a gloss adjusting agent, a lubricant, an antistatic agent, an anti-condensation agent, an antibacterial agent, and an antifungal agent can be appropriately added. In addition, the top coat layer 9 is composed of two or more layers having different glosses, and one or more of them are provided in a pattern shape to obtain a decorative sheet having a material feeling and a visual three-dimensional effect due to changes in surface gloss. You can also.
[0041]
There is no particular limitation on the method for forming the top coat layer 9, for example, gravure coating method, roll coating method, dip coating method, air knife coating method, knife coating method, comma coating method, die coating method, lip coating method, kiss coating method, Any conventionally known coating method such as rod coating method, spray coating method, flow coating method and the like can be appropriately applied.
[0042]
If the adhesion between the polyester-based thermoplastic resin layer 1 and the topcoat layer 9 is insufficient, the surface of the polyester-based thermoplastic resin layer 1 is, for example, a corona before the topcoat layer 9 is formed. Adhesion between the polyester-based thermoplastic resin layer 1 and the topcoat layer 9 is improved by performing surface treatment such as treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment. can do.
[0043]
As described above, the decorative sheet of the present invention is similar to the conventional decorative sheet, for example, a woody base material such as plywood or particle board, an inorganic base material such as calcium silicate board or wood wool cement board, FRP ( fiber reinforced plastics), etc., which are used by being affixed to the surface of various base materials such as synthetic resin base materials. An adhesive is used, but depending on the type of resin constituting the thermoplastic resin base sheet 3, the adhesiveness with the general-purpose laminating adhesive may be insufficient. In preparation for such a case, it is preferable to provide a primer layer 10 made of a resin excellent in adhesiveness with the general-purpose adhesive described above on the back surface of the thermoplastic resin base sheet 3.
[0044]
Various primer agents such as urethane, acrylic, ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer system, etc. are known as the primer layer 10, and among these, a thermoplastic resin base material is used. Select the one that matches the sheet 3 and use it. In addition, if powders such as silica, alumina, calcium carbonate, and barium sulfate are added to the primer layer 10, for example, the surface of the primer layer 10 can be roughened to prevent blocking when the decorative sheet is wound and stored. In addition, the adhesiveness with the laminating adhesive due to the anchoring effect can be improved.
[0045]
The decorative sheet of the present invention is not only excellent in three-dimensional formability and scratch resistance on the surface due to the configuration as described above, but also has many advantages in common with decorative sheets using various conventional polyester-based thermoplastic resins. It is equipped with. For example, in the case of using a transparent polyester-based thermoplastic resin, the excellent transparency unique to the polyester-based thermoplastic resin makes it easy to create a decorative sheet with excellent pattern sharpness and high surface gloss. Can be obtained. Moreover, since the polyester-type thermoplastic resin is excellent also in hot water resistance and oil resistance, it can be used suitably also for uses, such as around a bathroom or a kitchen, for example.
[0046]
【Example】
A polypropylene resin colored by adding an inorganic pigment and an organic pigment is heated and melted, and the wetness index is adjusted to 38 dyn / cm or more by performing corona treatment on both sides while extruding without stretching to 120 μm in thickness by an extruder. A base sheet was prepared.
[0047]
On the other hand, the thickness is 50 μm, the glass transition point is 78 ° C., and the tensile modulus is 200 kgf / c m ² First, a wood grain pattern is printed on the lower surface of the copolyester film (Spectar: Eastman Chemical Japan Co., Ltd.) using a conventional urethane-based gravure printing ink for building materials, and then concealed. Gravure printing with urethane resin ink containing pigment composition composed mainly of inorganic inorganic pigments (iron oxide-based tea, iron oxide-based ocher and titanium oxide-based white) mixed with a small amount of carbon black, cobalt blue and phthalocyanine blue A concealed solid layer was printed by the method, and a thermoplastic urethane anchor agent was applied to a coating amount of 6 μm after drying.
[0048]
Thereafter, the printed surface of the copolymer polyester film is polymerized on the surface of the base sheet via a two-component urethane dry laminate adhesive, and the temperature is 120 ° C. and the pressure is 25 kgf / cm. ² Then, dry lamination was performed at a line speed of 20 m / min.
[0049]
Next, a top coat layer is formed by coating the upper surface of the copolyester film with an acrylate-based UV curable resin added with 0.2 wt% stabilizer and 0.3 wt% UV absorber to a thickness of 20 μm. Furthermore, embossing of the conduit handle was performed with a metal embossing roll at 180 ° C. Thereafter, the back surface of the base material sheet is subjected to corona treatment to adjust the wetting index to 38 yn / cm or more, and the urethane resin primer containing silica powder is applied to a coating amount of 1 g / m @ 2 after drying by the gravure coating method. And a primer layer was formed to complete the decorative sheet of the present invention.
[0050]
The obtained decorative sheet is spray-coated with 10 g / m2 (dry) of an aqueous two-component urethane adhesive on a polyester resin-based three-dimensional base material having a radius of curvature of 0.5 and dried, and then the sheet temperature is set to 80 ° C. Three-dimensionally laminated to make a decorative material.
[0051]
The resulting cosmetic material has scratch resistance of 2H in pencil hardness, passes stain resistance (JAS special plywood), and hot water resistance test (60 ° C for 10 days), and has high surface gloss with no whitening and cracking. A cosmetic material with good contamination and scratch resistance was obtained.
[0052]
【The invention's effect】
As described in detail above, the decorative sheet of the present invention has a glass transition point of 60 ° C. or higher and 85 ° C. or lower and a tensile modulus of 100 kgf / cm. ² 300 kgf / cm ² By comprising at least a polyester-based thermoplastic resin layer that is the following, not only lamination to a flat substrate and V-cut processing, but also lapping lamination to a columnar substrate and three-dimensional uneven substrate Even in the three-dimensional molded laminate, there are no problems such as cracking, whitening, wrinkles, drawdown, etc., and there is a remarkable effect that it is excellent in various surface properties such as scratch resistance. .
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing a laminated structure of an example of a decorative sheet of the present invention.
[Explanation of symbols]
1. Polyester thermoplastic layer
2 ... Pattern layer
3 ... Thermoplastic resin base sheet
4 ... Hiding layer
5 ... Adhesive layer
6, 6 '... Anchor layer
7. Emboss
8 Colorant
9 ... top coat layer
10 ... Primer layer

Claims (3)

A glass transition point of 60 ° C. or higher 85 ° C. or less, tensile decorative sheet elastic modulus, characterized in that at least comprising a thermoplastic polyester resin layer is 100 kgf / cm ² or more 300 kgf / cm ² or less. The decorative sheet according to claim 1, wherein a pattern layer and the transparent polyester-based thermoplastic resin layer are at least sequentially laminated on a thermoplastic resin base sheet. The decorative sheet according to claim 2, wherein the thermoplastic resin base sheet is made of a polyolefin-based thermoplastic resin.

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