WO2022210875A1 - 化粧シート及びこれを用いた化粧部材 - Google Patents
化粧シート及びこれを用いた化粧部材 Download PDFInfo
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- WO2022210875A1 WO2022210875A1 PCT/JP2022/015967 JP2022015967W WO2022210875A1 WO 2022210875 A1 WO2022210875 A1 WO 2022210875A1 JP 2022015967 W JP2022015967 W JP 2022015967W WO 2022210875 A1 WO2022210875 A1 WO 2022210875A1
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Images
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Definitions
- the present invention relates to a decorative sheet and a decorative member using the same.
- the decorative sheet has, for example, a structure having a surface protective layer on the base material layer.
- Benzophenone-based UV absorbers and benzotriazole-based UV absorbers have been used as UV absorbers, but these have not always been satisfactory in terms of performance. Specifically, when attempting to obtain sufficient weather resistance with benzophenone-based UV absorbers and benzotriazole-based UV absorbers, there is a problem that the amount of UV absorbers added increases and the UV absorbers tend to bleed. rice field. In addition, benzophenone-based UV absorbers and benzotriazole-based UV absorbers deteriorate significantly over time, making it difficult to maintain weather resistance over a long period of time.
- the decorative sheets of Patent Documents 1 and 2 can suppress bleeding out and have good long-term weather resistance compared to decorative sheets using benzophenone-based UV absorbers and benzotriazole-based UV absorbers.
- Patent Documents 1 and 2 are better in suppressing bleed-out and maintaining long-term weather resistance than conventional decorative sheets, there are cases where these performances cannot be satisfied when used in harsh environments. There is a need for further improvement.
- an object of the present disclosure is to provide a decorative sheet and a decorative member that can suppress bleed-out and deterioration of long-term weather resistance, and suppress deterioration of appearance.
- the present disclosure provides the following decorative sheet and decorative member.
- It has a substrate layer and a surface protective layer, the surface protective layer contains a resin, an ultraviolet absorber and particles, and the indentation depth measured in accordance with the Erichsen test method specified in JIS Z2247: 2006 is 4.0 mm.
- a cosmetic sheet that is above.
- a decorative member comprising an adherend and the decorative sheet according to 1 above.
- a decorative sheet and a decorative member capable of suppressing bleed-out and deterioration of long-term weather resistance, and suppressing deterioration of appearance.
- FIG. 1 is a cross-sectional view showing one embodiment of a decorative sheet of the present disclosure
- FIG. 1 is a cross-sectional view showing one embodiment of a decorative sheet of the present disclosure
- FIG. 1 is a cross-sectional view showing one embodiment of a decorative sheet of the present disclosure
- this embodiment An embodiment of the present disclosure (hereinafter sometimes referred to as “this embodiment") will be described below.
- numerical values related to "greater than”, “less than or equal to”, and “to” regarding the description of numerical ranges are numerical values that can be arbitrarily combined, and the numerical values in the examples are numerical values that can be used for the upper and lower limits of the numerical range. is.
- the decorative sheet of the present embodiment has a substrate layer and a surface protective layer, the surface protective layer contains a resin, an ultraviolet absorber and particles, and is measured according to the Erichsen test method specified in JIS Z2247:2006.
- the depth of indentation (hereinafter sometimes simply referred to as “depth of indentation”) is 4.0 mm or more.
- the processing step for example, wrapping the adherend, vacuum forming, V-cutting, etc.
- the surface of the decorative sheet may be damaged or cracked due to external force.
- the decorative sheet may be damaged or cracked due to contact between the decorative members during storage.
- the decorative member is used for a long period of time, especially as an exterior member, the surface may be scratched or cracked due to contact with sand, fallen leaves, or the like.
- the inventors of the present invention have found that the causes of bleed-out and deterioration of long-term weather resistance are common in that scratches and cracks occur on the surface of the decorative sheet, from the knowledge about the situations listed in (i) to (iii) above. I noticed that there was Then, in these cases, it was thought that bleeding out and deterioration of long-term weather resistance would occur due to scratches and cracks, as described below.
- the minute scratches, cracks (cracks), or delamination gradually grow over time as the sheet is used as a decorative member after being processed.
- the surface protective layer becomes easy to partially peel off. Where the surface protective layer is peeled off, not only does the surface protective layer lose its ability to protect the substrate layer, etc., but the ultraviolet absorber used as a weather resistant agent bleeds out, resulting in deterioration of the weather resistance of the decorative sheet as a whole. is considered to decrease. And, it is considered that such a problem will occur remarkably especially when exposed to the outdoors.
- Scratch resistance is basically a property when used as a decorative member by laminating it on an adherend as in (ii) and (iii) above, and in a processing step like (i) above. It is different from the property of suppressing the occurrence of cracks and scratches. In addition, it can be said that the improvement of scratch resistance tends to work disadvantageously in terms of suppressing the occurrence of cracks and scratches in the working process.
- the suppression of the occurrence of scratches and cracks depends on the cause of the occurrence, that is, the processing process or the use as a decorative member, and the desired surface protection, particularly in terms of hardness
- the properties of the layers are diametrically opposed. Therefore, although it can be said that the hardness of the surface protective layer must be a certain level or higher to suppress the occurrence of cracks and scratches, it can be suppressed simply by increasing or decreasing the hardness of the cured product of the resin composition that forms the surface protective layer. is difficult.
- the Erichsen test method is usually a test method for understanding the plastic deformation characteristics of sheet metal processing, especially deep drawing, and is a widely used test method in the field of metal processing.
- the "push depth" measured by the normal Erichsen test method is to push a punch with a spherical end into the test piece (measurement object) clamped between the wrinkle holder and the die.
- the indentation depth of the punch at the time when a penetrating crack occurs also referred to as the “Erichsen value”.
- the Erichsen test method is sometimes used to measure the adhesion peel strength, film strength, etc. of a paint film.
- the inventors of the present invention believe that the "indentation depth" is a property that the decorative sheet can have, not only the hardness described above, but also the resistance to various processing such as bending. I thought that it could be regarded as an index showing characteristics close to "flexibility". Furthermore, having a property close to "flexibility” is strong in resistance to various processing such as bending, that is, it may be excellent in resistance to external forces, which is also described in (i) above. By imparting properties close to "flexibility" to the decorative sheet, it may be possible to simultaneously suppress scratches and cracks that occur on the surface of the decorative sheet, such as those listed in (i) to (iii) above. thought.
- the present inventors found that in order to reduce the occurrence of scratches and cracks such as those listed in (i) to (iii) above, the depth of indentation of the decorative sheet by the Erichsen test was increased. It was found that a configuration of 4.0 mm or more should be adopted. By reducing the occurrence of scratches and cracks, the present invention has led to the decorative sheet of the present embodiment, which can suppress bleed-out and deterioration of long-term weather resistance, and can suppress deterioration of appearance.
- the decorative sheet of the present embodiment is required to have an indentation depth of 4.0 mm or more, which is measured by performing an Erichsen test using the decorative sheet as a test piece. If it is less than 4.0 mm, scratches and cracks are likely to occur under the conditions (i) to (iii) above, resulting in bleed-out and deterioration in long-term weather resistance, and deterioration in appearance. It will happen.
- the indentation depth is preferably 4.5 mm or more, more preferably 5.0 mm or more.
- the upper limit of the indentation depth is not particularly limited, and the larger the depth, the better. 15.0 mm or less.
- the "indentation depth” is measured according to the Erichsen test method defined in JIS Z2247:2006.
- the "push depth” in the present disclosure is a test piece (measurement object) clamped between the wrinkle holder and the die, and a punch with a spherical end is pushed from the base layer side of the decorative sheet. By this, it means the depth of punching at the time when fine cracks are generated in the surface protective layer. Specifically, it is measured by the method described in Examples using an Erichsen tester (JIS B7729:2005 compliant).
- the depth of indentation is mainly adjusted by the material constituting the base material layer, the thickness of the base material layer, the material (type of resin) constituting the surface protective layer, and the thickness of the surface protective layer. can be done. Moreover, when layers other than the base material layer and the surface protective layer are employed, which are provided as desired, it is also possible to adjust the materials, thicknesses, etc. of these layers.
- the depth of depression of the decorative sheet of the present embodiment can be easily adjusted by adopting the preferred aspects described later for the materials constituting each layer, the thickness of each layer, and the like.
- FIG. 1 is a cross-sectional view showing a representative embodiment of the decorative sheet 100 of this embodiment
- FIG. 2 is a cross-sectional view showing a preferred embodiment of the decorative sheet 100 of this embodiment.
- the Z-axis direction indicates the thickness direction
- the plane formed by the X-axis and Y-axis indicates a plane of the decorative member observed from the Z-axis direction.
- the decorative sheet 100 of FIG. 1 has the surface protective layer 10 on the base material layer 60 .
- the decorative sheet 100 of FIG. 2 has a decorative layer 50 , an adhesive layer 40 , a transparent resin layer 30 and a primer layer 20 between the base material layer 60 and the surface protective layer 10 .
- the decorative sheet of the present embodiment has a basic structure comprising a surface protective layer on a base material layer
- various forms of lamination structure can be selected according to usage, required performance, and the like.
- the decorative sheet of the present embodiment includes a decorative layer, an adhesive layer, a transparent resin layer and a primer layer as layers other than these layers between the base material layer and the surface protective layer.
- Laminated structures that the decorative sheet of the present embodiment can take include, for example, the following laminated structures (1) to (7), that is, between the base material layer and the surface protective layer, a decorative layer, an adhesive layer, and a transparent layer.
- a laminate structure having one or more layers selected from a resin layer and a primer layer is preferred.
- the decorative sheet 100 has the following lamination structure (2)
- the decorative sheet 100 has the following lamination structure (1).
- Base material layer 60/decorative layer 50/adhesive layer 40/transparent resin layer 30/primer layer 20/surface protective layer 10 (2) Base layer 60/surface protective layer 10 (3) Base layer 60/primer layer 20/surface protective layer 10 (4) Base material layer 60/adhesive layer 40/transparent resin layer 30/surface protective layer 10 (5) Base layer 60/decoration layer 50/surface protective layer 10 (6) Base material layer 60/adhesive layer 40/transparent resin layer 30/decorative layer 50/surface protective layer 10 (7) Base material layer 60/adhesive layer 40/transparent resin layer 30/decorative layer 50/primer layer 20/surface protective layer 10
- the base material layer is a layer that functions as a support for the surface protective layer of the decorative sheet of the present embodiment, and also contributes to ease of adhesion to an adherend when used for decoration of a decorative member.
- Examples of the substrate layer include films, sheets and plates made of various papers, plastics, metals, woven fabrics, non-woven fabrics, wood, ceramic materials, and the like.
- planar substrate layers having a predetermined thickness are referred to as films, sheets, and plates in descending order of thickness, but in the present disclosure, there is no particular need to distinguish between different thicknesses. Therefore, in this specification, even if these names are appropriately replaced with each other, they are handled as if there is no particular essential difference. Moreover, these differences in designation (differences in thickness) do not cause any difference in the interpretation of the claims of the present disclosure.
- plastic sheets include plastic films, sheets and plates.
- a plastic sheet is preferable in consideration of the ease of adjusting the depth of indentation and the ease of handling of the decorative sheet as a whole.
- the resin constituting the plastic sheet include polypropylene resin, polyethylene resin, polymethylpentene resin, polyolefin thermoplastic elastomer, polyolefin resin such as ionomer; polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer.
- Vinyl chloride resin such as coalescence; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester resin such as polyester thermoplastic elastomer; polymethyl Acrylic resins such as (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer; polyamide resins represented by nylon 6, nylon 66, etc.; cellulose triacetate, cellophane, celluloid cellulose resins such as polystyrene, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene resins (ABS resins) and other styrene resins; polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, thermoplastic resins
- polyolefin resins one selected from polyolefin resins, vinyl chloride resins, polyester resins and acrylic resins considering the ease of adjusting the indentation depth, weather resistance, water resistance, printability, moldability and price. The above is preferable.
- polyolefin resins are preferable in that the effects of the present disclosure can be exhibited more easily, and in particular, in terms of easiness in adjusting the indentation depth.
- the polyolefin resin is preferably, for example, a polyethylene resin or a polypropylene resin, and more preferably a polypropylene resin.
- the polyethylene resin may be a homopolymer of ethylene, that is, polyethylene (low density, medium density, high density), or ethylene and other comonomers copolymerizable with ethylene (eg, propylene, 1-butene , 1-hexene, 1-octene, and other ⁇ -olefins; vinyl acetate, vinyl alcohol, etc.). These polyethylene resins may be used individually by 1 type, and may use 2 or more types together.
- the polypropylene resin may be a homopolymer of propylene, that is, polypropylene, as with the polyethylene resin, or may be propylene and other comonomers copolymerizable with propylene (for example, ethylene, 1-butene, 1-hexene). , 1-octene; vinyl acetate, vinyl alcohol, etc.). These polypropylene resins may be used singly or in combination of two or more.
- polyethylene low density, medium density, high density
- polypropylene ethylene-propylene copolymer
- propylene-butene copolymer propylene-butene copolymer
- polypropylene is more preferable.
- the substrate layer may be colorless and transparent, or may be colored from the viewpoint of design.
- coloring agents such as dyes and pigments can be added to the substrate layer.
- pigments that tend to suppress fading are preferred.
- Pigments include, for example, white pigments such as zinc white, white lead, lithopone, titanium dioxide (titanium white), precipitated barium sulfate and barite; black pigments such as carbon black, aomethine azo black pigments, and perylene black pigments; lead Red pigments such as tan, iron oxide red, quinacridone red, and polyazo red; Blue pigments such as Prussian blue (potassium iron ferrocyanide) can be mentioned.
- the thickness of the substrate layer is not particularly limited, but when the substrate layer is a plastic sheet, it is preferably 20 to 320 ⁇ m, more preferably 40 to 160 ⁇ m, especially considering the ease of adjusting the depth of indentation. 40 to 100 ⁇ m is more preferred. From the same point of view, when the substrate layer is paper, the basis weight is preferably 20 to 150 g/m 2 , more preferably 30 to 100 g/m 2 .
- the shape of the substrate layer is not limited to a flat plate shape, and may be a special shape such as a three-dimensional shape.
- the base layer may be subjected to physical surface treatment such as an oxidation method or roughening method, or a chemical surface treatment on one or both sides of the base layer. A surface treatment such as treatment may be applied, or a primer layer may be formed.
- the substrate layer may contain an ultraviolet absorber from the viewpoint of improving long-term weather resistance.
- ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers. Among these, hydroxyphenyltriazine-based UV absorbers are preferred. The hydroxyphenyltriazine-based ultraviolet rays preferably used in the base material layer will be described later. In this embodiment, one type of ultraviolet absorber may be used alone, or a plurality of types may be used in combination.
- the content of the ultraviolet absorber is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, with respect to 100 parts by weight of the resin of the base layer.
- the base layer may contain a light stabilizer from the viewpoint of improving weather resistance.
- light stabilizers include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers.
- UV absorbers and light stabilizers that are preferably used as components of the base material layer each contain a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, vinyl group, or allyl group in the molecule. may have.
- Additives may be added to the base material layer as necessary.
- additives in addition to weathering agents such as the above ultraviolet absorbers and light stabilizers, for example, inorganic particles such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, oxidation Inhibitors are included.
- the amount of the additive to be added is not particularly limited as long as it does not impair the depth of indentation, surface properties, etc., and can be appropriately set according to the required properties.
- the surface protective layer contains a resin and an ultraviolet absorber and is a layer for protecting the surface of the decorative sheet of the present embodiment.
- the surface protective layer is required to have at least scratch resistance, particularly from the viewpoint of suppressing the occurrence of scratches and cracks (cracks), and is also required to have surface properties such as weather resistance and stain resistance.
- the surface protective layer is composed of, for example, a resin composition containing a resin component, an ultraviolet absorber, and particles (hereinafter also referred to as a "resin composition for forming a surface protective layer").
- the resin composition preferably contains a curable resin as a resin component
- the surface protective layer contains a curable resin, an ultraviolet absorbing It is preferably composed of a cured product of a resin composition containing an agent and particles. That is, the resin contained in the surface protective layer may be a cured resin obtained by curing a curable resin.
- the depth of depression of the decorative sheet can be adjusted by the material (type of resin component) forming the surface protective layer and the thickness of the surface protective layer. Therefore, it can be said that the structure of the surface protective layer, particularly the resin component, is one of the factors that directly affect the depth of depression of the decorative sheet. Therefore, the hardness of the cured product of the resin composition is set to a certain level or higher to improve the scratch resistance, and not only to suppress the occurrence of scratches and cracks (cracks) when used as a decorative member, but also to improve flexibility.
- the resin composition constituting the surface protective layer It is important to adopt the resin component contained.
- the resin component forming the surface protective layer will be described in more detail below.
- the resin component is preferably a curable resin, and more preferably a thermosetting resin or an ionizing radiation curable resin, from the viewpoint of improving surface properties, particularly scratch resistance. Furthermore, considering the ease of adjusting the indentation depth and the fact that adjusting the indentation depth can suppress bleedout and deterioration of long-term weather resistance and suppress deterioration of appearance, ionizing radiation curing more preferred is a flexible resin.
- the ionizing radiation-curable resin is a resin having a group that is cross-linked and cured by irradiation with ionizing radiation (hereinafter sometimes referred to as an “ionizing radiation-curable functional group”), and is cross-linked and cured by irradiation with ionizing radiation. It's about resin.
- a resin composition containing an ionizing radiation-curable resin as a resin component is a resin composition that is crosslinked and cured by irradiation with ionizing radiation, and can also be referred to as an ionizing radiation-curable resin composition.
- the ionizing radiation-curable functional group is a group that is cross-linked and cured by irradiation with ionizing radiation, and preferably includes functional groups having an ethylenic double bond such as (meth)acryloyl group, vinyl group, and allyl group.
- ionizing radiation refers to electromagnetic waves or charged particle beams having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. , and also include electromagnetic waves such as X-rays and ⁇ -rays, and charged particle beams such as ⁇ -rays and ion beams.
- Examples of ionizing radiation curable resins include electron beam curable resins and ultraviolet curable resins.
- electron beam curable resins are preferred from the viewpoints of low environmental load because they can be applied without a solvent and no need for a polymerization initiator.
- the resin composition for forming a surface protective layer preferably contains a weather resistant agent such as an ultraviolet absorber from the viewpoint of improving weather resistance
- an electron beam curable resin composition is preferred over an ultraviolet curable resin composition. Since it is easy to increase the crosslink density, it is advantageous in terms of surface properties such as scratch resistance and stain resistance.In addition, since it is easy to adjust the indentation depth, long-term weather resistance is improved and the appearance is reduced. can be further suppressed.
- the ionizing radiation-curable compound can be appropriately selected and used from polymerizable monomers and polymerizable oligomers commonly used as ionizing radiation-curable resins.
- a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is preferable.
- (meth)acrylate means "acrylate or methacrylate”.
- polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group. be done.
- the number of functional groups of the polyfunctional (meth)acrylate monomer is preferably 2 or more and 8 or less. 2 or more and 6 or less are more preferable, 2 or more and 4 or less are still more preferable, and 2 or more and 3 or less are still more preferable. These polyfunctional (meth)acrylates may be used alone or in combination.
- polymerizable oligomers examples include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups as the functional groups.
- examples thereof include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.
- polymerizable oligomers there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain.
- oligomers having cationic polymerizable functional groups A cyclohexyl (meth)acrylate oligomer can also be used.
- urethane (meth)acrylate oligomer epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer , polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers are preferred, urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are further preferred. preferable.
- the number of functional groups of these polymerizable oligomers makes it easy to adjust the indentation depth, and by adjusting the indentation depth, it is possible to suppress bleedout and deterioration of long-term weather resistance, and to suppress deterioration of appearance.
- it is preferably 2 or more and 8 or less, and the upper limit is more preferably 6 or less, further preferably 4 or less, and more preferably 3 or less. More preferred.
- the weight average molecular weight of these polymerizable oligomers makes it easy to adjust the indentation depth, and by adjusting the indentation depth, suppresses bleedout and deterioration of long-term weather resistance, and also prevents deterioration of appearance. Considering that it can be suppressed and improvement of surface properties such as scratch resistance, weather resistance, and stain resistance, it is preferably 1,100 or more, more preferably 1,250 or more, still more preferably 1,500 or more, and more More preferably 1,750 or more, particularly preferably 1,900 or more.
- the weight average molecular weight of the polymerizable oligomer is preferably 7,500 or less, more preferably 7,000 or less, still more preferably 6,000 or less.
- the weight average molecular weight is the average molecular weight measured by gel permeation chromatography (GPC) analysis and converted to standard polystyrene.
- a monofunctional (meth)acrylate can be used together in the ionizing radiation-curable resin composition for the purpose of reducing the viscosity of the ionizing radiation-curable resin composition.
- These monofunctional (meth)acrylates may be used alone or in combination.
- thermosetting resin is a resin that is cured by heating, and a resin composition containing a thermosetting resin as a resin component can also be referred to as a thermosetting resin composition that is cured by heating.
- thermosetting resins examples include acrylic polyol resins, acrylic resins, urethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. These thermosetting resins preferably have two or more functional groups such as a hydroxyl group, an amino group, a carboxyl group and an epoxy group in the molecule. If necessary, a curing agent is added to these curable resins in the thermosetting resin composition.
- Curing agents include, for example, isocyanate compounds.
- the isocyanate-based compound is preferably a polyisocyanate compound having two or more isocyanate groups in the molecule.
- polyisocyanate compounds include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and hydrogenated compounds thereof, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI ).
- the ratio of the curable resin to the total resin components contained in the resin composition for forming the surface protective layer makes it easy to adjust the indentation depth. is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and even more preferably 90% by mass or more, considering that it is possible to suppress the deterioration of the appearance. .
- the resin composition for forming the surface protective layer may contain, for example, a thermoplastic resin as a resin component in order to adjust the indentation depth. That is, the surface protective layer may contain a thermoplastic resin.
- the thermoplastic resin include the same thermoplastic resins as those exemplified as the resin constituting the plastic sheet of the base material layer.
- the surface protective layer preferably contains an ultraviolet absorber. That is, the surface protective layer-forming resin composition preferably contains an ultraviolet absorber.
- ultraviolet absorbers examples include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers. Among these, hydroxyphenyltriazine-based UV absorbers are preferred. In this embodiment, one type of ultraviolet absorber may be used alone, or a plurality of types may be used in combination.
- a hydroxyphenyltriazine-based ultraviolet absorber is, for example, an ultraviolet absorber represented by general formula (I).
- R 11 is a single bond or a divalent organic group
- R 12 is a hydrocarbon group
- R 13 , R 14 , R 15 , R 16 and R 17 are each independently a monovalent organic group
- n 11 and n Each 12 is independently an integer of 0-5.
- the hydroxyphenyltriazine-based ultraviolet absorber Since the hydroxyphenyltriazine-based ultraviolet absorber has a large molecular structure as represented by the general formula (1), from the viewpoint of steric hindrance, the molecular structure makes it difficult to bleed out and escape from the base material layer and the surface protective layer. It has the above characteristics. Therefore, long-term weather resistance is improved.
- the effect of using a hydroxyphenyltriazine-based ultraviolet absorber that is, suppression of bleed-out and improvement of long-term weather resistance, is further improved by using it in a decorative sheet having a predetermined indentation depth.
- aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group are preferred from the viewpoint of weather resistance.
- the number of carbon atoms in these aliphatic hydrocarbon groups is preferably 1 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 4 or less.
- the alkylene group and alkenylene group may be linear, branched, or cyclic, but preferably linear or branched.
- Examples of monovalent organic groups for R 12 include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups and arylalkyl groups, with alkyl groups being preferred.
- the number of carbon atoms in the alkyl group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and still more preferably 12 or less.
- the alkyl group and alkenyl group may be linear, branched or cyclic, preferably linear or branched, more preferably branched.
- Examples of monovalent organic groups for R 13 and R 14 include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups, and aromatic hydrocarbon groups such as aryl groups and arylalkyl groups. is preferred, and an aryl group is preferred.
- the number of carbon atoms in the aryl group of R 13 and R 14 is preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, still more preferably 10 or less.
- the number of carbon atoms in the arylalkyl group is preferably 7 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and still more preferably 10 or less.
- Examples of monovalent organic groups for R 15 , R 16 and R 17 include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups and arylalkyl groups, and aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups. groups are preferred, and alkyl groups are more preferred.
- R 15 , R 16 and R 17 are alkyl groups and alkenyl groups, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and still more preferably. is 12 or less, more preferably 10 or less.
- R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 groups have substituents such as halogen atoms, hydroxyl groups, amino groups and alkyl groups having 1 to 4 carbon atoms.
- n 11 and n 12 are each independently an integer of 0-5, preferably an integer of 1-3, more preferably an integer of 1-2.
- the plurality of R 13 and R 14 may be the same or different, and are preferably the same from the viewpoint of availability.
- hydroxyphenyltriazine-based ultraviolet absorbers represented by the general formula (1)
- hydroxyphenyltriazine compounds A to C represented by the following chemical formulas (2) to (4) are particularly preferred.
- the hydroxyphenyltriazine compound A represented by the chemical formula (2) is an acyloxy group represented by R 16 (R 16 is 3-heptyl group), R 13 and R 14 are hydrogen atoms, and it is available as, for example, a commercial product (“ADEKA STAB LA-46 (product number)” manufactured by ADEKA Corporation).
- the hydroxyphenyltriazine compound B represented by the chemical formula (3) is a 2,3-butylene group for R 11 and an alkoxy group represented by -OR 17 for R 12 (R 17 is an isooctyl group) in the above general formula (1).
- R 13 and R 14 are phenyl groups, and n 11 and n 12 are 1.
- it is available as a commercial product (“Tinuvin 479 (product number)” manufactured by Ciba Specialty Chemicals Co., Ltd.).
- the hydroxyphenyltriazine compound C represented by the chemical formula (4) is represented by the above general formula (1), wherein R 11 is a single bond, R 12 is an isooctyl group, R 13 and R 14 are phenyl groups, and n 11 and n 12 is 1, and is available, for example, as a commercial product (“Tinuvin 1600 (product number)”, manufactured by Ciba Specialty Chemicals Co., Ltd.).
- hydroxyphenyltriazine compound D represented by the following general formula (5) is also preferable as a hydroxyphenyltriazine-based ultraviolet absorber.
- the hydroxyphenyltriazine compound D represented by the chemical formula (5) is a compound of the general formula (1) in which R 11 is a single bond, R 12 is a hexyl group, and R 13 and R 14 are hydrogen atoms. ("Tinuvin 1577 (product number)", manufactured by Ciba Specialty Chemicals Co., Ltd.).
- a hydroxyphenyltriazine-based ultraviolet absorber When a hydroxyphenyltriazine-based ultraviolet absorber is used in the surface protective layer, a combination of a hydroxyphenyltriazine compound A and a hydroxyphenyltriazine compound B is preferred from the viewpoint of suppressing bleedout and improving long-term weather resistance. preferable.
- the content of hydroxyphenyltriazine compound B is preferably 50% by mass or less, more preferably It is 45% by mass or less, more preferably 40% by mass or less, and the lower limit is preferably 1% by mass or more, more preferably 5% by mass, and still more preferably 10% by mass or more.
- the combination of hydroxyphenyltriazine compound A and hydroxyphenyltriazine compound C is also preferable from the viewpoint of improving long-term weather resistance.
- the content of hydroxyphenyltriazine compound C relative to the total amount of these is preferably 50% by mass or less, more preferably It is 45% by mass or less, more preferably 40% by mass or less, and the lower limit is preferably 1% by mass or more, more preferably 5% by mass, and still more preferably 10% by mass or more.
- the content of the hydroxyphenyltriazine-based ultraviolet absorbent relative to the total amount of the ultraviolet absorbent used in the surface protective layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and more More preferably, it is 90% by mass or more.
- the ultraviolet absorber the more the hydroxyphenyltriazine-based ultraviolet absorber, the better.
- the content of the ultraviolet absorber is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more based on 100 parts by mass of the resin.
- the content of the ultraviolet absorber is at least the above lower limit, the effect of using the ultraviolet absorber and the weather resistance due to the ultraviolet absorbing performance can be sufficiently obtained.
- the upper limit of the content of the ultraviolet absorber with respect to 100 parts by mass of the resin is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, even more preferably 8 parts by mass or less, and even more preferably 7 parts by mass. It is below.
- the content of the ultraviolet absorber is equal to or less than the above upper limit, the ultraviolet absorber is less likely to bleed out, improving long-term weather resistance, further suppressing deterioration of appearance, and efficiently absorbing ultraviolet rays. Provides weather resistance through performance.
- the surface protective layer comprises a first ultraviolet absorbent having an absorption peak at a first wavelength, a second ultraviolet absorbent having an absorption peak at a second wavelength longer than the first wavelength, and a second ultraviolet absorbent having an absorption peak at a second wavelength longer than the first wavelength.
- a third ultraviolet absorber having an absorption peak at a third wavelength longer than the two wavelengths may also be included.
- Each absorption peak is based on an absorbance spectrum measured using a UV-Vis-NIR spectrophotometer.
- the first ultraviolet absorber has an absorption peak at the first wavelength.
- the first wavelength is preferably in the range of 270 nm or more and 300 nm or less, more preferably in the range of 270 nm or more and 290 nm or less, and even more preferably in the range of 270 nm or more and 280 nm or less.
- the second ultraviolet absorber has an absorption peak at the second wavelength.
- the second wavelength is preferably in the range of 310 nm or more and 330 nm or less, and more preferably in the range of 310 nm or more and 325 nm or less.
- the third ultraviolet absorber has an absorption peak at the third wavelength.
- the third wavelength is preferably in the range of 340 nm or more and 370 nm or less, and more preferably in the range of 345 nm or more and 365 nm or less.
- the above absorption peak preferably means the maximum absorption peak in the wavelength range of 270 nm or more and 380 nm or less.
- the maximum absorption peak is preferably in the range of 270 nm or more and 300 nm or less.
- the difference between the second wavelength and the first wavelength is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, preferably 60 nm or less, more preferably 55 nm or less, still more preferably 50 nm or less.
- the difference between the third wavelength and the second wavelength is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, preferably 60 nm or less, more preferably 55 nm or less, still more preferably 50 nm or less.
- the difference between the third wavelength and the first wavelength is preferably 40 nm or more, more preferably 50 nm or more, still more preferably 60 nm or more, and preferably 100 nm or less, more preferably 95 nm or less, still more preferably 90 nm or less.
- Examples of the first to third ultraviolet absorbers include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers, which are excellent in weather resistance and absorbance and wavelength selectivity. From the point of view, a triazine-based ultraviolet absorber is preferable.
- hydroxyphenyltriazine-based UV absorbers are preferable from the viewpoint of weather resistance.
- Specific examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3 ,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5 -triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy- 3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin
- the total content of the first UV absorber, the second UV absorber, and the third UV absorber is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the resin. , more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less.
- the total content of the ultraviolet absorbers is at least the lower limit, the weather resistance of the decorative sheet tends to be further improved.
- the total content of the ultraviolet absorbers is equal to or less than the upper limit, there is a tendency that the bleed-out of the ultraviolet absorbers can be suppressed.
- the content of the first ultraviolet absorber with respect to 100 parts by mass of the resin is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.3 parts by mass. It is at least 1 part by mass, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less. This tends to improve weather resistance, for example.
- the content of the second ultraviolet absorber with respect to 100 parts by mass of the resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass. or more, preferably 8 parts by mass or less, more preferably 6 parts by mass or less, and even more preferably 5 parts by mass or less. This tends to improve weather resistance, for example.
- the content of the third ultraviolet absorber with respect to 100 parts by mass of the resin is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.3 parts by mass. It is at least 1 part by mass, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less. This tends to improve weather resistance, for example.
- the content of the second ultraviolet absorbent is greater than the content of the first ultraviolet absorbent and greater than the content of the third ultraviolet absorbent. This allows the surface protective layer to absorb a wide range of wavelengths, and tends to improve weather resistance, for example.
- the resin composition for forming the surface protective layer contains, in addition to the resin component and the ultraviolet absorber, for example, a weather resistance agent such as a light stabilizer, particles such as a filler, an antioxidant, an ultraviolet shielding agent, a polymerization inhibitor, and a cross-linking agent. , an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a coupling agent, a plasticizer, an antifoaming agent, an antiblocking agent, a lubricant, a solvent, and other additives.
- the surface protective layer may contain the above additives in addition to the above resin and UV absorber.
- light stabilizers are preferable from the viewpoint of improving long-term weather resistance.
- the light stabilizer that can be used in the surface protective layer is the same as the light stabilizer that can be used in the substrate layer.
- the surface protective layer-forming resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
- additives such as a photopolymerization initiator and a photopolymerization accelerator.
- photopolymerization initiators include one or more selected from acetophenone, benzophenone, ⁇ -hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate, ⁇ -acyloxime ester, thioxanthones, and the like.
- the photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing speed.
- one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. is mentioned.
- the surface protective layer preferably contains particles. By containing particles in the surface protective layer, it is possible to improve the matte feeling of the surface protective layer (for example, the matte design). The use of particles also improves the scratch resistance of the surface protective layer.
- the surface protective layer contains particles such as silica, fine cracks may occur in the surface protective layer starting from the particles, resulting in deterioration of weather resistance.
- the indentation depth measured in accordance with the decorative sheet Erichsen test method is 4.0 mm or more, the occurrence of such fine cracks can be suppressed. That is, when the surface protective layer contains the above particles and has an indentation depth of 4.0 mm or more according to the Erichsen test method, it is possible to achieve both a matte feel and weather resistance of the surface protective layer.
- particles include fillers such as silica, talc, clay, barium sulfate, barium carbonate, calcium carbonate, and magnesium carbonate.
- Silica is preferable in consideration of the high degree of freedom in design and the ease of adjusting the properties as desired.
- the average particle diameter of the particles is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and still more preferably 0.2 ⁇ m or more, and the upper limit is preferably 15 ⁇ m or less, more preferably 13 ⁇ m or less, and still more preferably 10 ⁇ m or less. is.
- the surface protective layer can have a more improved matte feel.
- the average particle diameter of the particles is equal to or less than the upper limit, the particles can be prevented from falling off from the surface protective layer.
- the average particle size is the average value of particle sizes measured for non-agglomerates of randomly selected 100 particles by observing a cross section in the thickness direction of the decorative sheet with a scanning electron microscope (SEM). means (arithmetic (number) mean diameter). The above particle diameter is the major axis diameter of the particles.
- the ratio of A to B (A/B) is preferably 0.3 or more. , more preferably 0.5 or more, still more preferably 0.8 or more, particularly preferably 1.0 or more, preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less be.
- the above ratio is at least the lower limit, the surface protective layer can have a more matte feel.
- the above ratio is equal to or less than the upper limit, it is possible to prevent the particles from falling off from the surface protective layer.
- the content of the particles is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more with respect to 100 parts by mass of the resin component contained in the resin composition for forming a surface protective layer.
- the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less.
- the content of the particles is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, with respect to 100 parts by mass of the resin contained in the surface protective layer, and the upper limit is preferably 40 parts by mass. It is not more than 30 parts by mass, more preferably not more than 25 parts by mass. When the content of the particles is within the above range, it is possible to efficiently improve the matte feeling and scratch resistance of the surface protective layer, and to suppress the falling off of the particles from the surface protective layer.
- the thickness of the surface protective layer makes it easy to adjust the indentation depth, and by adjusting the indentation depth, it is possible to suppress bleeding out, suppress deterioration of long-term weather resistance, and suppress deterioration of appearance.
- the thickness is preferably 1.5 ⁇ m or more and 20 ⁇ m or less, more preferably 2 ⁇ m or more and 15 ⁇ m or less, and still more preferably 3 ⁇ m or more and 10 ⁇ m or less. Further, when the thickness of the surface protective layer is within the above range, the surface properties such as scratch resistance, matt feeling, weather resistance, and stain resistance are improved in a well-balanced manner.
- the decorative sheet of this embodiment may have other layers such as a primer layer, a transparent resin layer, a decorative layer, and an adhesive layer in addition to the base layer and the surface protective layer.
- a primer layer a transparent resin layer
- a decorative layer a transparent resin layer
- an adhesive layer in addition to the base layer and the surface protective layer.
- the decorative sheet of the present embodiment preferably has a primer layer in contact with the surface of the surface protective layer on the substrate layer side. Adhesion between the base material layer and the surface protective layer due to the decorative sheet having a primer layer, and adhesion between the transparent resin layer and the surface protective layer when the decorative sheet has a transparent resin layer described later, improves.
- the adhesion between these layers is improved, for example, when the decorative sheet of the present embodiment is used outdoors, delamination due to solar radiation or the like is less likely to occur, and deterioration of the decorative sheet is further suppressed.
- the primer layer contains an ultraviolet absorber, long-term weather resistance can be improved.
- a primer layer contains resin, for example.
- resins constituting the primer layer include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (polymer A polymer having a carbonate bond in its main chain and two or more hydroxyl groups in its terminals and side chains (urethane-acrylic copolymer derived from polycarbonate polyol), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride- Resin components such as vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrocellulose), and cellulose acetate resin are preferred, and these can be used alone or in combination.
- the resin contained in the primer layer may be a cured resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resin components and cross-linking and curing.
- a cured resin obtained by crosslinking and curing a polyol resin such as an acrylic polyol resin with an isocyanate curing agent is preferable, and a cured resin obtained by crosslinking and curing an acrylic polyol resin with an isocyanate curing agent is more preferable.
- the primer layer is formed, for example, from a primer layer-forming resin composition mainly composed of a resin component.
- the primer layer may contain additives such as ultraviolet absorbers and light stabilizers, if necessary. That is, the primer layer may be formed of a resin composition containing resin components and additives.
- the ultraviolet absorber that can be used in the primer layer is the same as the ultraviolet absorber that can be used in the surface protective layer, and is preferably a hydroxyphenyltriazine-based ultraviolet absorber as in the surface protective layer.
- the light stabilizer that can be used in the primer layer is the same as the light stabilizer that can be used in the substrate layer.
- the content of the ultraviolet absorber is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and even more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the resin of the primer layer.
- the content of the ultraviolet absorber is within the above range, weather resistance can be efficiently obtained.
- the thickness of the primer layer is preferably 1 ⁇ m or more and 10 ⁇ m or less, more preferably 2 ⁇ m or more and 8 ⁇ m or less.
- the thickness of the primer layer is within the above range, the effect of providing the primer layer, that is, interlayer adhesion can be efficiently obtained. In addition, it becomes easier to adjust the depth of pressing of the decorative sheet.
- the decorative sheet may have a back primer layer on the opposite side of the base material layer to the surface protective layer for the purpose of improving adhesion to the adherend.
- the decorative sheet of this embodiment may have a transparent resin layer between the base material layer and the surface protective layer from the viewpoint of increasing the strength. Since the decorative sheet has a transparent resin layer, it becomes easier to adjust the depth of pressing of the decorative sheet.
- the transparent resin layer is preferably positioned between the base material layer and the primer layer.
- the transparent resin layer is preferably positioned between the decorative layer and the surface protective layer from the viewpoint of protecting the decorative layer.
- the resin constituting the transparent resin layer examples include the same thermoplastic resins as the resin constituting the plastic sheet of the base material layer.
- these resins polyolefin resins are preferable, and polypropylene resins are preferable in consideration of ease of adjustment of the depth of indentation, as in the base layer.
- the transparent resin layer may be a mixture of the thermoplastic resins described above, or may be a resin layer obtained by combining one or more of the thermoplastic resins described above.
- the content of the polyolefin resin in the transparent resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total resin in the transparent resin layer, in consideration of the ease of adjusting the indentation depth. and more preferably 90% by mass or more.
- the transparent resin layer may be transparent to the extent that the base material side of the transparent resin layer is visible, and if it has a decorative layer, it may be transparent to the extent that the decorative layer can be visually recognized. In addition, it may be colored, transparent, or translucent. That is, in the present specification, "transparency” means colorless transparency, as well as colored transparency and semi-transparency.
- the transparent resin layer may contain additives such as ultraviolet absorbers, light stabilizers and other weather resistance agents, and colorants and the like.
- the ultraviolet absorber that can be used in the transparent resin layer is the same as the ultraviolet absorber that can be used in the surface protective layer, and is preferably a hydroxyphenyltriazine-based ultraviolet absorber as in the case of the surface protective layer.
- the light stabilizer that can be used in the transparent resin layer is the same as the light stabilizer that can be used in the base material layer, and the coloring agent that can be used in the base layer is the same as the coloring agent that can be used in the base material layer. is similar to
- the content of the ultraviolet absorber is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the resin of the transparent resin layer. .
- the lower limit of the content of the ultraviolet absorber may be 0.1 parts by mass.
- the thickness of the transparent resin layer is preferably 20 ⁇ m or more and 150 ⁇ m or less, more preferably 40 ⁇ m or more and 120 ⁇ m or less, and still more preferably 50 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the transparent resin layer is within the above range, it is easy to adjust the indentation depth, the effect of the transparent resin layer, that is, the strength of the decorative sheet is enhanced, and when the decorative layer is provided, the strength of the decorative layer is improved. The effect of protection is obtained efficiently.
- the transparent resin layer contains an ultraviolet absorber, the weather resistance can be efficiently improved.
- the decorative sheet of the present embodiment preferably has a decorative layer at an arbitrary portion of the decorative sheet.
- the location where the decoration layer is formed is preferably on the side closer to the base material layer.
- the decorative layer is preferably positioned between the base layer and the primer layer.
- the decorative layer is preferably positioned between the substrate layer and the transparent resin layer.
- the decorative layer may be, for example, a colored layer covering the entire surface (so-called solid colored layer), or a pattern layer formed by printing various patterns using ink and a printing machine. Alternatively, a combination of a colored layer and a pattern layer may be used.
- the patterns (patterns) of the pattern layer include wood grain patterns such as annual rings and conduit grooves on the surface of wood boards, stone grain patterns on the surface of stone boards such as marble and granite, texture patterns on the surface of fabrics, grain patterns on the surface of leather, and geometric patterns. Patterns, letters, graphics, or combinations of these may be used.
- the ink used for the decorative layer is a resin composition obtained by appropriately mixing a resin component with coloring agents such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers, etc. things are used.
- coloring agents such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers, etc. things are used.
- Resins constituting the decorative layer include, for example, urethane resins, acrylic polyol resins, acrylic resins, polyesters, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, and vinyl chloride.
- -vinyl acetate-acrylic copolymer chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin.
- various types of resins can be used, such as a one-pack curable resin and a two-pack curable resin with a curing agent such as an isocyanate compound.
- the colorant pigments with excellent hiding properties and weather resistance are preferred. Pigments similar to those exemplified for the base material layer can be used.
- the content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the resin constituting the decorative layer. More preferred are:
- the decorative layer may contain additives such as UV absorbers and weathering agents such as light stabilizers.
- the ultraviolet absorber that can be used in the decorative layer is the same as the ultraviolet absorber that can be used in the surface protective layer, and is preferably a hydroxyphenyltriazine-based ultraviolet absorber as in the surface protective layer.
- the light stabilizer that can be used in the transparent resin layer is the same as the light stabilizer that can be used in the substrate layer.
- the content of the ultraviolet absorber is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and even more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the resin of the decorative layer.
- the content of the ultraviolet absorber is within the above range, weather resistance can be efficiently obtained.
- the thickness of the decorative layer may be appropriately selected according to the desired pattern, but from the viewpoint of concealing the background color of the adherend and improving the design, it is preferably 0.5 ⁇ m or more and 20 ⁇ m or less, more preferably 0.5 ⁇ m or more and 20 ⁇ m or less. is 1 ⁇ m or more and 10 ⁇ m or less, more preferably 2 ⁇ m or more and 5 ⁇ m or less.
- the decorative sheet of the present embodiment has the transparent resin layer, it is preferable to form an adhesive layer between the substrate layer and the transparent resin layer in order to improve adhesion between the two layers.
- the decorative sheet further has a decorative layer between the base material layer and the transparent resin layer
- the positional relationship between the adhesive layer and the decorative layer is not particularly limited, and the decorative sheet is positioned close to the base material layer, for example.
- the decorative layer, the adhesive layer, and the transparent resin layer may be provided in this order from the bottom, or the adhesive layer, the decorative layer, and the transparent resin layer may be provided in this order from the side closer to the base material layer.
- the adhesive layer may be, for example, an adhesive layer.
- the adhesive layer can be composed of, for example, a general-purpose adhesive such as a urethane-based adhesive, an acrylic adhesive, an epoxy-based adhesive, or a rubber-based adhesive. Among these adhesives, urethane-based adhesives are preferable in terms of adhesive strength.
- urethane-based adhesives include adhesives using two-liquid curing urethane resins containing various polyol compounds such as polyether polyols, polyester polyols and acrylic polyols, and curing agents such as isocyanate compounds.
- the thickness of the adhesive layer is preferably 0.1 ⁇ m or more and 30 ⁇ m or less, more preferably 1 ⁇ m or more and 15 ⁇ m or less, and still more preferably 2 ⁇ m or more and 10 ⁇ m or less, from the viewpoint of efficiently obtaining the desired adhesive strength.
- the decorative sheet shown in FIG. It can be manufactured by a manufacturing method having, in order, a forming step and a surface protective layer forming step of providing a surface protective layer.
- the adhesive layer forming step may be performed, for example, after the decorative layer forming step and before the transparent resin layer forming step.
- the resin composition for forming each layer (the adhesive layer is an adhesive) is applied by a gravure printing method, a bar coating method, a roll It can be formed by coating by a known method such as a coating method, a reverse roll coating method, a comma coating method, etc., and drying and curing as necessary.
- the surface protective layer is taken as an example.
- the resin component contained in the resin composition for forming a surface protective layer is a thermosetting resin
- the surface protective layer can be formed by heating and curing under heating conditions according to the type of the thermosetting resin. can.
- the irradiation dose of ionizing radiation is preferably an amount that saturates the crosslink density of the resin layer, and is usually 5 to 300 kGy (0. 5 to 30 Mrad), preferably 10 to 200 kGy (1 to 20 Mrad).
- the electron beam source is not particularly limited, and examples include various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. can be used.
- ultraviolet rays When using ultraviolet rays as ionizing radiation, light containing ultraviolet rays with a wavelength of 190 to 380 nm is irradiated.
- the ultraviolet light source There are no particular restrictions on the ultraviolet light source, and for example, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps can be used.
- the transparent resin layer can be formed by heat-melt extruding a resin composition that forms the transparent resin layer, or by laminating resin sheets that form the transparent resin layer by dry lamination. .
- a transparent resin layer is formed on the laminate having the substrate layer, the decorative layer, and the adhesive layer.
- a layered product is laminated by hot melt extrusion, or a laminate having a base material layer, a decorative layer and an adhesive layer and a resin sheet forming a transparent resin layer are dry-laminated to form a base material layer.
- a decorative layer, an adhesive layer and a transparent resin layer are dry-laminated to form a base material layer.
- the resin composition for forming a primer layer is applied onto the transparent resin layer, and cured if necessary to form a primer layer.
- a decorative sheet having a decorative layer, an adhesive layer, a transparent resin layer, a primer layer and a surface protective layer on the base layer can be obtained by curing with to form the surface protective layer.
- the decorative sheet of the present embodiment may be provided (also referred to as shaping) with a desired uneven shape (also referred to as an uneven pattern) by embossing or the like.
- embossing for example, the decorative sheet is preferably heated to 80° C. or higher and 260° C. or lower, more preferably 85° C. or higher and 200° C. or lower, still more preferably 100° C. or higher and 180° C. or lower, and an embossing plate is pressed onto the decorative sheet. embossing can be performed.
- the portion where the embossing plate is pressed is preferably on the side of the surface protective layer of the decorative sheet.
- the decorative member of the present embodiment includes an adherend and the above-described decorative sheet of the present embodiment. Specifically, the surface of the adherend requiring decoration and the base layer side surface of the decorative sheet are laminated facing each other.
- adherend examples include plate materials such as flat plates and curved plates made of various materials described later; three-dimensional articles such as cylinders and polygonal columns made of various materials described later; and sheets and films made of various materials described later. .
- wood veneers made of various types of wood such as cedar, cypress, pine, and lauan, wood plywood, laminated lumber, particle board, wood members such as wood fiber boards such as MDF (medium density fiber board); Metal members such as iron, aluminum, copper, or alloys containing one or more of these metals; glass, ceramics such as ceramics, gypsum, cement, ALC (light cellular concrete), non-ceramic ceramic materials such as calcium silicate, etc.
- ceramic members such as polyolefin resins such as acrylic resins, polyesters, polystyrenes and polypropylenes, ABS (acrylonitrile-butadiene-styrene copolymer) resins, phenolic resins, vinyl chloride resins, cellulose resins, and resin members such as rubbers. These materials can be used singly or in combination.
- the adherend may be appropriately selected from the above depending on the application.
- interior or exterior members of buildings such as walls, ceilings, floors, window frames, doors, handrails, baseboards, curbs, malls, etc.
- wooden members, metal members and a resin member is preferably used as the adherend.
- the adherend is preferably made of at least one member selected from metal members and resin members.
- the thickness of the adherend may be appropriately selected according to the application and material, preferably 0.1 mm or more and 100 mm or less, more preferably 0.3 mm or more and 5 mm or less, and even more preferably 0.5 mm or more and 3 mm or less.
- the adherend and the decorative sheet are preferably attached via an adhesive layer in order to obtain excellent adhesiveness. That is, the decorative member may have an adhesive layer between the adherend and the decorative sheet.
- Specific-purpose heat-sensitive adhesives, pressure-sensitive adhesives, etc. can be used as the adhesive that constitutes the adhesive layer.
- adhesives constituting the adhesive layer include resins such as acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyesters, and polyamides. Those containing one selected or two or more are included.
- Examples of the adhesive constituting the adhesive layer include a two-liquid curing type polyurethane adhesive and a polyester adhesive using an isocyanate compound or the like as a curing agent.
- the thickness of the adhesive layer is not particularly limited, it is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 5 ⁇ m or more and 50 ⁇ m or less, and still more preferably 10 ⁇ m or more and 30 ⁇ m or less, from the viewpoint of efficiently obtaining excellent adhesiveness.
- the decorative member can be manufactured through a process of laminating a decorative sheet and an adherend.
- This step is a step of laminating the adherend and the decorative sheet of the present disclosure, in which the surface of the adherend requiring decoration faces the base layer side surface of the decorative sheet.
- a lamination method in which the decorative sheet is laminated on the plate-shaped adherend by pressing with a pressure roller via an adhesive layer.
- the heating temperature is preferably 160° C. or higher and 200° C. or lower, although it depends on the type of resin that constitutes the adhesive. °C or higher and 130 °C or lower. Moreover, in the case of vacuum forming, it is common to carry out while heating, and the temperature is preferably 80° C. or higher and 130° C. or lower, more preferably 90° C. or higher and 120° C. or lower.
- the decorative member obtained as described above can be arbitrarily cut, and arbitrary decorations such as grooving and chamfering can be applied to the surface and the butt end using a cutting machine such as a router or cutter.
- a cutting machine such as a router or cutter.
- various uses for example, interior members of buildings such as walls, ceilings and floors; In addition to fittings or fixtures such as malls, it can be used for kitchens, furniture or home appliances, surface decorative boards for cabinets such as OA equipment, interior members for vehicles, exterior members, and the like.
- the present disclosure relates to, for example, the following [1] to [10].
- [1] It has a substrate layer and a surface protective layer, the surface protective layer contains a resin, an ultraviolet absorber and particles, and the indentation depth measured in accordance with the Erichsen test method specified in JIS Z2247:2006.
- a decorative sheet having a length of 4.0 mm or more.
- [2] The decorative sheet according to [1] above, wherein the substrate layer contains a polyolefin resin.
- [3] The decorative sheet according to [1] or [2] above, wherein the substrate layer has a thickness of 40 ⁇ m or more and 100 ⁇ m or less.
- R 11 is a single bond or a divalent organic group
- the ultraviolet absorber includes a hydroxyphenyltriazine compound A represented by the following chemical formula (2) and a hydroxyphenyltriazine compound B represented by the following chemical formula (3) Described cosmetic sheet.
- the ultraviolet absorber includes a hydroxyphenyltriazine compound A represented by the following chemical formula (2) and a hydroxyphenyltriazine compound C represented by the following chemical formula (4).
- Described cosmetic sheet [9] Any one of the above [1] to [8], having one or more layers selected from a decorative layer, an adhesive layer, a transparent resin layer and a primer layer between the substrate layer and the surface protective layer.
- Described cosmetic sheet [10] A decorative member comprising an adherend and the decorative sheet according to any one of [1] to [9] above.
- the decorative sheet was taken out, and after wiping off the white marker in a flat state, the surface of the surface protective layer was observed with a microscope (optical microscope, 500x), and the distance traveled by the punch when microcracks occurred was measured. (mm). If the surface protective layer is cracked, the presence or absence of the crack can be confirmed because the white marker remains only in the cracked portion.
- the decorative sheet obtained in each example and comparative example was measured using a sunshine weather meter ("WEL-300", manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ° C. for 120 minutes (18 minutes rainfall in 120 minutes). ) was left for 4000 hours under the conditions of one cycle.
- the surface of the decorative sheet on the surface protective layer side was measured using a gloss meter ("Microgloss (model name)", manufactured by BYK Gardner) in accordance with JIS K 5600-4-7: 1999. Then, the 60° gloss value was measured.
- 1 The rate of change in gloss value before and after the weather resistance test was less than 20%.
- the rate of change in gloss value before and after the weather resistance test was 20% or more and less than 40%.
- the rate of change in gloss value before and after the weather resistance test was 40% or more.
- the base layer side surface of the decorative sheet was attached to the surface of a flat aluminum plate (thickness: 0.5 mm) via a two-liquid curing urethane adhesive.
- the coating amount of the two-liquid curing urethane adhesive was set to 20 g/m 2 .
- the obtained test piece is bent at a bending angle of 1 mmR using a bending tester, and the bent portion (bending angle: 1 mmR) is visually observed or observed with a microscope (optical microscope, 500 times).
- the occurrence of cracks was evaluated according to the following criteria. 1 and 2 pass. 1: No scratches or cracks were observed even with a microscope. 2: No scratches or cracks were visually observed, but very slight scratches or cracks were confirmed by observation with a microscope. 3: Scratches and cracks were visually observed.
- Example 1 A polypropylene resin sheet having a thickness of 60 ⁇ m and having both sides subjected to corona discharge treatment was prepared as a base layer.
- an adhesive layer having a thickness of 3 ⁇ m was formed on the decorative layer using a urethane resin-based adhesive.
- a transparent polypropylene resin composition containing 0.12 parts by mass of a hydroxyphenyltriazine-based ultraviolet absorber (trade name: TINUVIN400, BASF) based on 100 parts by mass of polypropylene resin was prepared.
- a transparent polypropylene resin composition was heat-melt extruded on the adhesive layer by a T-die extruder to form a transparent resin layer having a thickness of 80 ⁇ m.
- the following resin composition for forming a primer layer was applied and dried to form a primer layer having a thickness of 4 ⁇ m, and further a primer layer for forming a surface protective layer described below.
- a surface protective layer having a thickness of 5 ⁇ m was formed by coating the composition and irradiating it with an electron beam to crosslink and cure the composition for forming a surface protective layer.
- the decorative sheet of Example 1 was obtained. The obtained decorative sheet was evaluated as described above. Table 1 shows the results.
- Resin composition for forming surface protective layer ⁇ Ionizing radiation curable resin: 100 parts by mass (bifunctional urethane acrylate oligomer, weight average molecular weight: 4,000) ⁇ Filler: 20 parts by mass (silica particles, average particle size: 5 ⁇ m) ⁇ Hydroxyphenyltriazine-based UV absorber: 3 parts by mass (trade name: TINUVIN479, BASF) - Light stabilizer: 3 parts by mass (trade name: TINUVIN123, BASF)
- Example 2 A decorative sheet was prepared in the same manner as in Example 1, except that the ionizing radiation-curable resin in the resin composition for forming a surface protective layer was changed to a bifunctional urethane acrylate oligomer (weight average molecular weight: 2,000). made. The obtained decorative sheet was evaluated as described above. Table 1 shows the results.
- Example 3 A decorative sheet was prepared in the same manner as in Example 1, except that the ionizing radiation-curable resin in the resin composition for forming a surface protective layer was changed to a trifunctional urethane acrylate oligomer (weight average molecular weight: 2,000). made. The obtained decorative sheet was evaluated as described above. Table 1 shows the results.
- Example 4 A decorative sheet was produced in the same manner as in Example 1, except that the amount of the filler in the resin composition for forming a surface protective layer was changed to 30 parts by mass. The obtained decorative sheet was evaluated as described above. Table 1 shows the results.
- Example 5 A decorative sheet was produced in the same manner as in Example 4, except that the ultraviolet absorber in the resin composition for forming a surface protective layer was changed as follows. The obtained decorative sheet was evaluated as described above. Table 1 shows the results. - First ultraviolet absorber 0.5 parts by mass hydroxyphenyltriazine-based ultraviolet absorber, Product name: ADEKA STAB LA-46, ADEKA, Absorption peak wavelength: 275 nm - Second UV absorber 3 parts by mass Hydroxyphenyltriazine-based UV absorber, Product name: TINUVIN479, BASF Corporation, Absorption peak wavelength: 322 nm - Third ultraviolet absorber 0.5 parts by mass hydroxyphenyltriazine-based ultraviolet absorber, Product name: TINUVIN477, BASF Corporation, Absorption peak wavelength: 356 nm
- Example 1 A decorative sheet was prepared in the same manner as in Example 1, except that the ionizing radiation-curable resin in the resin composition for forming a surface protective layer was changed to a bifunctional urethane acrylate oligomer (weight average molecular weight: 1,000). made. The obtained decorative sheet was evaluated as described above. Table 1 shows the results.
- Example 2 In Example 1, the ionizing radiation-curable resin in the resin composition for forming the surface protective layer was replaced by a thermosetting resin (an isocyanate-curable acrylic resin composition (polyisocyanate A decorative sheet was produced in the same manner as in Example 1, except that the amount added: 10 parts by weight with respect to the main agent (acrylic polyol resin)). The number of functional groups and weight average molecular weight shown in Table 1. Values for acrylic polyol resins. The obtained decorative sheet was evaluated as described above. Table 1 shows the results.
- the decorative sheets of Examples 1 to 5 have indentation depths of 7 mm, 5 mm, 6 mm, and 4 mm or more, respectively, and are excellent in both the evaluation of scratches and cracks and the evaluation of appearance. was confirmed. It can be seen that the decorative sheets of Examples 1 to 5 are less likely to be scratched or cracked, and thus are excellent in suppressing bleeding out and excellent in long-term weather resistance.
- the indentation depth was 3 mm, which was less than 4 mm.
- the decorative sheets of Comparative Examples 1 and 2 are prone to bleed-out due to the occurrence of scratches and cracks, resulting in a decrease in long-term weather resistance.
- the decorative sheet of the present disclosure is not limited by the description of the above examples, and the above examples and specification are merely for explaining the principles of the present disclosure. Various modifications or improvements may be made without departing from the spirit and scope, and all such modifications or improvements are included within the scope of the claimed disclosure. Moreover, what is claimed by this disclosure includes not only the recitation of the claims, but also their equivalents.
- the decorative sheet of the present disclosure can suppress bleed-out and deterioration of long-term weather resistance, as well as suppress deterioration of appearance. Therefore, the decorative sheet of the present disclosure is suitably used as a decorative sheet for members used in an environment exposed to direct sunlight, such as exterior members such as entrance doors, and fittings such as window frames and doors.
- Decorative sheet 10 Surface protective layer 20: Primer layer 30: Transparent resin layer 40: Adhesive layer 50: Decorative layer 51: Colored layer 52: Pattern layer 60: Base material layer
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Abstract
Description
1.基材層及び表面保護層を有し、表面保護層が樹脂、紫外線吸収剤及び粒子を含み、JIS Z2247:2006に規定されるエリクセン試験方法に準拠して測定される押込み深さが4.0mm以上である化粧シート。
2.被着材と上記1に記載の化粧シートとを有する化粧部材。
本実施形態の化粧シートは、基材層及び表面保護層を有し、表面保護層が樹脂、紫外線吸収剤及び粒子を含有し、JIS Z2247:2006に規定されるエリクセン試験方法に準拠して測定される押込み深さ(以下、単に「押込み深さ」と称することがある。)が4.0mm以上であることを特徴とする。
(i)化粧シートを上記の建築物の内装部材や外装部材等の表面を装飾して化粧部材を得るために場合、その加工工程(例えば、被着材へのラッピング加工、真空成型、Vカット加工等の各種加工工程)、すなわち化粧シートを被着材に積層させる工程において、外力をもって積層させるため、化粧シートの表面に傷や割れが生じる場合がある。
上記(i)のような加工工程だけでなく、加工して化粧部材を得た後にも、
(ii)被着材の材質として金属等の硬い部材を用いる場合、化粧部材を保管する際に、化粧部材同士の接触により化粧シートに傷や割れが生じる場合がある。
(iii)化粧部材を特に外装部材として長期使用していると、砂、落ち葉等が触れることで、その表面に傷や割れが生じる場合がある。
本実施形態の化粧シートは、化粧シートを試験片としてエリクセン試験を行い測定される押込み深さが、4.0mm以上であることを要する。4.0mm未満であると、上記(i)~(iii)のような状況下において傷や割れが生じやすく、結果としてブリードアウトと長期耐候性の低下とが進行し、外観の低下も進行することとなる。
図1は、本実施形態の化粧シート100の代表的な一実施の形態を示す断面図であり、図2は、本実施形態の化粧シート100の好ましい一実施の形態を示す断面図である。図1及び図2において、Z軸方向は厚さ方向を示し、X軸及びY軸から形成される面は化粧部材をZ軸方向から観察した平面を示す。
(2)基材層60/表面保護層10
(3)基材層60/プライマー層20/表面保護層10
(4)基材層60/接着層40/透明性樹脂層30/表面保護層10
(5)基材層60/装飾層50/表面保護層10
(6)基材層60/接着層40/透明性樹脂層30/装飾層50/表面保護層10
(7)基材層60/接着層40/透明性樹脂層30/装飾層50/プライマー層20/表面保護層10
基材層は、本実施形態の化粧シートが有する表面保護層の支持体として機能する層であり、化粧部材の装飾に用いる際には被着材との接着のしやすさにも寄与する層である。基材層としては、各種の紙類、プラスチック、金属、織布、不織布、木材及び窯業系素材等からなる、フィルム、シート及び板が挙げられる。
基材層を着色する場合、基材層中には、染料及び顔料等の着色剤を添加することができる。これら着色剤の中では、退色を抑制しやすい顔料が好ましい。顔料としては、例えば、亜鉛華、鉛白、リトポン、二酸化チタン(チタン白)、沈降性硫酸バリウム及びバライト等の白色顔料;カーボンブラック、アオメチンアゾ系黒顔料、ペリレン系黒顔料等の黒色顔料;鉛丹、酸化鉄赤、キナクリドンレッド、ポリアゾレッド等の赤色顔料;黄鉛、亜鉛黄(亜鉛黄1種、亜鉛黄2種)、イソインドリノンイエロー、ニッケル-アゾ錯体等の黄色顔料;ウルトラマリン青、プロシア青(フェロシアン化鉄カリ)等の青色顔料が挙げられる。
基材層は、化粧シートの他の層や被着材との密着性を高めるために、基材層の片面又は両面に、酸化法、凹凸化法等の物理的表面処理、又は化学的表面処理等の表面処理を施したり、プライマー層を形成したりしてもよい。
紫外線吸収剤としては、例えば、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤、ヒドロキシフェニルトリアジン系紫外線吸収剤が挙げられる。これらの中でも、ヒドロキシフェニルトリアジン系紫外線吸収剤が好ましい。基材層において好ましく用いられるヒドロキシフェニルトリアジン系紫外線については、後述する。本実施形態においては、紫外線吸収剤は一種単独で用いてもよいし、複数種を組み合わせて用いてもよい。
表面保護層は、樹脂及び紫外線吸収剤を含有し、本実施形態の化粧シートの表面を保護するための層である。表面保護層は、特に傷や割れ(亀裂)の発生を抑制する観点から、少なくとも耐擦傷性が求められ、また耐候性、耐汚染性等の表面特性も求められる層である。
以下、表面保護層を形成する樹脂成分について、より詳細に説明する。
既述のように、樹脂成分としては、表面特性、特に耐擦傷性の向上の観点から、硬化性樹脂が好ましく、中でも熱硬化性樹脂、電離放射線硬化性樹脂が好ましい。さらに、押込み深さの調整のしやすさ、押込み深さを調整することで、ブリードアウトと長期耐候性の低下とを抑制し、かつ外観の低下を抑制し得ることを考慮すると、電離放射線硬化性樹脂がより好ましい。
電離放射線硬化性樹脂は、電離放射線の照射によって架橋硬化する基(以下、「電離放射線硬化性官能基」と称することがある。)を有する樹脂のことであり、電離放射線の照射により架橋硬化する樹脂のことである。電離放射線硬化性樹脂を樹脂成分として含有する樹脂組成物は、電離放射線の照射により架橋硬化する樹脂組成物であり、電離放射線硬化性樹脂組成物とも称し得る。
また、シクロヘキシル(メタ)アクリレートオリゴマーを用いることもできる。
押込み深さの調整のしやすさ、耐擦傷性、耐候性、耐汚染性等の表面特性の向上を考慮すると、ウレタン(メタ)アクリレートオリゴマー、エポキシ(メタ)アクリレートオリゴマー、ポリエステル(メタ)アクリレートオリゴマー、ポリエーテル(メタ)アクリレートオリゴマー、ポリカーボネート(メタ)アクリレートオリゴマー、アクリル(メタ)アクリレートオリゴマーが好ましく、ウレタン(メタ)アクリレートオリゴマー、ポリカーボネート(メタ)アクリレートオリゴマーがより好ましく、ウレタン(メタ)アクリレートオリゴマーが更に好ましい。
熱硬化性樹脂は、加熱することにより硬化する樹脂のことであり、樹脂成分として熱硬化性樹脂を含有する樹脂組成物は、加熱することにより硬化する熱硬化性樹脂組成物とも称し得る。
表面保護層は、長期耐候性の向上の観点から、紫外線吸収剤を含有することが好ましい、すなわち、表面保護層形成用樹脂組成物は、紫外線吸収剤を含有することが好ましい。
表面保護層形成用樹脂組成物は、上記樹脂成分及び紫外線吸収剤の他、例えば、光安定剤等の耐候剤、充填剤等の粒子、酸化防止剤、紫外線遮蔽剤、重合禁止剤、架橋剤、赤外線吸収剤、帯電防止剤、接着性向上剤、レベリング剤、カップリング剤、可塑剤、消泡剤、ブロッキング防止剤、滑剤、溶剤等の添加剤を含有してもよい。表面保護層は、上記樹脂及び紫外線吸収剤の他、上記添加剤を含有してもよい。
本開示において、平均粒子径は、化粧シートの厚さ方向の断面を走査型電子顕微鏡(SEM)で観察し、無作為に選択した100個の粒子の非凝集体について測定した粒子径の平均値(算術(個数)平均径)を意味する。上記粒子径は、粒子の長軸径とする。
既述のように、本実施形態の化粧シートは、基材層及び表面保護層の他、プライマー層、透明性樹脂層、装飾層、また接着層等のその他の層を有し得る。以下、本実施形態の化粧シートが好ましく有し得る、これらのその他の層について説明する。
本実施形態の化粧シートは、表面保護層の基材層側の面に接してプライマー層を有することが好ましい。化粧シートがプライマー層を有することにより、基材層と表面保護層との密着性、また化粧シートが後述する透明性樹脂層を有する場合は、透明性樹脂層と表面保護層との密着性、が向上する。
プライマー層を構成する樹脂としては、例えば、ウレタン樹脂、アクリルポリオール樹脂、アクリル樹脂、エステル樹脂、アミド樹脂、ブチラール樹脂、スチレン樹脂、ウレタン-アクリル共重合体、ポリカーボネート系ウレタン-アクリル共重合体(ポリマー主鎖にカーボネート結合を有し、末端、側鎖に2個以上の水酸基を有する重合体(ポリカーボネートポリオール)由来のウレタン-アクリル共重合体)、塩化ビニル-酢酸ビニル共重合体樹脂、塩化ビニル-酢酸ビニル-アクリル共重合体樹脂、塩素化プロピレン樹脂、ニトロセルロース樹脂(硝化綿)、酢酸セルロース樹脂等の樹脂成分が好ましく挙げられ、これらを単独で、又は複数種を組み合わせて用いることができる。
本実施形態の化粧シートは、強度を高めるなどの観点から、基材層と表面保護層との間に透明性樹脂層を有してもよい。化粧シートが透明性樹脂層を有することにより、化粧シートの押込み深さの調整がしやすくなる。
本実施形態の化粧シートは、意匠性を向上させる観点から、化粧シートの任意の箇所に装飾層を有することが好ましい。装飾層を形成する箇所は、装飾層を保護する観点から、基材層に近い側であることが好ましい。例えば、化粧シートがプライマー層を有する場合、装飾層は、基材層とプライマー層との間に位置することが好ましい。また、化粧シートが透明性樹脂層を有する場合、装飾層は、基材層と透明性樹脂層との間に位置することが好ましい。
装飾層に用い得る紫外線吸収剤は、上記表面保護層に用い得る紫外線吸収剤と同様であり、表面保護層と同様に、ヒドロキシフェニルトリアジン系紫外線吸収剤が好ましい。透明性樹脂層に用い得る光安定剤は、上記基材層に用いられ得るものとして例示した光安定剤と同様である。
本実施形態の化粧シートが上記透明性樹脂層を有する場合、基材層と透明性樹脂層との間には、両層の密着性を向上するために接着層を形成することが好ましい。
本実施形態の化粧シートの製造方法について、図2に示される、基材層60上に、装飾層50、接着層40、透明性樹脂層30、プライマー層20及び表面保護層10を有する化粧シートを例にとって説明する。
表面保護層形成用樹脂組成物に含まれる樹脂成分が熱硬化性樹脂である場合は、熱硬化性樹脂の種類に応じた加熱条件で加熱して硬化させて、表面保護層を形成することができる。
本実施形態の化粧部材は、被着材と上記の本実施形態の化粧シートとを有し、具体的には、被着材の装飾を要する面と、化粧シートの基材層側の面とを対向させて積層したものである。
被着材としては、例えば、後述する各種素材からなる平板、曲面板等の板材;後述する各種素材からなる円柱、多角柱等の立体形状物品;後述する各種素材からなるシート、フィルムが挙げられる。
被着材と化粧シートとは、優れた接着性を得るため、接着剤層を介して貼着されることが好ましい。すなわち化粧部材は、被着材と化粧シートとの間に、接着剤層を有してもよい。
化粧部材は、化粧シートと被着材とを積層する工程を経て製造することができる。
本工程は、被着材と、本開示の化粧シートとを積層する工程であり、被着材の装飾を要する面と、化粧シートの基材層側の面とを対向させて積層する。被着材と化粧シートとを積層する方法としては、例えば、接着剤層を介して化粧シートを板状の被着材に加圧ローラーで加圧して積層するラミネート方法が挙げられる。
[1]基材層及び表面保護層を有し、表面保護層が、樹脂、紫外線吸収剤及び粒子を含有し、JIS Z2247:2006に規定されるエリクセン試験方法に準拠して測定される押込み深さが、4.0mm以上である、化粧シート。
[2]基材層が、ポリオレフィン樹脂を含有する、上記[1]に記載の化粧シート。
[3]基材層の厚さが、40μm以上100μm以下である、上記[1]又は[2]に記載の化粧シート。
[4]表面保護層における上記樹脂が、官能基数2以上の電離放射線硬化性樹脂の硬化樹脂を含む、上記[1]~[3]のいずれかに記載の化粧シート。
[5]表面保護層における上記樹脂が、重量平均分子量が1,100以上7,500以下の電離放射線硬化性樹脂の硬化樹脂を含む、上記[1]~[4]のいずれかに記載の化粧シート。
[6]紫外線吸収剤が、一般式(1)で示されるヒドロキシフェニルトリアジン化合物である、上記[1]~[5]のいずれかに記載の化粧シート。
[7]紫外線吸収剤が、下記化学式(2)で示されるヒドロキシフェニルトリアジン化合物A及び下記化学式(3)で示されるヒドロキシフェニルトリアジン化合物Bを含む、上記[1]~[6]のいずれかに記載の化粧シート。
[10]被着材と、上記[1]~[9]のいずれかに記載の化粧シートと、を有する化粧部材。
(押込み深さの測定)
各実施例及び比較例で得られた化粧シート(寸法:100mm×100mm)について、エリクセン試験機(東洋精機製)を用いて球状のパンチ(直径:20mm)を基材層側から、移動速度12mm/minで、一定の押込み深さで押し込んだ。その状態で、表面保護層に白マーカーを塗布した。その後化粧シートを取り出し、平らな状態で白マーカーをふき取った後、マイクロスコープ(光学顕微鏡、500倍)で表面保護層の表面を観察し、微細割れの発生した際のパンチの移動距離を押し込み深さ(mm)とした。表面保護層に割れが発生していると、当該割れている部分にのみ白マーカーが残るため、割れの発生の有無を確認できる。
各実施例及び比較例で得られた化粧シートについて、サンシャインウェザーメーター(「WEL-300」、スガ試験機株式会社製)を用いて、ブラックパネル温度63℃、120分(120分中18分降雨)を1サイクルとする条件下で4000時間放置する耐候試験を行った。耐候試験の前及び後に、化粧シートの表面保護層側の面について、グロスメータ(「マイクログロス(機種名)」、BYKガードナー社製)を用いて、JIS K 5600-4-7:1999に準拠して60°グロス値を測定した。
1:耐候試験前後のグロス値の変化率が20%未満であった。
2:耐候試験前後のグロス値の変化率が20%以上40%未満であった。
3:耐候試験前後のグロス値の変化率が40%以上であった。
平らなアルミニウム板(厚さ:0.5mm)の表面に、2液硬化型ウレタン系接着剤を介して化粧シートの基材層側の面を貼り合わせた。2液硬化型ウレタン系接着剤の塗布量は、20g/m2とした。得られた試験片を曲げ試験機を用いて曲げ角度:1mmRで曲げて、その曲げ部分(曲げ角度:1mmR)を目視、又はマイクロスコープ(光学顕微鏡、500倍)で観察したときの、傷や割れの発生状況について、以下の基準で評価した。1及び2であれば合格である。
1:マイクロスコープを用いても、傷や割れは全く確認されなかった。
2:目視にて傷や割れは確認されなかったが、マイクロスコープを用いて観察したところ、極わずかな傷や割れが確認された。
3:目視にて傷や割れが確認された。
各実施例及び比較例で得られた化粧シートについて、表面保護層側の面を、100g/m2の荷重でスチールウール(「ボンスター#0000」、日本スチールウール社製)を20往復させて、ラビング試験を行った。ラビング試験の前及び後に、グロスメータ(「マイクログロス(機種名)」、BYKガードナー社製)を用いて、JIS K 5600-4-7:1999に準拠して60°グロス値を測定した。ラビング試験前のグロス値をG0、ラビング試験後のグロス値をG1とし、ラビング試験前後のグロス値の変化率(G0-G1)/G0(%)を算出した。1及び2であれば合格である。
1:グロス値の変化率が10%未満であった。
2:グロス値の変化率が10%以上20%未満であった。
3:グロス値の変化率が20%以上であった。
両面コロナ放電処理を施した厚さ60μmのポリプロピレン樹脂シートを基材層として準備した。基材層の一方の面に、樹脂成分である2液硬化型アクリル-ウレタン樹脂100質量部に対して、着色剤を30質量部含有する印刷インキを、グラビア印刷法で塗布して、木目模様の厚さ3μmの装飾層を設けた。次いで、装飾層上に、ウレタン樹脂系接着剤を用いて厚さ3μmの接着層を形成した。
以上のようにして、実施例1の化粧シートを得た。
得られた化粧シートについて、上記評価を行った。その結果を表1に示す。
・(主剤)ポリカーボネート系ウレタン-アクリル共重合体及びアクリルポリオール樹脂を含有する組成物: 100質量部
・(硬化剤)ヘキサメチレンジイソシアネート: 5質量部
・電離放射線硬化性樹脂: 100質量部
(2官能ウレタンアクリレートオリゴマー、重量平均分子量:4,000)
・充填剤: 20質量部
(シリカ粒子、平均粒子径:5μm)
・ヒドロキシフェニルトリアジン系紫外線吸収剤: 3質量部
(商品名:TINUVIN479、BASF社)
・光安定剤: 3質量部
(商品名:TINUVIN123、BASF社)
実施例1において、表面保護層形成用樹脂組成物における電離放射線硬化性樹脂を、2官能ウレタンアクリレートオリゴマー(重量平均分子量:2,000)に変更した以外は実施例1と同様にして化粧シートを作製した。得られた化粧シートについて、上記評価を行った。その結果を表1に示す。
実施例1において、表面保護層形成用樹脂組成物における電離放射線硬化性樹脂を、3官能ウレタンアクリレートオリゴマー(重量平均分子量:2,000)に変更した以外は実施例1と同様にして化粧シートを作製した。得られた化粧シートについて、上記評価を行った。その結果を表1に示す。
実施例1において、表面保護層形成用樹脂組成物における充填剤の配合量を30質量部に変更した以外は実施例1と同様にして化粧シートを作製した。得られた化粧シートについて、上記評価を行った。その結果を表1に示す。
実施例4において、表面保護層形成用樹脂組成物における紫外線吸収剤を以下のとおり変更した以外は実施例4と同様にして化粧シートを作製した。得られた化粧シートについて、上記評価を行った。その結果を表1に示す。
・第1の紫外線吸収剤 0.5質量部
ヒドロキシフェニルトリアジン系紫外線吸収剤、
商品名:アデカスタブLA-46、ADEKA社、
吸収ピークの波長:275nm
・第2の紫外線吸収剤 3質量部
ヒドロキシフェニルトリアジン系紫外線吸収剤、
商品名:TINUVIN479、BASF社、
吸収ピークの波長:322nm
・第3の紫外線吸収剤 0.5質量部
ヒドロキシフェニルトリアジン系紫外線吸収剤、
商品名:TINUVIN477、BASF社、
吸収ピークの波長:356nm
実施例1において、表面保護層形成用樹脂組成物における電離放射線硬化性樹脂を、2官能ウレタンアクリレートオリゴマー(重量平均分子量:1,000)に変更した以外は実施例1と同様にして化粧シートを作製した。得られた化粧シートについて、上記評価を行った。その結果を表1に示す。
実施例1において、表面保護層形成用樹脂組成物における電離放射線硬化性樹脂を、熱硬化性樹脂(アクリルポリオール樹脂を主剤、ポリイソシアネートを硬化剤としたイソシアネート硬化型アクリル系樹脂組成物(ポリイソシアネート添加量:主剤(アクリルポリオール樹脂)に対して10重量部))とした以外は実施例1と同様にして化粧シートを作製した。表1に記載の官能基数及び重量平均分子量は。アクリルポリオール樹脂についての値である。得られた化粧シートについて、上記評価を行った。その結果を表1に示す。
10:表面保護層
20:プライマー層
30:透明性樹脂層
40:接着層
50:装飾層
51:着色層
52:絵柄層
60:基材層
Claims (10)
- 基材層及び表面保護層を有し、
前記表面保護層が、樹脂、紫外線吸収剤及び粒子を含有し、
JIS Z2247:2006に規定されるエリクセン試験方法に準拠して測定される押込み深さが、4.0mm以上である、
化粧シート。 - 前記基材層が、ポリオレフィン樹脂を含有する、請求項1に記載の化粧シート。
- 前記基材層の厚さが、40μm以上100μm以下である、請求項1又は2に記載の化粧シート。
- 前記表面保護層における前記樹脂が、官能基数2以上の電離放射線硬化性樹脂の硬化樹脂を含む、請求項1~3のいずれか1項に記載の化粧シート。
- 前記表面保護層における前記樹脂が、重量平均分子量が1,100以上7,500以下の電離放射線硬化性樹脂の硬化樹脂を含む、請求項1~4のいずれか1項に記載の化粧シート。
- 前記基材層と前記表面保護層との間に、装飾層、接着層、透明性樹脂層及びプライマー層から選ばれる一以上の層を有する、請求項1~8のいずれか1項に記載の化粧シート。
- 被着材と、
請求項1~9のいずれかに記載の化粧シートと、
を有する化粧部材。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013056424A (ja) * | 2011-09-07 | 2013-03-28 | Toray Advanced Film Co Ltd | 成型用積層フィルム |
JP5196042B2 (ja) | 2005-03-31 | 2013-05-15 | 大日本印刷株式会社 | 化粧シート |
JP2014069447A (ja) * | 2012-09-28 | 2014-04-21 | Dainippon Printing Co Ltd | 加飾シート、及び加飾樹脂成形品 |
JP5540589B2 (ja) | 2009-07-08 | 2014-07-02 | 株式会社トッパン・コスモ | 化粧シート |
JP2018051864A (ja) * | 2016-09-28 | 2018-04-05 | 大日本印刷株式会社 | 化粧シート及びこれを用いた成型品 |
JP2018167504A (ja) * | 2017-03-30 | 2018-11-01 | 凸版印刷株式会社 | 化粧シートおよびそれを用いた金属化粧部材および金属化粧板 |
JP2020055290A (ja) * | 2018-09-28 | 2020-04-09 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
WO2020203957A1 (ja) * | 2019-03-29 | 2020-10-08 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材、並びに表面保護層用樹脂組成物 |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5196042B2 (ja) | 2005-03-31 | 2013-05-15 | 大日本印刷株式会社 | 化粧シート |
JP5540589B2 (ja) | 2009-07-08 | 2014-07-02 | 株式会社トッパン・コスモ | 化粧シート |
JP2013056424A (ja) * | 2011-09-07 | 2013-03-28 | Toray Advanced Film Co Ltd | 成型用積層フィルム |
JP2014069447A (ja) * | 2012-09-28 | 2014-04-21 | Dainippon Printing Co Ltd | 加飾シート、及び加飾樹脂成形品 |
JP2018051864A (ja) * | 2016-09-28 | 2018-04-05 | 大日本印刷株式会社 | 化粧シート及びこれを用いた成型品 |
JP2018167504A (ja) * | 2017-03-30 | 2018-11-01 | 凸版印刷株式会社 | 化粧シートおよびそれを用いた金属化粧部材および金属化粧板 |
JP2020055290A (ja) * | 2018-09-28 | 2020-04-09 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
WO2020203957A1 (ja) * | 2019-03-29 | 2020-10-08 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材、並びに表面保護層用樹脂組成物 |
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