Transfer sheets, decorative materials, and exterior components

Abstract

The present invention provides a transfer sheet in which the surface protective layer of the decorative sheet transferred from the transfer sheet has excellent adhesion to the underlying layer, excellent surface hardness and scratch resistance, excellent processability, and after the transfer of the decorative sheet, the decorative sheet has excellent weather-resistant adhesion and weather resistance of the design. [Solution] A transfer sheet having at least a surface protective layer and a release film, wherein the surface protective layer contains a cross-linked curing resin. In the infrared spectroscopic measurement of the aforementioned surface protective layer, 855-1325 cm⁻¹ -1 Let A be the height of the peak that appears, between 1650 and 1800 cm. -1 When the peak height appearing is B, the peak height ratio of A to B ((A / B) × 100 (%)) is between 105% and 400%. In the infrared spectral measurement of the aforementioned surface protective layer, 3200-3500 cm⁻¹ -1 When the peak height appearing is C, the peak height ratio of B to C ((B / C) × 100 (%)) is between 1000% and 6000%. A transfer sheet characterized by the following features.

Description

[Technical Field]

[0001] This invention relates to transfer sheets, decorative materials, and exterior components. [Background technology]

[0002] Decorative sheets are used by being applied to the surface of wood panels, plastic panels, etc., for purposes such as surface protection and decoration. The resulting decorative materials are then used in a variety of applications, including decorative items, building materials, and furniture.

[0003] For decorative sheets used in the applications described above, the surface protective layer must adhere to the underlying layer. In particular, films with a small number of polar groups are sometimes used on the surface of the underlying layer, and the surface protective layer of the decorative sheet must also adhere to such films.

[0004] As a decorative sheet having a surface protective layer that adheres to the film, a hard-coat film has been proposed in which a hard-coat layer is provided on at least one side of the base film (see Patent Document 1).

[0005] However, the hard coat film with a hard coat layer described in Patent Document 1 does not exhibit sufficient adhesion between the base film and the hard coat film when used in various applications, and there is room for improvement.

[0006] Furthermore, since decorative sheets are used by being attached to the surface of wood panels, plastic panels, etc., they may be subjected to impacts. For this reason, the surface of the decorative sheet is required to have surface hardness and scratch resistance.

[0007] Furthermore, since decorative sheets are used by being attached to the surface of articles for decorative purposes, they need to conform to the shape of the article. For this reason, decorative sheets require processability that allows them to be processed to conform to the shape of the article. The hard coat film described in Patent Document 1 has the problem of poor processability because processability has not been considered.

[0008] Furthermore, in the field of building materials and other exterior components, decorative sheets are commonly used when it is desired to decorate the components being used. When decorative sheets are used in such fields, they are sometimes applied to the surface of existing components. In particular, in the case of exterior components, they may also be used on installed exterior components, so it may be necessary to apply the decorative sheet by transferring it using a transfer sheet in which the decorative sheet is formed on a release film.

[0009] As an example of such a transfer sheet, a transfer sheet has been proposed in which a transfer layer that can be peeled off from the support sheet is located on one side of the support sheet (see Patent Document 2).

[0010] While this type of transfer sheet is excellent, its adhesion to the layer beneath the surface protective layer has not been considered, and there is room for further improvement.

[0011] Furthermore, since exterior components are used outdoors, weather resistance is required. In other words, the transfer sheet used to apply decorative sheets to exterior components must maintain adhesion to the underlying layer of the decorative sheet's surface protective layer even after outdoor use following the transfer of the decorative sheet; that is, weather-resistant adhesion is required. Moreover, the transfer sheet used to apply decorative sheets to exterior components must suppress discoloration of the decorative sheet's surface protective layer and maintain its aesthetic appeal even after outdoor use following the transfer of the decorative sheet; that is, weather resistance of the design is required.

[0012] Therefore, there is a need for the development of a transfer sheet in which the surface protective layer of the decorative sheet transferred from the transfer sheet has excellent adhesion to the underlying layer, excellent surface hardness and scratch resistance, excellent processability, and in which the decorative sheet has excellent weather-resistant adhesion and weather resistance of its design after transfer. [Prior art documents] [Patent Documents]

[0013] [Patent Document 1] Japanese Patent Publication No. 2017-177667 [Patent Document 2] Japanese Patent Publication No. 2001-180190 [Overview of the project] [Problems that the invention aims to solve]

[0014] The present invention aims to provide a transfer sheet in which the surface protective layer of the decorative sheet transferred from the transfer sheet has excellent adhesion to the underlying layer, excellent surface hardness and scratch resistance, excellent processability, and after the transfer of the decorative sheet, the decorative sheet has excellent weather-resistant adhesion and weather resistance of the design. [Means for solving the problem]

[0015] As a result of diligent research, the present inventors have found a transfer sheet having at least a surface protective layer and a release film, wherein the surface protective layer contains a cross-linked curable resin, and the infrared spectroscopic spectral measurement of the surface protective layer shows 855 to 1325 cm⁻¹ -1 Let A be the height of the peak that appears, between 1650 and 1800 cm. -1 When the peak height appearing is B, the peak height ratio of A to B ((A / B) × 100(%)) is between 105% and 400%, and in the infrared spectroscopic spectral measurement of the surface protective layer, at 3200~3500 cm⁻¹ -1 We discovered that the above objective can be achieved by using a transfer sheet in which the peak height ratio ((B / C) × 100 (%)) of B to C, where C is the peak height appearing in the sample, is between 1000% and 6000%, and thus completed the present invention.

[0016] In other words, the present invention relates to the following transfer sheets, decorative materials, and exterior components. 1. A transfer sheet having at least a surface protective layer and a release film, The aforementioned surface protective layer contains a cross-linked curing resin, In the infrared spectroscopic measurement of the aforementioned surface protective layer, 855-1325 cm⁻¹ -1 Let A be the height of the peak that appears, between 1650 and 1800 cm. -1When the peak height appearing is B, the peak height ratio of A to B ((A / B) × 100 (%)) is between 105% and 400%. In the infrared spectral measurement of the aforementioned surface protective layer, 3200-3500 cm⁻¹ -1 When the peak height appearing is C, the peak height ratio of B to C ((B / C) × 100 (%)) is between 1000% and 6000%. A transfer sheet characterized by the following features. 2. The transfer sheet according to item 1, wherein the peak height ratio of A to B is 110% or more and 300% or less, and the peak height ratio of B to C is 1300% or more and 5500% or less. 3. The transfer sheet according to item 1 or 2, wherein the cross-linked curable resin includes an ionizing radiation curable resin. 4. The transfer sheet according to item 3, wherein the ionizing radiation-curable resin includes an acrylic resin having a (meth)acryloyl group. 5. The transfer sheet according to any one of claims 1 to 4, wherein the surface protective layer comprises at least one selected from the group consisting of antibacterial agents, antiviral agents, and allergen reducing agents. 6. A transfer sheet according to any one of items 1 to 5, wherein the surface protective layer has a back adhesive layer on the side opposite to the release film. 7. The transfer sheet according to item 6, having a pattern layer between the surface protective layer and the back adhesive layer. 8. The surface protective layer is a transfer sheet according to any one of items 1 to 7, having a ridged shape. 9. The transfer sheet according to item 8, wherein the surface protective layer has an arithmetic mean roughness Ra of 0.2 μm or more and 3.0 μm or less, an average length RSm of the curved elements of 50.0 μm or more and 100.0 μm or less, and a 60-degree specular gloss of 1 or more and 10 or less as measured in accordance with JIS Z8741:1997. 10. A decorative material having a decorative sheet transferred from a transfer sheet described in any of items 1 to 9 on a substrate. 11. An exterior component having at least a surface protective layer and a substrate, The aforementioned surface protective layer contains a cross-linked curing resin, In the infrared spectroscopic measurement of the surface protective layer, the peak height that appears at 855 to 1325 cm -1 is taken as A, and when the peak height that appears at 1650 to 1800 cm -1 is taken as B, the peak height ratio (A / B) × 100 (%) of A to B is 105% or more and 400% or less, and in the infrared spectroscopic measurement of the surface protective layer, when the peak height that appears at 3200 to 3500 cm -1 is taken as C, the peak height ratio (B / C) × 100 (%) of B to C is 1000% or more and 6000% or less, An exterior member characterized by this. 12. The exterior member according to item 11, wherein the substrate is an acrylic plate, a polycarbonate plate, a non-combustible plate, a metal plate, a vinyl chloride plate, a melamine plate, or a carbon fiber reinforced plastic plate.

Effect of the Invention

[0017] The transfer sheet of the present invention has a surface protective layer of a decorative sheet transferred from the transfer sheet that is excellent in adhesion to the lower layer, excellent in surface hardness and scratch resistance, excellent in workability, and after the transfer of the decorative sheet, the decorative sheet is excellent in weather resistance adhesion and design weather resistance. Therefore, the decorative material manufactured using the transfer sheet of the present invention can be used for various applications such as various building materials and furniture, and in particular, can be usefully used as an exterior member.

Brief Description of the Drawings

[0018] [Figure 1] It is a figure which shows an example of the result of the infrared spectroscopic measurement of the surface protective layer of the transfer sheet of this invention. [Figure 2] It is a figure explaining the method of determining the peak height in the infrared spectroscopic measurement of the surface protective layer of the transfer sheet of this invention. [Figure 3] It is a figure explaining the method of determining the peak height in the infrared spectroscopic measurement of the surface protective layer of the transfer sheet of this invention. [Figure 4] It is a figure which shows an example of the layer structure of the transfer sheet of this invention. [Figure 5] This figure shows an example of the layer structure of the transfer sheet of the present invention. [Figure 6] This figure shows an example of a layered structure in which the transfer sheets of the present invention are laminated on a substrate. [Figure 7] This figure shows an example of the layer configuration when peeling off the release film from a state in which the transfer sheet of the present invention is laminated on a substrate. [Figure 8] This figure shows an example of hydrogen bonding between molecules in a cross-linked curing resin. [Figure 9] This is a schematic diagram illustrating a test method for determining how easily a fire spreads. [Figure 10] This is a schematic diagram illustrating a test method for determining how easily a fire spreads. [Modes for carrying out the invention]

[0019] 1. Transfer sheet The transfer sheet of the present invention is a transfer sheet having at least a surface protective layer and a release film, wherein the surface protective layer contains a cross-linked curable resin, and the infrared spectroscopic spectral measurement of the surface protective layer shows 855 to 1325 cm⁻¹ -1 Let A be the height of the peak that appears, between 1650 and 1800 cm. -1 When the peak height appearing is B, the peak height ratio of A to B ((A / B) × 100(%)) is between 105% and 400%, and in the infrared spectroscopic spectral measurement of the surface protective layer, at 3200~3500 cm⁻¹ -1 The transfer sheet is characterized in that the peak height ratio ((B / C) × 100(%)) of B to C, where C is the peak height appearing in the image, is between 1000% and 6000%. Because the transfer sheet of the present invention has the above characteristics, the surface protective layer of the decorative sheet transferred from the transfer sheet has excellent adhesion to the underlying layer, excellent surface hardness and scratch resistance, excellent processability, and after the transfer of the decorative sheet, the decorative sheet has excellent weather resistance and weather resistance of the design. Therefore, decorative materials manufactured using the transfer sheet of the present invention can be used for various applications such as various building materials and furniture, and can be particularly useful as exterior components.

[0020] As described above, the transfer sheet of the present invention exhibits an infrared spectral measurement of the surface protective layer at 855-1325 cm⁻¹. -1 Let A be the height of the peak that appears, between 1650 and 1800 cm. -1 When the peak height appearing at is denoted as B, the peak height ratio of A to B ((A / B) × 100 (%)) is between 105% and 400%, and in infrared spectroscopic spectral measurement of the surface protective layer, at 3200-3500 cm⁻¹, -1 When the peak height appearing in the graph is C, the peak height ratio of B to C ((B / C) × 100 (%)) is between 1000% and 6000%. This will be explained using a diagram below.

[0021] Figure 1 shows an example of the results of infrared spectral (hereinafter also referred to as "IR") measurement of the surface protective layer of the transfer sheet of the present invention. In Figure 1, A represents the peak due to ether bonding, B represents the peak due to ester bonding, and C represents the peak due to urethane bonding.

[0022] In this specification, the height of each peak is measured as follows: As shown in Figure 2, two base points b1 and b2 are taken for each peak, and a baseline bL is drawn by connecting the base points with a straight line. Next, a vertical line is drawn downward from the position p of the peak top, and the intersection point bp with the baseline bL is specified. The length h between p and bp is taken as the peak height.

[0023] Furthermore, as shown in Figure 3, if peak A has multiple peaks, the peak heights are measured as follows: That is, if there are two adjacent peaks as shown in Figure 3, and the heights h1-1 and h2-1 from the valley between the two peaks to the peak apex are 0.010 Abs or greater, the two peak heights h1 and h2 are added together to determine the peak height. Note that in Figure 3, the peak with peak top p2 has adjacent peaks p1 and p3 on both sides, and there are two heights, h2-1 and h2-2, from the valley between the two peaks to the peak apex. In this case, the shorter height, h2-1, is used to determine whether it is 0.010 Abs or greater.

[0024] In this specification, the infrared spectroscopic spectrum of the surface protective layer can be measured using commercially available infrared spectroscopic spectroscopy equipment.

[0025] The transfer sheet of the present invention exhibits an infrared spectral measurement of the surface protective layer at 855-1325 cm⁻¹. -1 Let A be the height of the peak that appears, between 1650 and 1800 cm. -1 The peak height ratio of A to B ((A / B) × 100(%)), where B is the peak height appearing in the sample, is between 105% and 400%. If the peak height ratio of A to B is less than 105%, there are too many ester bonds in the surface protective layer, making the surface protective layer too hard and reducing the processability of the transfer sheet. If the peak height ratio of A to B exceeds 400%, there are too many ether bonds, making the surface protective layer too soft and reducing the surface hardness and scratch resistance of the decorative sheet transferred from the transfer sheet. The peak height ratio of A to B is preferably between 110% and 300%, and more preferably between 150% and 250%.

[0026] The transfer sheet of the present invention exhibits an infrared spectral measurement of the surface protective layer, with a range of 3200 to 3500 cm⁻¹. -1The peak height ratio of B to C ((B / C) × 100(%)), where C is the peak height appearing in the sample, is between 1000% and 6000%. If the peak height ratio of B to C is less than 1000%, there are too many urethane bonds in the surface protective layer, and the hydrogen bonds between the -NH groups and -C=O groups in the urethane bonds increase excessively, as shown in Figure 8, making the surface protective layer too hard and reducing the processability of the transfer sheet. If the peak height ratio of B to C exceeds 6000%, there are too few urethane bonds in the surface protective layer, making the surface protective layer too soft and reducing the surface hardness and scratch resistance of the decorative sheet transferred from the transfer sheet. The peak height ratio of B to C is preferably between 1300% and 5500%, and more preferably between 1500% and 5200%.

[0027] One adjustment method for adjusting the peak height ratio between A and B, and the peak height ratio between B and C, to within the above range is to change the formulation of the cross-linked curable resin used to form the surface protective layer. When the cross-linked curable resin formulation contains many ether bonds and few ester bonds, the peak height ratio between A and B increases. Conversely, when the cross-linked curable resin formulation contains few ether bonds and many ester bonds, the peak height ratio between A and B decreases. Also, when the cross-linked curable resin formulation contains many ester bonds and few urethane bonds, the peak height ratio between B and C increases. Conversely, when the cross-linked curable resin formulation contains few ester bonds and many urethane bonds, the peak height ratio between B and C decreases.

[0028] The following describes in detail each layer of the transfer sheet of the present invention. In the transfer sheet of the present invention, the surface is the so-called "front surface," which is the surface opposite to the surface that comes into contact with the substrate when the transfer sheet of the present invention is laminated onto a substrate or the like, and is the surface on the release film side. In this specification, the direction of the surface of the transfer sheet of the present invention may be referred to as "front" or "top," and the opposite side may be referred to as "back" or "bottom." In the following description, the lower and upper limits of a numerical range represented by "~" mean "greater than or equal to or less than or equal to" (for example, α~β means α or greater and β or less).

[0029] Furthermore, the layer thickness in this specification is the value measured in a location on the decorative sheet that constitutes the transfer sheet and remains laminated on the substrate after the release film has been peeled off, where there are no uneven shapes such as embossing or protruding fine particles.

[0030] (Layer structure of the transfer sheet of the present invention) The transfer sheet of the present invention only needs to have at least a surface protective layer and a release film, and it is preferable that the surface protective layer is located on the outermost surface of the decorative sheet transferred from the transfer sheet. The specific configuration can be appropriately set according to the application of the transfer sheet. For example, as shown in Figure 4, the layer configuration of the transfer sheet of the present invention includes a back adhesive layer 115, a surface protective layer 114, and a release film 10 in that order. In the transfer sheet of the present invention, a layer configuration in which the back adhesive layer 115 is located on the side of the surface protective layer 114 opposite to the release film 10 is preferred. Alternatively, as shown in Figure 5, the layer configuration of the transfer sheet of the present invention includes a back adhesive layer 115, a base sheet 111, a pattern layer 112 (solid ink layer and / or pattern ink layer), an adhesive layer (not shown), a transparent resin layer 113, a surface protective layer 114, and a release film 10 in that order. In Figure 4, the back adhesive layer 115 and the surface protective layer 114 constitute the decorative sheet 11, and in Figure 5, the back adhesive layer 115, the base sheet 111, the pattern layer 112 (solid ink layer and / or pattern ink layer), the adhesive layer (not shown), the transparent resin layer 113, and the surface protective layer 114 constitute the decorative sheet 11. In other words, in the transfer sheet of the present invention, a release film 10 is laminated on the surface (surface protective layer side) of the decorative sheet 11.

[0031] Figure 6 shows an example of a layer configuration in which the transfer sheet of the present invention is laminated on a base body 2. As shown in Figure 6, the transfer sheet of the present invention is laminated on a base body 2, and then, as shown in Figure 7, the release film 10 is peeled off to transfer the decorative sheet 11 onto the base body 2, making it possible to easily manufacture a decorative material having the decorative sheet 11 transferred from the transfer sheet 1 on the base body 2. In other words, the decorative material is a decorative material having the decorative sheet 11 on the base body 2. This decorative material can be usefully used as an exterior component.

[0032] The following will provide a specific example of a transfer sheet with such a layered structure.

[0033] (Release film) The transfer sheet of the present invention comprises at least a surface protective layer and a release film.

[0034] The release film is preferably a resin film. Examples of resins that can be included in the resin film include ester resins, olefin resins, styrene resins, vinyl resins, (meth)acrylic resins, amide resins, imide resins, and carbonate resins. Among these, ester resins and olefin resins can be preferably used.

[0035] Examples of ester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymers. Among these, PET or PBT are preferred, and PET is more preferred, from the viewpoint of suppressing thermal shrinkage during the manufacture of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0036] Examples of olefin resins include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer. Among these, polypropylene is preferred from the viewpoint of suppressing thermal shrinkage during the manufacture of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0037] The surface of the release film facing the protective layer is preferably mirror-finished. Having a mirror-finish surface on the protective layer side of the release film allows for easy peeling of the release film after lamination of the transfer sheet of the present invention onto the substrate, thereby facilitating the easier manufacture of the decorative material and exterior component of the present invention.

[0038] The thickness of the release film is, for example, 10 μm or more and 300 μm or less, and may be 20 μm or more and 200 μm or less, or 20 μm or more and 100 μm or less.

[0039] (Surface protective layer) The transfer sheet of the present invention comprises at least a surface protective layer and a release film. In this specification, the surface protective layer contains a cross-linked curable resin.

[0040] Examples of cross-linked curable resins include thermosetting resins and ionizing radiation curable resins (e.g., electron beam curable resins). Depending on the application, one or more of the above cross-linked curable resins may be used. In particular, from the viewpoint of scratch resistance due to high surface hardness, retention of convex shapes, and productivity, it is preferable that the surface protective layer contains an ionizing radiation curable resin, and it is even more preferable that the resin constituting the surface protective layer is an ionizing radiation curable resin.

[0041] Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea cocondensation resins, silicon resins, polysiloxane resins, unsaturated polyester resins, and silicone resins.

[0042] The above resins may be given curing agents such as crosslinking agents and polymerization initiators, polymerization accelerators, etc. For example, isocyanates and organic sulfonates can be added to unsaturated polyester resins and polyurethane resins as curing agents, organic amines can be added to epoxy resins, and peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutylnitrile can be added to unsaturated polyester resins.

[0043] Methods for forming a surface protective layer with a thermosetting resin include, for example, applying a solution of the thermosetting resin using a coating method such as roll coating or gravure coating, and then drying and curing it.

[0044] Ionizing radiation-curable resins are not limited to resins that undergo a crosslinking polymerization reaction upon irradiation with ionizing radiation and transform into a three-dimensional polymer structure. For example, one or more prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in their molecules that can be crosslinked by irradiation with ionizing radiation can be used. Examples include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; and epoxy resins.

[0045] The ionizing radiation-curable resin preferably contains an acrylic resin having (meth)acryloyl groups. By including an acrylic resin having (meth)acryloyl groups as the ionizing radiation-curable resin, hydrogen bonds are formed between the molecules of the ionizing radiation-curable resin, further improving the surface hardness and scratch resistance of the surface protective layer.

[0046] Ionizing radiation includes visible light, ultraviolet light (near-ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, and ion beams, but among these, ultraviolet light and / or electron beams are preferred.

[0047] Suitable ultraviolet light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, blacklight fluorescent lamps, and metal halide lamps. The wavelength of ultraviolet light is approximately 190-380 nm.

[0048] Various electron beam accelerators can be used as electron sources, such as Cockcroftwald type, Van de Graft type, resonant transformer type, insulated core transformer type, linear type, Dynamitron type, and high-frequency type. The electron beam energy is preferably around 100 to 1000 keV, and more preferably around 100 to 300 keV. The electron beam irradiation dose is preferably around 2 to 15 Mrad.

[0049] Ionizing radiation-curable resins can be sufficiently cured by irradiation with electron beams, but when curing by irradiation with ultraviolet light, it is preferable to add a photopolymerization initiator (sensitizer).

[0050] For resin systems having radically polymerizable unsaturated groups, at least one of the following photopolymerization initiators can be used: acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N,N-dimethylaminobenzoate, etc. For resin systems having cationic polymerizable functional groups, at least one of the following can be used: aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, fryloxysulfoxonium diallylodosyl salt, etc.

[0051] The amount of photopolymerization initiator added is not particularly limited, but is generally about 0.1 to 10 parts by mass per 100 parts by mass of ionizing radiation-curable resin.

[0052] Furthermore, in recent years, the use of biomass-derived resins, which have a low environmental impact, has been explored in various fields. The resin forming the surface protective layer of the transfer sheet of the present invention can also contain biomass-derived components, and specifically, biomass polyolefins and the like can be used.

[0053] The surface protection layer may be a single layer or a multi-layer structure of two or more layers. In this invention, if the surface protection layer consists of multiple layers, each layer contains a cross-linked curable resin. Furthermore, when the surface protection layer consists of multiple layers, the infrared spectral measurement of the surface protection layer is performed by measuring the infrared spectral spectrum of the stacked surface protection layers starting from the outermost surface protection layer.

[0054] The thickness of the surface protective layer is not particularly limited as long as it does not hinder the effects of the present invention, but is preferably 1 to 200 μm, more preferably 1 to 100 μm, even more preferably 3 to 50 μm, and particularly preferably 4 to 40 μm.

[0055] The surface protective layer may contain fine particles. Examples of fine particles include inorganic fillers such as silica, aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, corundum, and glass fibers; and organic material powders or beads such as acrylic, cross-linked alkyl, cross-linked styrene, benzoguanamine resin, urea-formaldehyde resin, phenolic resin, polyethylene, and nylon. One or more types of the fine particles can be used.

[0056] The average particle size of the fine particles is preferably greater than or equal to the thickness of the surface protective layer, and to exhibit scratch resistance, it is preferably less than "thickness of the surface protective layer + 40 μm", and more preferably "thickness of the surface protective layer + 30 μm" or less.

[0057] The average particle diameter of fine particles can be measured by known methods such as laser diffraction, Coulter counter, and sedimentation. Note that the average particle diameter refers to the mode diameter.

[0058] The content of fine particles in the surface protective layer is preferably 3 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of the resin component forming the surface protective layer.

[0059] Silica has siloxane bonds (-Si-O-Si-), which are similar to ether bonds (-COC-). Therefore, if the surface protective layer contains silica, it may affect the peak height A mentioned above. However, even if the surface protective layer contains silica, if the peak height ratio ((A / B) × 100 (%)) of the peak heights A and B mentioned above is between 105% and 400%, the surface protective layer of the transfer sheet of the present invention can exhibit the desired performance.

[0060] Silicone may be added to the surface protective layer. When silicone is added to the surface protective layer, the amount of silicone added is preferably 0.1 to 1 part by mass, and more preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the resin (resin component) constituting the surface protective layer, from the viewpoint of achieving both ease of wiping and slipperiness.

[0061] The surface protective layer may contain various additives as needed, such as solvents, dyes, pigments and other colorants, fillers such as inorganic fillers, defoamers, leveling agents, thixotropy-imparting agents, flame retardants, antibacterial agents, antiviral agents, and allergen-reducing agents.

[0062] As an inorganic filler, it can be used as a means of imparting a predetermined surface property to the surface protective layer by incorporating an inorganic filler larger than the thickness of the surface protective layer into the surface protective layer. Furthermore, the inorganic filler can also be used as a matting agent, and by including the inorganic filler in the surface protective layer, it is expected that the hardening shrinkage of the surface protective layer will be suppressed. Therefore, in this invention, it is preferable that the inorganic filler is surface-treated (hydrophobic treatment). In addition, among these additives, it is preferable to include at least one selected from the group consisting of antibacterial agents, antiviral agents, and allergen reducing agents in the surface protective layer, which is the outermost layer, in order to easily obtain the effect.

[0063] Examples of inorganic fillers include silica, aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, corundum, and glass fibers.

[0064] The method for surface treatment (hydrophobic treatment) of inorganic fillers is not particularly limited and can be carried out by known methods. Examples include: hydrophobic treatment of inorganic fillers with a silicone oil-based treatment agent; treatment of inorganic fillers with an alkylsilazane-based treatment agent, a trimethylsilylating agent, and / or an alkoxysilane, followed by hydrophobic treatment of the inorganic fillers with the aforementioned silicone oil-based treatment agent; hydrophobic treatment of inorganic fillers with a silicone oil-based treatment agent, followed by further treatment with a trimethylsilylating agent or an alkylsilazane-based treatment agent; hydrophobic treatment of inorganic fillers with an alkoxysilane; treatment of inorganic fillers with an alkoxysilane, followed by further treatment with a silicone oil-based treatment agent, or a silicone oil-based treatment agent and an alkoxysilane; and treatment of inorganic fillers with dimergol siloxane, and / or trimethylsilanol or a cyclic siloxane. In addition to the hydrophobic treatment methods described above, other methods of hydrophobic treatment include treatment with various coupling agents such as silane coupling agents, titanate coupling agents, and aluminate coupling agents; surfactants such as phosphoric acid-based and fatty acid-based surfactants; and treatment with oils, stearic acid, etc. Hereinafter, all of the above-mentioned products for hydrophobic treatment of untreated inorganic fillers (for example, all of the treatment agents such as silicone oil-based treatment agents, silane coupling agents, surfactants, etc.) will be collectively referred to as hydrophobic treatment agents.

[0065] The method for hydrophobizing inorganic fillers with a hydrophobic treatment agent is not particularly limited and can be carried out by known methods. For example, methods include adding (e.g., spraying) a stock solution of the hydrophobic treatment agent or a solution of the hydrophobic treatment agent diluted in water or an organic solvent to untreated inorganic fillers (dry treatment method); or treating (e.g., immersing) the untreated inorganic fillers in a stock solution of the hydrophobic treatment agent, an aqueous solution containing the hydrophobic treatment agent, or an organic solvent containing the hydrophobic treatment agent, and then drying them (wet treatment method). Such treatment results in (a) the inorganic filler surface being coated with the hydrophobic treatment agent, (b) the hydrophobic treatment agent being adsorbed, or (c) the inorganic filler being coated with and adsorbed by the hydrophobic treatment agent (a combination of (a) and (b)). As a result, hydrophobized inorganic fillers are obtained. Note that the hydrophobic treatment agent may be used alone or in combination of two or more types.

[0066] Furthermore, in order to impart a predetermined surface shape to the surface protective layer of the decorative sheet transferred from the transfer sheet, the surface protective layer may be laminated after forming an uneven shape on the surface protective layer side of the release film, thereby imparting an uneven shape to the surface protective layer. Examples of uneven shapes to be formed on the release film include embossed shapes and wrinkled shapes. According to the above method, there is no need to add fillers or the like to the surface protective layer forming composition for forming the surface protective layer, so there is no concern about a decrease in the chemical resistance of the surface protective layer after transfer due to the addition of fillers or the like, or about fillers or the like falling off due to wear of the surface protective layer after transfer. If a wrinkled shape is given to the surface protective layer as an uneven shape, it is possible to lower the glossiness of the surface protective layer of the decorative sheet transferred from the transfer sheet, making it suitable when a low-gloss design is required.

[0067] To form an uneven surface on the release film, an uneven surface-forming resin layer may be provided on the surface of the release film facing the protective layer. The resin forming the uneven surface-forming resin layer may be at least one of the curable resins, such as thermoplastic resins, thermosetting resins, and ionizing radiation-curable resins. Below, as an example, an uneven surface-forming resin layer using an ionizing radiation-curable resin will be described. It is preferable that the uneven surface-forming resin layer contains a cured product of the ionizing radiation-curable resin.

[0068] Ionizing radiation-curable resins are not limited to resins that undergo a crosslinking polymerization reaction upon irradiation with ionizing radiation and transform into a three-dimensional polymer structure. For example, one or more prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in their molecules that can be crosslinked by irradiation with ionizing radiation can be used. Examples include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; and epoxy resins.

[0069] Ionizing radiation includes ultraviolet rays (near-ultraviolet rays, vacuum ultraviolet rays, etc.), X-rays, electron beams, and ion beams, among which ultraviolet rays or electron beams are preferred, and electron beams are more preferred.

[0070] Suitable ultraviolet light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, blacklight fluorescent lamps, and metal halide lamps. The wavelength of ultraviolet light is approximately 190-380 nm.

[0071] Suitable electron sources include, for example, Cockcroftwald type, Van de Graft type, resonant transformer type, insulated core transformer type, linear type, Dynamitron type, and high-frequency type electron beam accelerators. The electron beam energy is preferably around 100 to 1000 keV, and more preferably around 100 to 300 keV. The electron beam irradiation dose is preferably around 2 to 15 Mrad.

[0072] Ionizing radiation-curable resins can be sufficiently cured by irradiation with electron beams, but when curing by irradiation with ultraviolet light, it is preferable to add a photopolymerization initiator (sensitizer).

[0073] For resin systems having radically polymerizable unsaturated groups, at least one of the following photopolymerization initiators can be used: acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N,N-dimethylaminobenzoate, etc. For resin systems having cationic polymerizable functional groups, at least one of the following can be used: aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, fryloxysulfoxonium diallylodosyl salt, etc.

[0074] The amount of photopolymerization initiator added is not particularly limited, but is generally about 0.1 to 10 parts by mass per 100 parts by mass of ionizing radiation-curable resin.

[0075] When forming a textured resin layer using an ionizing radiation-curable resin, for example, a solution of the ionizing radiation-curable resin (including additives as appropriate; hereinafter also referred to as "ionizing radiation-curable resin composition") can be applied by a coating method such as gravure coating or roll coating, and then the coating film can be irradiated with ionizing radiation to form the textured layer.

[0076] Furthermore, the above-mentioned textured resin layer has an uneven surface, thereby giving the surface protective layer of the decorative sheet transferred from the transfer sheet a predetermined specular gloss characteristic. Here, the method for forming the uneven surface of the textured resin layer is not limited, but one example is to perform the following irradiation treatments (A) and (B) in this order on a coating film of an ionizing radiation-curable resin composition. (A) Irradiation treatment with a first wavelength light having a wavelength of 100 nm or more and less than 200 nm. (B) Irradiation treatment with at least one of an electron beam and a second wavelength light having a wavelength of 200 nm or more and 400 nm or less.

[0077] It is preferable to form a textured resin layer on the outermost surface by the above irradiation treatment, which has an uneven surface, particularly a wrinkled shape (especially a random wrinkled shape). The irradiation treatments (A) and (B) described above will be explained in detail below.

[0078] First, when the irradiation treatment with low-wavelength (short-wavelength) ultraviolet light (first wavelength light) as described in (A) above is performed, the energy of the ultraviolet light penetrates only to the surface portion, and the energy does not reach the layers below it. As a result, only the surface portion of the coating film begins to harden, and it is thought that only the surface hardens and shrinks, forming a wrinkle structure (preferably formed randomly). Thus, it is thought that the formation of the wrinkle structure occurs when only a certain thickness from the surface of the coating film hardens due to irradiation with low-wavelength (short-wavelength) ultraviolet light.

[0079] Next, by irradiating with at least one of the electron beam and ultraviolet light of high wavelength (long wavelength) of 200 nm to 400 nm as described in (B) above, the wrinkle structure formed on the surface of the coating film can be maintained while promoting hardening from the near surface to the deeper parts in the depth direction, where hardening progresses slowly.

[0080] Although the coating can harden throughout its entire thickness with the irradiation treatment described in (A) above, the hardening state is further improved by combining it with the irradiation treatment described in (B) above. As a result, it is thought that a wrinkle structure is more likely to appear on the surface of the surface layer.

[0081] In the irradiation process described in (A) above, the first wavelength light with a wavelength of 100 nm or more and less than 200 nm is preferably "excimer light" which includes light in the ultraviolet wavelength range from gases such as noble gases like Ar, Kr, Xe, and Ne, halides of noble gases such as F, Cl, I, and Br, or dimers of excited states formed by the discharge of mixed gases thereon, i.e., excimers. The wavelength of the excimer light and the excimer that serves as the light source can preferably include, for example, light with a wavelength of 126 nm (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), and 193 nm (ArF) emitted from an Ar2 excimer. As the excimer light, either spontaneous emission light or highly coherent laser light produced by stimulated emission can be used, but usually spontaneous emission light is sufficient. These discharge lamps that emit light (ultraviolet light) are also called "excimer lamps."

[0082] Excimer light is characterized by a single wavelength peak and a narrower full width at half maximum compared to ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). Using such excimer light makes it easier to induce wrinkle structures.

[0083] For the same reasons as above, the wavelength of the first wavelength light is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, and even more preferably 155 nm or more. Also, the wavelength of the first wavelength light is less than 200 nm, and particularly preferably 172 nm (Xe2).

[0084] The integrated light intensity of the first wavelength is preferably 1 mJ / cm². 2 More preferably 2 mJ / cm 2 More preferably 5 mJ / cm² 2That concludes the explanation. Furthermore, there is no particular upper limit to the integrated light intensity of the first wavelength light. Considering the reduction in the number of lamps required for irradiation with the first wavelength light and the improvement of productivity such as production efficiency, the integrated light intensity of the first wavelength light is preferably 1,000 mJ / cm². 2 More preferably 300 mJ / cm² 2 More preferably, 100 mJ / cm² 2 The following is particularly preferable: 30 mJ / cm² 2 The following applies:

[0085] The ultraviolet irradiance is preferably 1 mW / cm². 2 More preferably 5 mW / cm² 2 More preferably 10 mW / cm² 2 That concludes the explanation. Furthermore, the ultraviolet irradiance is preferably 10 W / cm². 2 More preferably 3 W / cm 2 More preferably, 1 W / cm 2 The following applies, especially considering productivity: UV irradiance should be 500 mW / cm². 2 The following is preferable: 300 mW / cm² 2 The following is more preferable: 150 mW / cm² 2 The following are even more preferable.

[0086] Furthermore, the oxygen concentration when irradiating with the first wavelength light is preferably lower, preferably 1000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and particularly preferably 100 ppm or less.

[0087] In the process of forming the uneven resin layer described above, it is preferable to perform irradiation with at least one of the electron beam and the second wavelength light of 200 nm to 400 nm described above, following the irradiation treatment with the first wavelength light of 100 nm to less than 200 nm described above (A).

[0088] The irradiation conditions for the electron beam used in the irradiation treatment described in (B) above are not particularly limited as long as the ionizing radiation-curable resin composition is cured. The electron beam acceleration voltage is preferably 10kV or higher, more preferably 30kV or higher, even more preferably 50kV, and even more preferably 75kV or higher. The electron beam acceleration voltage is also preferably 300kV or lower, more preferably 250kV or lower, and even more preferably 200kV or lower. When the electron beam acceleration voltage is within the above range, the cured product tends to retain the shape of the wrinkle structure, so the contact angle with water is within a specific range due to the wrinkle structure, making it easier to obtain excellent antifouling properties. In addition, surface performance other than antifouling properties, namely scratch resistance, strength and weather resistance, as well as processing performance, are improved. For the same reasons as above, the electron beam irradiation dose is preferably 5kGy or higher, more preferably 10kGy or higher, and even more preferably 15kGy or higher. Furthermore, the electron beam irradiation dose is preferably 150 kGy or less, more preferably 125 kGy or less, and even more preferably 100 kGy or less.

[0089] The electron source is not particularly limited as long as it can achieve the above irradiation conditions. For example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graft type, resonant transformer type, insulated core transformer type, and linear type, dynamitron type, and high-frequency type can be used.

[0090] The second wavelength light between 200 nm and 400 nm used in the irradiation process described in (B) above can be irradiated using an ultraviolet irradiation device that uses, for example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp as a light source. Alternatively, excimer light between 200 nm and 400 nm, such as 222 nm (KrCl), 247 nm (KrF), or 308 nm (XeCl), may be used.

[0091] The wavelength of the second wavelength light used in the irradiation process described in (B) above is preferably 330 nm or more and 390 nm or less. When the wavelength of the second wavelength light is within this range, it is easier to maintain the shape of the wrinkle structure. For the same reasons as above, the output of the ultraviolet irradiation device is preferably 50 W / cm or more, more preferably 100 W / cm or more. The output of the ultraviolet irradiation device is preferably 300 W / cm or less, more preferably 200 W / cm or less. The irradiation speed is preferably 1 r / min or more, more preferably 3 r / min or more. The irradiation speed is preferably 50 r / min or less, more preferably 10 r / min or less.

[0092] Furthermore, before the irradiation treatments described in (A) and (B) above, the irradiation treatment for pre-curing (C) may be performed. Pre-curing the entire coating film by the irradiation treatment for pre-curing (C) above imparts appropriate viscosity to the ionizing radiation-curable resin composition. As a result, the sagging of the wrinkle structure formed by the irradiation treatment described in (A) above is suppressed, and the retention of the wrinkle structure can be improved.

[0093] The wavelength of ionizing radiation used in the irradiation treatment for pre-curing described in (C) above may be, for example, light with a wavelength greater than 320 nm, preferably light with a wavelength greater than 320 nm and less than or equal to 400 nm, and more preferably light with a wavelength of 385 nm and less than or equal to 400 nm (ultraviolet light). By using the above wavelength of light (ultraviolet light) in the irradiation treatment described in (C) above, the overall pre-curing of the coating film can be efficiently performed.

[0094] The ultraviolet irradiance in the irradiation treatment described in (C) above is preferably 0.01 W / cm². 2 More preferably, 0.1 W / cm² 2 More preferably 0.3 W / cm² 2 That concludes the explanation. Furthermore, the ultraviolet irradiance is preferably 5 W / cm². 2 More preferably 3 W / cm 2 More preferably, 2 W / cm 2The following applies: When the ultraviolet irradiance is within the above range, the coating can be efficiently pre-cured overall without the coating becoming completely hardened.

[0095] The wavelength light used in the irradiation process described in (C) above can be irradiated using an ultraviolet irradiation device that uses, for example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp, or an LED light as a light source.

[0096] Furthermore, the specific surface properties of the irregularities formed by the wrinkle shape (especially random wrinkle shape) obtained through the above process are not limited as long as the transfer sheet of the present invention exhibits the characteristics of a predetermined specular gloss. However, the wrinkle shape (wrinkle structure) formed on the surface protective layer of the transfer sheet preferably has the following surface properties.

[0097] (i) Ra (arithmetic mean roughness) As for surface properties, it is preferable that the Ra (arithmetic mean roughness), a parameter in the height direction of the contour curve as defined in JIS B0601:2013, is 0.10 μm or more. Ra (arithmetic mean roughness) is one of the parameters in the height direction of the contour curve, and is the average value of the height difference from the average surface in the contour curve over a reference length. The larger the Ra (arithmetic mean roughness) value, the greater the height difference tends to be between the convex parts and the correspondingly formed recesses in the wrinkle structure of the surface shape. When the height difference is large, the convex parts become more prominent.

[0098] The above Ra (arithmetic mean roughness) is more preferably 0.3 μm or more, and even more preferably 0.4 μm or more. On the other hand, there is no particular upper limit to the above Ra (arithmetic mean roughness), but considering ease of manufacture and other factors, it is preferably 4.00 μm or less, more preferably 3.00 μm or less, and even more preferably 1.00 μm or less.

[0099] In this specification, the cutoff value for measuring Ra (arithmetic mean roughness) is 0.8 mm. Furthermore, in this specification, the above Ra (arithmetic mean roughness) is the average value of measurements taken at any 10 locations.

[0100] (ii) RSm (average length of curve elements) As a surface property, it is preferable that the RSm (average length of curve elements), which is a lateral parameter of the contour curve as defined in JIS B0601:2013, is 110.00 μm or less. RSm (average length of curve elements) is a lateral parameter of the contour curve and is the average length of the contour curve elements in a reference length. The smaller the RSm, the more densely the vertices of the convex parts in the wrinkle structure of the surface shape tend to be present.

[0101] The above RSm (average length of the curved element) is more preferably 100.00 μm or less, and even more preferably 90.00 μm or less. The lower limit of the above RSm (average length of the curved element), taking into consideration ease of manufacturing, is preferably 40.00 μm or more, more preferably 60.00 μm or more, and even more preferably 80.00 μm or more.

[0102] In this specification, the cutoff value for measuring RSm (average length of the curved element) is 0.8 mm. Furthermore, in this specification, the above RSm (average length of the curved element) is the average value of measurements taken at any 10 locations.

[0103] The above-mentioned antibacterial agents include inorganic antibacterial agents and organic antibacterial agents. In particular, inorganic antibacterial agents are generally safer than organic antibacterial agents and are preferable because they also have superior durability and heat resistance. Inorganic antibacterial agents are antibacterial metals such as silver, copper, and zinc supported on various inorganic carriers. When included in a surface protective layer, the amount of antibacterial agent added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the resin component of the surface protective layer, but the details can be adjusted as appropriate depending on the type of antibacterial agent.

[0104] The above-mentioned antiviral agents can generally be broadly classified into organic and inorganic types. Organic antiviral agents include quaternary ammonium salts, quaternary phosphonium salts, pyridines, pyrithiones, benzimidazoles, organic iodines, isothiazolins, anions, and ethers. Inorganic antiviral agents include metal ions such as silver, copper, and zinc supported on carriers such as zeolites, apatite, zirconia, glass, and molybdenum oxide. When included in a surface protective layer, the amount of antiviral agent added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the resin component of the surface protective layer, but the details can be appropriately adjusted depending on the type of antiviral agent.

[0105] Among the above organic antiviral agents, benzimidazole-based antiviral agents, anionic-based antiviral agents, or ether-based antiviral agents that maintain their particle shape are particularly preferred. Here, "maintaining particle shape" means that they exist in a granular state without dissolving in the composition (ink before curing) that becomes the curable resin of the surface protective layer. Therefore, in the process of forming the surface protective layer, the particles of imidazole-based compounds, anionic-based compounds, or ether-based compounds tend to float to the surface, making it easier to unevenly distribute the particles of imidazole-based compounds, anionic-based compounds, or ether-based compounds to the outermost surface of the surface protective layer. By unevenly distributing the particles of imidazole-based compounds, anionic-based compounds, or ether-based compounds to the outermost surface of the surface protective layer, the amount of antiviral agent required to obtain the desired antiviral effect can be suppressed, thus making it easier to suppress the decrease in the scratch resistance of the surface protective layer.

[0106] The above-mentioned anionic antiviral agents preferably include, for example, styrene resin, styrene polymer derivative compounds, and unsaturated carboxylic acid derivative compounds. Furthermore, the above-mentioned styrene polymer derivative compounds and unsaturated carboxylic acid derivative compounds preferably contain at least one structure from among styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably contain all of these structures. This is because viruses can be broadly classified into two types based on whether or not they have an envelope, and it is thought that the structure of the antiviral agent that can effectively inhibit the activity of each type is different. Therefore, for example, if the expectation is to be effective only against influenza viruses, which are non-enveloped viruses, it is sufficient to include only styrene polymer derivative compounds, and in some cases, sufficient effect can be obtained by including only styrene resin.

[0107] Among the inorganic antiviral agents mentioned above, silver-based antiviral agents are preferred from the viewpoint of having no biotoxicity and excellent safety, and among them, phosphate-based glass silver-supported compounds or silver zeolite compounds, and molybdenum silver oxide double salt compounds are even more preferred because they exhibit antiviral performance even in small amounts, thus allowing for a reduction in the amount added.

[0108] When the above-mentioned silver-based antiviral agent is included in the surface protective layer, discoloration may occur depending on the surface protective layer (discoloration may occur due to heat and light in the state of the paint in which it is added, or due to heat and light after the surface protective layer has been formed). In this case, it is possible to improve the situation by adding UV inhibitors, light stabilizers, etc., in a timely manner. For example, with respect to the above-mentioned silver molybdenum oxide double salt compound, a discoloration improvement effect can be expected by using a benzotriazole compound.

[0109] The above-mentioned allergen reducing agent contains either an inorganic compound or an organic compound, and each may be used individually or mixed with two or more different types. The inorganic compound is preferably a material supporting a metal. When included in a surface protective layer, the amount of allergen reducing agent added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the resin component of the surface protective layer, but the details can be appropriately adjusted depending on the type of allergen reducing agent.

[0110] A method for forming a surface protective layer containing an ionizing radiation-curable resin includes, for example, a method in which a solution (composition for forming a surface protective layer) containing (1) a resin such as an ionizing radiation-curable resin, and (2) optionally other resins, fine particles, ultraviolet absorbers, antibacterial agents, and the above-mentioned various additives is applied by a coating method such as gravure coating or roll coating, and then the ionizing radiation-curable resin is cured to form the surface protective layer.

[0111] (Adhesive layer on the back) The transfer sheet of the present invention may have a back adhesive layer on the side opposite to the release film of the surface protective layer. If the transfer sheet of the present invention includes a design layer as described later, the back adhesive layer may have a design layer on the side opposite to the surface protective layer of the design layer.

[0112] The adhesive layer on the back is preferably the layer that comes into contact with the substrate in the decorative sheet (transfer layer) that is transferred from the transfer sheet. In this case, the adhesive layer on the back is arranged to improve the adhesion between the decorative sheet being transferred and the substrate. The adhesive layer on the back preferably contains an adhesive component. Examples of adhesive components include (meth)acrylic resins, vinyl chloride-vinyl acetate copolymers, vinyl acetate resins, ester resins, epoxy resins, imide resins, and rubber resins.

[0113] The adhesive layer on the back may be a so-called tacky layer. The tacky layer is tacky at room temperature. Examples of resins included in the tacky layer are (meth)acrylic resins, silicone resins, vinyl resins, ester resins, urethane resins, amide resins, epoxy resins, rubber resins, and ionomer resins.

[0114] Furthermore, the adhesive layer on the back may be a so-called heat-seal layer. The heat-seal layer becomes tacky when heated. Examples of resins included in the heat-seal layer include thermoplastic resins. Examples of thermoplastic resins include acrylic resins, polyacrylic polyols, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, acrylic-vinyl acetate copolymers, polyester resins, amide resins, cyanoacrylate resins, epoxy resins, etc., and these can be used individually or in combination of two or more. Among these, at least one of acrylic resins, polyacrylic polyols, and urethane resins is preferred, with acrylic resin being more preferred, from the viewpoint of improving processability during the manufacture of exterior components and the adhesion between the transferred decorative sheet (transfer layer) and the substrate.

[0115] A known printing method can be used to form the adhesive layer on the back.

[0116] The thickness of the adhesive layer on the back surface is not particularly limited, but the thickness after drying is approximately 0.1 to 30 μm, preferably 1 to 20 μm.

[0117] The adhesive layer on the back may contain a coloring agent. Examples of coloring agents include those used in the design layer described later. By including a coloring agent in the adhesive layer on the back, the decorative sheet (transfer layer) transferred from the transfer sheet can be given a design. In other words, the adhesive layer on the back may be a layer that performs the same function as the pattern layer described later.

[0118] (Base sheet) The transfer sheet of the present invention may have a base sheet. The base sheet is a layer on which patterns and designs are sequentially laminated on its surface (front side).

[0119] Suitable base sheets include, for example, sheets (films) formed from thermoplastic resins. Specifically, examples include olefin resins such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylic acid ester copolymer; polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, ionomer, acrylic acid ester polymer, and methacrylic acid ester polymer. In recent years, the use of biomass-derived resins, which have a low environmental impact, has been explored in many fields, and the resin used to form the base sheet of the transfer sheet of the present invention can also contain biomass-derived components. Specifically, biomass polyolefins can be used. The base sheet is formed by using these resins individually or in combination of two or more types.

[0120] In this specification, "(meth)acrylic acid" means acrylic acid and / or methacrylic acid, and the same applies to other parts that are indicated with "(meth)".

[0121] The base sheet may be colored. In this case, the thermoplastic resin described above can be colored by adding a coloring agent (pigment or dye). As coloring agents, inorganic pigments such as titanium dioxide, carbon black, and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. One or more of these can be selected from publicly known or commercially available products. The amount of coloring agent added can also be set appropriately according to the desired color.

[0122] The base sheet may contain various additives as needed, such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers.

[0123] In the base sheet, the UV absorber, light stabilizer, and flame retardant can be the same as those used in the transparent resin layer described later, and in the same amounts.

[0124] The thickness of the base sheet can be set appropriately depending on the application and method of use of the final product, but generally 20 to 300 μm is preferred.

[0125] The base sheet may, if necessary, be subjected to corona discharge treatment on its surface (front side) to improve the adhesion of the ink forming the pattern layer. The method and conditions for corona discharge treatment should be carried out according to known methods. In addition, if necessary, corona discharge treatment may be applied to the back side of the base sheet, or a primer layer may be formed on the back side.

[0126] (Pattern layer) The transfer sheet of the present invention may have a pattern layer. In this specification, if the transfer sheet of the present invention has a pattern layer and a colored opacity layer described later, these will be collectively referred to as the "design layer".

[0127] When the transfer sheet of the present invention has a pattern layer, preferably the pattern layer is located between the surface protective layer and the back adhesive layer.

[0128] The pattern layer applies a desired pattern (design) to the decorative sheet that makes up the transfer sheet, and the types of patterns are not limited. Examples include wood grain patterns, leather patterns, stone patterns, sand patterns, tile patterns, brick patterns, fabric patterns, geometric figures, letters, symbols, abstract patterns, etc.

[0129] The method for forming the pattern layer is not particularly limited. For example, it may be formed on the surface of the substrate sheet by a printing method using an ink obtained by dissolving (or dispersing) a known coloring agent (dye or pigment) together with a binder resin in a solvent (or dispersion medium). From the viewpoint of reducing the VOCs of the decorative sheet, an aqueous composition may also be used as the ink.

[0130] Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc oxide, iron oxide, Prussian blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metallic powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium dioxide-coated mica and bismuth oxide; fluorescent pigments; and luminescent pigments. These colorants can be used individually or in combination of two or more. These colorants may also be used with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants, etc.

[0131] As binder resins, in addition to hydrophilic treated polyester-based urethane resins, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivatives, alcohol adducts of styrene-maleic anhydride copolymer, and cellulose resins can also be used. More specifically, for example, polyacrylamide resins, poly(meth)acrylic acid resins, polyethylene oxide resins, poly-N-vinylpyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino resins, water-soluble phenolic resins, and other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, and polysaccharides can also be used. Furthermore, for example, modified natural rubber, synthetic rubber, polyvinyl acetate resins, (meth)acrylic resins, polyvinyl chloride resins, polyurethane-polyacrylic resins, etc., or mixtures of the above natural rubber, etc., and other resins can also be used. The above binder resins can be used alone or in combination of two or more types.

[0132] Examples of solvents (or dispersion media) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion media) can be used individually or in combination of two or more.

[0133] Furthermore, in recent years, the use of biomass-derived resins, which have a low environmental impact, has been explored in many fields, and the binder resin that forms the pattern layer of the transfer sheet of the present invention can also contain biomass-derived components. For example, biomass-derived urethane (meth)acrylate can be used, and specifically, a binder resin can be made that contains urethane (meth)acrylate containing at least a polyol, an isocyanate compound, and hydroxy(meth)acrylate, and at least one selected from the group consisting of the above polyol, isocyanate compound, and hydroxy(meth)acrylate is a biomass-derived component.

[0134] Printing methods used to form the pattern layer include known printing methods such as gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Furthermore, when forming a solid pattern layer covering the entire surface, various coating methods such as roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating can be used. Other methods such as hand-painting, suminagashi (marbling), photography, transfer, laser beam lithography, electron beam lithography, partial metal deposition, and etching may also be used, or combined with other formation methods.

[0135] The thickness of the pattern layer is not particularly limited and can be set appropriately according to the product characteristics, but the layer thickness is approximately 0.1 to 10 μm.

[0136] (Colored opacity layer) In the transfer sheet of the present invention, a colored opacity layer may be further formed between the base sheet and the pattern layer. In this specification, when the transfer sheet of the present invention has the above-mentioned pattern layer and colored opacity layer, these together will also be referred to as the "design layer".

[0137] The colored opacifying layer only needs to be able to conceal the base color of the substrate when the transfer sheet and the substrate are joined together, and is usually formed to cover the base sheet.

[0138] The above-mentioned known printing method can be used to form the colored opacity layer. Furthermore, the ink used to form the pattern layer can be used as is.

[0139] The application amount is 2-30g / m². 2 A range of this is desirable. The thickness of the colored opacity layer is usually about 0.1 to 20 μm, preferably about 1 to 10 μm.

[0140] (adhesive layer) To improve the adhesion between the transparent resin layer and the pattern layer, as described later, an adhesive layer may be formed on the pattern layer. The adhesive layer is preferably a transparent adhesive layer, and this transparent adhesive layer may include colorless transparent, colored transparent, or translucent.

[0141] The adhesive is not particularly limited, and any adhesive known in the field of transfer sheets can be used.

[0142] Adhesives known in the field of transfer sheets include, for example, thermoplastic resins such as polyamide resins, acrylic resins, and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives can be used individually or in combination of two or more. Two-component curing polyurethane resins or polyester resins using isocyanate as a curing agent can also be used.

[0143] The above-mentioned known printing methods can be used to form the transparent adhesive layer.

[0144] The thickness of the transparent adhesive layer is not particularly limited, but the thickness after drying is approximately 0.1 to 30 μm, preferably 1 to 20 μm.

[0145] (Transparent resin layer) The transfer sheet of the present invention may have a transparent resin layer.

[0146] The transparent resin layer is not particularly limited as long as it is transparent, and includes colorless transparent, colored transparent, translucent, etc. Examples of resins constituting the transparent resin layer include polypropylene such as polyethylene, ethylene-α-olefin copolymer, homopolypropylene, and random polypropylene; olefin resins such as polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and olefin-based elastomers; polyethylene terephthalate, polybutylene terephthalate, polyamide, ionomer, acrylic acid ester polymer, methacrylic acid ester polymer, polycarbonate, and cellulose triacetate. In recent years, the use of biomass-derived resins, which have a low environmental impact, has been explored in many fields, and the resin forming the transparent resin layer of the transfer sheet of the present invention can also contain biomass-derived components, specifically biomass polyolefins, etc. The transparent resin layer can be made using these resins individually or in combination of two or more types.

[0147] The transparent resin layer is preferably a transparent thermoplastic resin layer, more preferably an olefin-based resin such as polypropylene resin or polyethylene resin, and even more preferably the resin constituting the transparent resin layer is the above-mentioned olefin-based resin or ionomer-based resin.

[0148] The transparent resin layer may be colored as long as it remains transparent, but it is preferable not to include any coloring agents.

[0149] The transparent resin layer may further contain various additives as needed. Examples include lubricants such as silicone resin, wax, and fluororesin; colorants such as dyes and pigments; antioxidants; ultraviolet absorbers; light stabilizers; and flame retardants. The content of the above additives is not particularly limited, and for example, it is 0.1% by mass or more and 10% by mass or less, with the transparent resin layer being 100% by mass.

[0150] The transparent resin layer preferably contains an ultraviolet absorber from the viewpoint of providing weather resistance.

[0151] Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers. Among these, triazine-based UV absorbers are preferred. One or more types of UV absorbers can be used.

[0152] Among triazine-based UV absorbers, hydroxyphenyltriazine-based UV absorbers in which at least one organic group selected from hydroxyphenyl groups, alkoxyphenyl groups, and organic groups containing these groups is linked to a triazine ring are more preferred, and hydroxyphenyltriazine-based UV absorbers represented by the following general formula (A) are even more preferred. Because hydroxyphenyltriazine-based UV absorbers have a branched structure, they are expected to be less prone to bleeding out from the transparent resin layer, and thus provide superior weather resistance over a longer period.

[0153] [ka]

[0154] In general formula (A), R 11 R is a divalent organic group, 12 is -C(=O)OR 15 The ester group shown is R 13 , R 14 and R 15 Each of these is an independently monovalent organic group, n 11 and n 12 Each of these is an independent integer between 1 and 5.

[0155] R 11Examples of divalent organic groups include aliphatic hydrocarbon groups such as alkylene groups and alkenylene groups. From the viewpoint of weather resistance, alkylene groups are preferred, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, even more preferably 1 to 8, and particularly preferably 1 to 4. The alkylene group and alkenylene group may be linear, branched, or cyclic, but linear and branched are preferred.

[0156] Examples of alkylene groups having 1 to 20 carbon atoms include various propylene groups such as methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, and 2,2-propylene (hereinafter, "various" refers to linear, branched, and their isomers), various butylene, various pentylene, various hexylene, various heptylene, various octylene, various nonylene, various desilene, various undecylen, various dodecylen, various tridecylen, various tetradecylen, various pentadecylen, various hexadecylen, various heptadecylen, various octadecylen, various nonadecylen, and various eicosilene groups.

[0157] R 13 and R 14 Examples of monovalent organic groups include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups, with aromatic hydrocarbon groups such as aryl groups and arylalkyl groups being preferred, and aryl groups being particularly preferred. Among these, R 13 and R 14 A phenyl group is preferred as the monovalent organic group.

[0158] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms, such as phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups. The arylalkyl group is preferably an arylalkyl group having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 7 to 10 carbon atoms, such as benzyl group, phenethyl group, various phenylpropyl groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, and various hexylbenzyl groups.

[0159] R 15 Examples of monovalent organic groups include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and arylalkyl groups, with aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups being preferred, and alkyl groups being more preferred. That is, R 12 Preferably, alkyl ester groups and alkenyl ester groups are used, with alkyl ester groups being more preferred.

[0160] Examples of alkyl groups include alkyl groups having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and even more preferably 6 to 12 carbon atoms, such as methyl groups, ethyl groups, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, and various eicosyl groups.

[0161] Examples of alkenyl groups include, preferably, alkenyl groups having 2 to 20 carbon atoms, more preferably 3 to 16 carbon atoms, and even more preferably 6 to 12 carbon atoms, such as vinyl groups, various propenyl groups, various butenyl groups, various pentenyl groups, various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadecenyl groups, and various icocenyl groups.

[0162] More specifically, hydroxyphenyltriazine compounds used as hydroxyphenyltriazine-based ultraviolet absorbers represented by general formula (A) include R 11 is an alkylene group having 1 to 20 carbon atoms, and R 12 However, R 15 R is an alkyl ester group having 1 to 20 C12, 13 and R 14 is an aryl group having 6 to 20 carbon atoms, n 11 and n 12 A hydroxyphenyltriazine compound with 1 is preferred, R 11 is an alkylene group having 1 to 12 carbon atoms, R 12 However, R 15 R is an alkyl ester group having 2 to 16 C16 C16, 13 and R 14 is an aryl group having 6 to 12 carbon atoms, n 11 and n 12 A hydroxyphenyltriazine compound with 1 is more preferred, R 11 is an alkylene group having 1 to 8 carbon atoms, and R 12 However, R 15 R is an alkyl ester group having 6 to 12 C 13 and R 14 is an aryl group having 6 to 10 carbon atoms, n 11 and n 12 A hydroxyphenyltriazine compound with 1 is even more preferred, R 11is an alkylene group having 1 to 4 carbon atoms, R 12 However, R 15 R is an ester group which is an alkyl group having 8 carbon atoms, 13 and R 14 is a phenyl group, n 11 and n 12 A hydroxyphenyltriazine compound with a ratio of 1 is particularly preferred.

[0163] Examples of the above hydroxyphenyltriazine compounds include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-ethyl-hexanoic acid-2-[4-(4,6-diphenyl-[1,3,5]triazine-2-yl)-3-hydroxy- Examples include phenoxy-ethyl ester, octanoic acid-2-[4-(4,6-diphenyl-[1,3,5]triazine-2-yl)-3-hydroxyphenoxy]ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1-3-5-triazine, and mixtures thereof, modified products, polymers, derivatives, etc.

[0164] The amount of ultraviolet absorber is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 5.0 parts by mass, and even more preferably 1.0 to 4.0 parts by mass, per 100 parts by mass of the resin component constituting the transparent resin layer.

[0165] Examples of light stabilizers include aromatic compounds, amine compounds, organic acid compounds, catechin compounds, and hindered amine compounds, with hindered amine compounds being preferred. Hindered amine compounds are those having a structure that includes a 2,2,6,6-tetramethylpiperidine skeleton within the molecule.

[0166] The content of the light stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8.0 parts by mass, and even more preferably 1.0 to 5.0 parts by mass, per 100 parts by mass of the resin component constituting the transparent resin layer. It is preferable that the light stabilizer contains a hindered amine compound within the above range.

[0167] Examples of the above-mentioned flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, aluminum-based flame retardants, antimony-based flame retardants, magnesium-based flame retardants, boron-based flame retardants, and zirconium-based flame retardants. From an environmental standpoint, non-halogen-based flame retardants are more preferably used. The above-mentioned flame retardants can be used individually or in combination of two or more types.

[0168] Examples of phosphorus-based flame retardants include phosphinate metal salt-based flame retardants and phosphazene-based flame retardants. Furthermore, regardless of the type, the content of the flame retardant is preferably 3 parts by mass or more, and preferably 30 parts by mass or less, per 100 parts by mass of the resin component constituting the transparent resin layer. By staying within the above range, the flame retardancy of the decorative sheet transferred from the transfer sheet of the present invention is improved while suppressing the impairment of the required performance as a decorative sheet that was originally present.

[0169] The thickness of the transparent resin layer is usually around 20 to 200 μm, but it may exceed this range depending on the application of the transfer sheet.

[0170] (Primer layer) A primer layer may be provided on the transparent resin layer. The primer layer can be formed by applying a known primer to the surface of the transparent resin layer. Examples of primers include urethane resin primers made of acrylic-modified urethane resin (acrylic urethane resin), primers made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrate), and resin primers made of a block copolymer of acrylic and urethane. Additives may be added to the primer as needed. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The amount of additives can be appropriately set according to the product characteristics.

[0171] The amount of primer to be applied is not particularly limited, but is usually 0.1 to 100 g / m². 2 Preferably 0.1 to 50 g / m 2 It is to that extent.

[0172] The thickness of the primer layer is not particularly limited, but is usually 0.01 to 10 μm, preferably about 0.1 to 1 μm.

[0173] (Primer layer on the back) A backside primer layer may be provided on the back surface of the base sheet (the surface opposite to the surface on which the pattern layer is laminated), if necessary. This is effective, for example, when laminating a transfer sheet and a substrate (adherent) and peeling off the release film to produce a decorative material.

[0174] The backside primer layer can be formed by applying a known primer to the substrate sheet. Examples of primers include urethane resin primers made of acrylic-modified urethane resin (acrylic urethane resin), primers made of urethane-cellulose resin (for example, a resin made by adding hexamethylene diisocyanate to a mixture of urethane and nitrate), and resin primers made of acrylic and urethane block copolymers. Additives may be added to the primer as needed. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, UV absorbers, and light stabilizers. The amount of additives can be appropriately set according to the product characteristics.

[0175] The amount of primer to be applied is not particularly limited, but is usually 0.1 to 100 g / m². 2 Preferably 0.1 to 50 g / m 2 It is to that extent.

[0176] The thickness of the primer layer on the back surface is not particularly limited, but is usually 0.01 to 10 μm, preferably about 0.1 to 1 μm.

[0177] (Synthetic resin backing layer) A synthetic resin backer layer (hereinafter also simply referred to as the "backer layer") may be provided on the back surface of the base sheet. This synthetic resin layer enhances scratch resistance and mitigates the influence of the substrate (adhered material). The scratch resistance mentioned above refers specifically to resistance to dents caused by localized loads. The decorative sheet transferred from the transfer sheet of the present invention has sufficient scratch resistance even without a backer layer, but various performance characteristics such as scratch resistance can be further enhanced by providing a backer layer.

[0178] A suitable method for forming the backer layer is extrusion molding of molten resin, and for example, extrusion molding using a T-die is preferred.

[0179] Methods for bonding the back surface of the base sheet to the backer layer include bonding the base sheet and the backer layer obtained by extruding molten resin by heat fusion, and bonding by providing an adhesive layer (and a primer layer if necessary) between the base sheet and the backer layer.

[0180] The resins that make up the backer layer are not limited to these, but include thermoplastic resins such as polyethylene, polypropylene (PP), polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate (A-PET), highly heat-resistant polyalkylene terephthalate (for example, polyethylene terephthalate in which part of the ethylene glycol is replaced with 1,4-cyclohexanedimethanol or diethylene glycol, so-called trade name PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate (PBT), polycarbonate, polyarylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, and ABS (acrylonitrile-butadiene-styrene copolymer). In recent years, the use of biomass-derived resins with low environmental impact has been explored in many fields, and the resin forming the backer layer of the transfer sheet of the present invention can also contain biomass-derived components, specifically biomass polyolefins. These resins can be used individually or in combination of two or more.

[0181] The thickness of the backer layer can be set appropriately depending on the application and usage of the final product, and is generally preferred to be between 100 and 800 μm. Among these, 100 to 600 μm is more preferred.

[0182] The backer layer may be subjected to known easy-adhesion treatments on the bonding surface, such as corona discharge treatment, plasma treatment, degreasing treatment, or surface roughening treatment, as needed. Furthermore, a primer layer may be provided on the back surface to improve adhesion to the adherend.

[0183] (Vesiculation of various additives contained in each layer of the transfer sheet) The various additives added to each of the above-mentioned layers of the transfer sheet of the present invention (such as inorganic fillers added to the primer layer and surface protective layer) are preferably vesicled. The method for vesicling the various additives is not particularly limited and can be done by known methods, with supercritical reverse-phase evaporation being preferred.

[0184] Vesicle formation methods include the supercritical reverse-phase evaporation method, as well as the Bangham method, extrusion method, hydration method, reverse-phase evaporation method, and freeze-thaw method. Briefly explaining these vesicle formation methods, the Bangham method involves placing chloroform or a chloroform / methanol mixed solvent in a container such as a flask, then adding phospholipids and dissolving them. After that, the solvent is removed using an evaporator to form a thin film of lipids, and after adding a dispersion of additives, vesicles are obtained by hydrating and dispersing with a vortex mixer. The extrusion method involves preparing a phospholipid solution of the thin film and obtaining vesicles by passing it through a filter instead of using a mixer as an external perturbation in the Bangham method. The hydration method is almost the same preparation method as the Bangham method, but instead of using a mixer, vesicles are obtained by gently stirring and dispersing. The reverse-phase evaporation method involves dissolving phospholipids in diethyl ether or chloroform, adding a solution containing additives to create a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The freeze-thaw method uses cooling and heating as external perturbations, and vesicles are obtained by repeating this cooling and heating process.

[0185] The supercritical reverse-phase evaporation method is described in detail below. The supercritical reverse-phase evaporation method is a method for forming capsule-shaped vesicles containing the various additives as encapsulating materials in a single membrane by adding an aqueous phase containing various water-soluble or hydrophilic encapsulating materials to a mixture obtained by uniformly dissolving a substance that forms the outer membrane of a vesicle in carbon dioxide in a supercritical state or under temperature or pressure conditions above the supercritical point. Supercritical carbon dioxide refers to carbon dioxide in a supercritical state above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa), while carbon dioxide under temperature or pressure conditions above the critical point refers to carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, single-layer lamellar vesicles with a diameter of 50 to 800 nm can be obtained. Generally, a vesicle is a general term for a vesicle containing a liquid phase inside a vesicle with a closed spherical membrane structure, and in particular, those whose outer membrane is composed of biolipids such as phospholipids are called liposomes.

[0186] Examples of the phospholipids mentioned above include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soy lecithin, and hydrogenated soy lecithin, as well as sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0187] The materials that make up the outer film may also include nonionic surfactants or dispersants such as mixtures of nonionic surfactants with cholesterol or triacylglycerols.

[0188] As the nonionic surfactants mentioned above, one or more of the following can be used: polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc.

[0189] The above-mentioned cholesterols may include one or more types such as cholesterol, α-cholestanol, β-cholestanol, cholestan, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, and cholecalciferol.

[0190] The outer membrane of the liposome described above may be formed from a mixture of phospholipids and a dispersant. In the transfer sheet of the present invention, by using liposomes formed from phospholipids for the outer membrane, the compatibility between the resin composition, which is the main component of each layer, and various additives can be improved.

[0191] (Method of manufacturing transfer sheets) The transfer sheet of the present invention is obtained by forming at least a surface protective layer on a release film. For example, it can be obtained by forming a surface protective layer on a release film, and then laminating a primer layer, a transparent resin layer, a transparent adhesive layer, a pattern layer, a base sheet, and a back adhesive layer.

[0192] 2. Decorative materials The cosmetic material of the present invention is a cosmetic material having a transferred cosmetic sheet on a substrate, which is transferred from the above transfer sheet. The cosmetic material of the present invention has a transferred cosmetic sheet on a substrate. The cosmetic material of the present invention only needs the cosmetic sheet to be laminated on the substrate so that the surface protective layer of the cosmetic sheet becomes the outermost layer. That is, the cosmetic material of the present invention is an exterior member having at least a surface protective layer and a substrate, the surface protective layer contains a crosslinked curable resin, and in the infrared spectroscopic measurement of the surface protective layer, 855~1325cm -1 Let the height of the peak appearing at be A, and 1650~1800cm -1 When the height of the peak appearing at is B, the peak height ratio of A to B ((A / B)×100(%)) is 105% or more and 400% or less, and in the infrared spectroscopic measurement of the surface protective layer, 3200~3500cm -1 When the height of the peak appearing at is C, the peak height ratio of B to C ((B / C)×100(%)) is 1000% or more and 6000% or less, which is an exterior member.

[0193] The substrate (adhered material) is not limited, and a substrate used for a known exterior member can be used, such as plastics, wood materials, metals, ceramics, glass, etc. More specifically, as the substrate, an acrylic plate, a polycarbonate plate, a non-combustible plate, a metal plate, a vinyl chloride plate, a melamine plate, a carbon fiber reinforced plastic plate, etc. can be preferably used.

[0194] A pattern layer and / or a coloring concealment layer may be formed on the substrate. By having a pattern layer and / or a coloring concealment layer on the substrate, even if the transfer sheet has a layer structure without a pattern layer and a coloring concealment layer, the cosmetic material can be given a design property. As the pattern layer and the coloring concealment layer formed on the substrate, the same layers as the pattern layer and the coloring concealment layer formed on the above transfer sheet may be formed.

[0195] The method of laminating the transfer sheet and the substrate is not limited. For example, if the transfer sheet has a back adhesive layer on its back surface (the side opposite to the release film), the sheets can be laminated so that the back adhesive layer and the substrate are in contact, pressed together, and then the release film is peeled off. Alternatively, a method can be employed in which the transfer sheet is attached to the substrate with an adhesive and then the release film is peeled off. The adhesive can be appropriately selected from known adhesives depending on the type of substrate. Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, as well as butadiene / acrylonitrile rubber, neoprene rubber, and natural rubber. These adhesives can be used individually or in combination of two or more types.

[0196] The decorative material of the present invention, manufactured in this manner, can be suitably used as exterior components in the building materials field and the like. [Examples]

[0197] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[0198] (Preparation of transfer sheet) Example 1 A mirror-finish PET film (product name: E5001, manufactured by Toyobo Co., Ltd.) was prepared as the release film. A surface protective layer-forming composition containing an ionizing radiation-curable resin containing a urethane acrylate oligomer was applied to one side of the release film, with a dry coating amount of 10 g / m². 2 The surface was coated and dried in that manner.

[0199] Furthermore, as the urethane acrylate oligomer contained in the ionizing radiation-curable resin that forms the surface protective layer, a mixed resin was used, which was prepared by mixing the following urethane acrylate oligomers in the following proportions. A composition for forming the surface protective layer was prepared by adding the following ultraviolet absorber, light stabilizer, and additives in the following amounts to 100 parts by mass of the mixed resin. • Bifunctional urethane acrylate oligomer A (polyol component is polyester diol, Tg: 25℃, molecular weight 1500) • Hexafunctional aliphatic urethane acrylate oligomer B (Tg: 200℃ or higher, molecular weight 1500, manufactured by Kyoeisha Chemical Co., Ltd., UA306H) Mixing ratio (mass ratio) A:B=80:20 • UV absorber: Tinuvin 400 (manufactured by BASF Ltd.) 5 parts by mass • Light stabilizer: Tinuvin 123 (manufactured by BASF Corporation) 2 parts by mass (Additives) • Diluting solvent: 50 parts by mass of ethyl acetate • Gloss adjuster: Inorganic filler L-121 (manufactured by AGC SI-TEC Co., Ltd.) 8 parts by mass

[0200] Next, an electron beam (pressure voltage: 90kV, 5Mrad (50kGy)) was irradiated to form a surface protective layer with a thickness of 10μm.

[0201] A heat-sealing agent containing acrylic resin (polymethyl methacrylate) was applied to the formed surface protective layer and dried to form a 5 μm thick adhesive backing layer. This produced a transfer sheet having the release film, surface protective layer, and backing adhesive layer (heat-sealing layer) in this order in the thickness direction.

[0202] Example 2 As a release film, we prepared a mirror-finish PET film (product name: E5001, manufactured by Toyobo Co., Ltd.).

[0203] On one side of the release film, apply the following surface protective layer forming composition 2, with a coating amount of 5 g / m² after drying. 2 The surface was coated and dried. Next, an electron beam (pressure voltage: 90kV, 5Mrad (50kGy)) was irradiated to form a 5μm thick surface protective layer 2. Then, corona discharge treatment was performed on the obtained surface protective layer 2, the surface protective layer forming composition 1 was applied and dried to form a 5μm thick surface protective layer 1.

[0204] [Composition 1 for forming surface protective layer] Composition 1 for forming a surface protective layer was prepared by adding the following ultraviolet absorber, light stabilizer, and additives in the following amounts to 100 parts by mass of the main component. • Main component: Acrylic polyol (acrylic polyol containing urethane bonds, curing agent (forms urethane bonds through bonding with isocyanate containing NH groups)) (glass transition temperature approximately 100°C, weight-average molecular weight Mw approximately 40,000, hydroxyl value 12) • UV absorber: Tinuvin 399 (manufactured by BASF Corporation) 5 parts by mass • Light stabilizer: Tinuvin 123 (manufactured by BASF Corporation) 3 parts by mass (Additives) • Diluting solvent: 50 parts by mass of ethyl acetate • Gloss adjuster: Inorganic filler L-121 (manufactured by AGC SI-TEC Co., Ltd.) 15 parts by mass • Hardener: Duranate TAP-100 (manufactured by Asahi Kasei Corporation) 5 parts by mass

[0205] [Surface protective layer forming composition 2] A mixed resin was prepared by blending the following resins in a mass ratio of A:B:C = 60:30:10. A surface protective layer-forming composition 2 was prepared by adding the following light stabilizer, photopolymerization initiator, and additives to 100 parts by mass of the mixed resin in the amounts specified below. • Resin A: Polyfunctional urethane acrylate oligomer having 3 to 15 functional groups • Resin B: Polyfunctional urethane acrylate oligomer having 2 to 9 functional groups • Resin C: 100 parts by mass of acrylic polyol with a glass transition temperature of approximately 100°C, a weight-average molecular weight Mw of approximately 50,000, and a hydroxyl value of 15, per 5 parts by mass of the curing agent Duranate TAP-100 (manufactured by Asahi Kasei Corporation). • Light stabilizer: Sanol LS765 (manufactured by BASF Ltd.) 3 parts by mass • Photopolymerization initiator: Irgacure 907 (manufactured by BASF Ltd.) 2.5 parts by mass • Photopolymerization initiator: Irgacure 184 (manufactured by BASF Ltd.) 2.5 parts by mass (Additives) • Diluting solvent: 50 parts by mass of ethyl acetate • Gloss adjuster: Inorganic filler L-121 (manufactured by AGC SI-TEC Co., Ltd.) 10 parts by mass

[0206] On the obtained surface protective layer 1, the following ink composition containing resin components and pigments was applied by gravure coating and dried to form a design layer with a thickness of 3 to 5 μm, including a pattern layer and a solid print layer (color-opaque layer). On the obtained design layer, an adhesive composition containing acrylic resin and vinyl chloride-vinyl acetate copolymer in a 6:4 (mass ratio) ratio was applied by gravure coating and dried to form a back adhesive layer with a thickness of 2 μm.

[0207] [Ink composition] • Ink resin component (mixed resin of urethane resin and polyacrylic polyol (mass ratio 20:80)) • Pigments (organic pigments and inorganic pigments)

[0208] As a result, a transfer sheet was manufactured having a release film, a surface protection layer 2, a surface protection layer 1, a design layer (pattern layer and color-concealing layer), and a back adhesive layer in this order in the thickness direction.

[0209] Example 3 A mirror-finish PET film (product name: E5001, manufactured by Toyobo Co., Ltd.) was prepared as the release film. A surface protective layer-forming composition containing an ionizing radiation-curable resin containing a urethane acrylate oligomer was applied to one side of the release film, with a dry coating amount of 10 g / m². 2 The surface was coated and dried in that manner.

[0210] Furthermore, as the urethane acrylate oligomer contained in the ionizing radiation-curable resin that forms the surface protective layer, a mixed resin was used, which was prepared by mixing the following urethane acrylate oligomers in the following proportions. A composition for forming the surface protective layer was prepared by adding the following ultraviolet absorber, light stabilizer, and additives in the following amounts to 100 parts by mass of the mixed resin. • Bifunctional urethane acrylate oligomer A (polyol component is polyester diol, Tg: 25℃, molecular weight 1500) • Bifunctional urethane acrylate oligomer B (polyol component is polyester diol, Tg: -55℃, molecular weight 5000) • Hexafunctional urethane acrylate oligomer C (Tg: 200℃ or higher, molecular weight 1500, manufactured by Kyoeisha Chemical Co., Ltd., UA306H) Mixing ratio (mass ratio) A:B:C=60:10:30 • UV absorber: Tinuvin 400 (manufactured by BASF Ltd.) 5 parts by mass • Light stabilizer: Tinuvin 123 (manufactured by BASF Corporation) 2 parts by mass (Additives) • Diluting solvent: 50 parts by mass of ethyl acetate • Gloss adjuster: Inorganic filler L-121 (manufactured by AGC SI-TEC Co., Ltd.) 25 parts by mass

[0211] Next, an electron beam (pressure voltage: 90kV, 5Mrad (50kGy)) was irradiated to form a surface protective layer with a thickness of 10μm.

[0212] On the obtained surface protective layer, the following ink composition containing resin components and pigments was applied by gravure coating and dried to form a design layer with a thickness of 3 to 5 μm, including a pattern layer and a solid print layer (color-opaque layer). On the obtained design layer, an adhesive composition containing acrylic resin and vinyl chloride-vinyl acetate copolymer in a 6:4 (mass ratio) ratio was applied by gravure coating and dried to form a back adhesive layer with a thickness of 2 μm.

[0213] [Ink composition] • Ink resin component (mixed resin of urethane resin and polyacrylic polyol (mass ratio 20:80)) 80 parts by mass • Pigments (organic pigments and inorganic pigments) 20 parts by mass

[0214] As a result, a transfer sheet was manufactured having a release film, a surface protective layer, a design layer (pattern layer and color-concealing layer), and a back adhesive layer in this order in the thickness direction.

[0215] Example 4 As the urethane acrylate oligomer contained in the ionizing radiation-curable resin for forming the surface protective layer, a mixed resin obtained by mixing the following urethane acrylate oligomers in the following formulation was used. With respect to 100 parts by mass of the said mixed resin, the following ultraviolet absorber, light stabilizer, and additives were added in the following amounts to prepare a composition for forming a surface protective layer. Otherwise, in the same manner as in Example 3, a transfer sheet having a release film, a surface protective layer, a design layer (pattern layer and colored concealment layer), and an adhesive layer in this order in the thickness direction was manufactured. · Bifunctional urethane acrylate oligomer A (the polyol component is polyester diol, Tg: 25°C, molecular weight 1500) · Hexafunctional urethane acrylate oligomer C (Tg: 200°C or higher, molecular weight 1500, UA306H manufactured by Kyoeisha Chemical Co., Ltd.) Mixing ratio (mass ratio) A:B = 65:35 · Ultraviolet absorber: Tinuvin 400 (manufactured by BASF Corporation) 5 parts by mass · Light stabilizer: Tinuvin 123 (manufactured by BASF Corporation) 2 parts by mass (Additives) · Dilution solvent: Ethyl acetate 50 parts by mass · Gloss modifier: Inorganic filler L-121 (manufactured by AGC ST Co., Ltd.) 15 parts by mass

[0216] Comparative Example 1 As the resin for forming the surface protective layer, the urethane acrylate-based ultraviolet curable resin composition "TOMAX FA-3246" (solid content 40%, manufactured by Nippon Chemical Paint Co., Ltd.) and the urethane acrylate-based ultraviolet curable resin "Art Resin UN-904" (solid content 100%, number of (meth)acryloyloxy groups: 10, manufactured by Negami Kogyo Co., Ltd.) were used as the main agents, and they were blended so that the solid content blending ratio (mass ratio) of TOMAX FA-3246 and UN-904 was 80 / 20. Irgacure 184 (photoinitiator, manufactured by BASF) was added in an amount of 3 parts by mass based on the solid content of the resin composition, and then diluted with butyl acetate until the solid content concentration in the paint for forming the surface protective layer reached 30%, and thoroughly stirred to prepare the paint for forming the surface protective layer. The prepared paint for forming the surface protective layer was applied to the surface of the release film using a bar coater, and heat-dried in a drying oven at 80°C for 1 minute to form a coating layer with a coating film thickness of 5.0 μm. Next, using a UV irradiation device set at a height of 60 mm from the coated surface of the coating layer, UV irradiation was performed under the condition of a UV irradiation amount of 2 250 mJ / cm

[0217] (Production of decorative material (exterior member)) Example 1 As the substrate, an acrylic plate with a thickness of 2 mm (product name "Comoglas", manufactured by Kuraray Co., Ltd.) was prepared. The following ink composition containing a resin component and a pigment was applied onto the substrate by gravure coating and dried to form a design layer with a thickness of 3 - 5 μm including a pattern layer and a solid printing layer (colored concealment layer).

[0218] The surface on the side of the back adhesive layer of the transfer sheet manufactured in Example 1 was opposed to the design layer of the substrate and laminated. Using a laminator, heating and pressurization were performed from the transfer sheet side under the conditions of a laminating roll temperature of 170°C and a conveyance speed of 2 m / min to achieve adhesion. The release film was peeled off from the adhered transfer sheet to manufacture a decorative material (exterior member).

[0219] Examples 2-4, Comparative Example 1 As a substrate, a 10-mm thick non-combustible board (fiber-reinforced cement board) with an epoxy resin sealer treatment on the surface where the decorative sheet is to be transferred was prepared. Next, a hot-melt adhesive was applied to the surface on the design layer side of the transfer sheets of Examples 2 to 4 and Comparative Example 1 and dried to form a back adhesive layer. The surface of the substrate with the epoxy resin sealer treatment and the surface of the transfer sheet coated with the hot-melt adhesive (back adhesive layer) were opposed and laminated. Using a laminator, heating and pressing were performed from the transfer sheet side under the conditions of a laminating roll temperature of 170°C and a conveying speed of 2 m / min to achieve adhesion. The release film was peeled off from the adhered transfer sheet to manufacture a decorative material (exterior member).

[0220] Comparative Example 2 As a substrate, a 2-mm thick acrylic board (trade name "Komoglas", manufactured by Kuraray Co., Ltd.) was prepared. The following ink composition containing a resin component and a pigment was applied by gravure coating onto the substrate and dried to form a design layer with a thickness of 3 to 5 μm including a pattern layer and a solid printing layer (coloring concealment layer), thereby manufacturing a decorative material (exterior member).

[0221] Using the transfer sheets and decorative materials prepared in the examples and comparative examples, the following measurements were carried out.

[0222] [IR peak height ratio] Using an infrared spectrophotometer (IRAffinity-1A, manufactured by Shimadzu Corporation), the infrared spectrum of the surface of the surface protection layer of the decorative sheet was measured. On the spectrum chart with the absorbance on the vertical axis, the height of the peak appearing at 855 to 1325 cm[[ID=2I]] -1 was designated as A, the height of the peak appearing at 1650 to 1800 cm -1 was designated as B, and the height of the peak appearing at 3200 to 3500 cm -1 was designated as C. The ratios (A / B)×100 and (B / C)×100 were taken as the peak height ratios.

[0223] To measure peak height, a baseline was drawn for each wavelength range, and the length of the line connecting the peak apex to the baseline so that it was horizontal to the vertical axis was measured. If there were multiple peaks within a wavelength range, two peaks were considered "two peaks" if the difference between the peak and trough of adjacent peaks was 0.010 Abs or more, and the sum of the heights of these peaks was defined as the "peak height."

[0224] [Adhesion] A grid peel test was conducted on the surface protective layer of the decorative sheet under JIS-K5600-5-6 conditions, specifically at 25°C and 50% RH. Specifically, a cutter knife was used to make 11 vertical and 11 horizontal cuts at 1mm intervals in a grid pattern on the surface protective layer of the decorative sheet, creating a total of 100 squares. Adhesive tape No. 252 manufactured by Sekisui Chemical Co., Ltd. was then applied to these squares, pressed evenly with a spatula, and peeled off at a 60-degree angle. After repeating the pressing and peeling process five times at the same location, the number of remaining layers of the surface protective layer was measured and evaluated according to the evaluation criteria below. For evaluation of adhesion after the environmental test, the decorative sheet was left in a humid heat environment of 60°C and 90% RH for three weeks, and then the adhesion was evaluated at 25°C. Note that the vertical direction of the decorative sheet refers to the winding direction of the decorative sheet roll (MD direction in the manufacturing equipment), and the horizontal direction of the decorative sheet refers to the width direction of the decorative sheet roll (TD direction in the manufacturing equipment). (Evaluation Criteria) ++:100 pieces + :95 or more and 99 or less - :80 or more and 94 or less --:79 or less

[0225] [Scratch resistance] 300g / m² of steel wool (Bonstar Co., Ltd. #0000) is applied to the surface protective layer of the decorative sheet. 2 The materials were brought into contact with the surface under a load and a rubbing test was performed under the condition of 300 back-and-forth movements. In accordance with the test method of JIS-K5600-5-10, the surface protective layer side of the decorative sheet was rubbed 100 times back and forth with steel wool #0000 under a load of 1 kg, and the degree of scratching was evaluated according to the evaluation criteria below. (Evaluation Criteria) ++: No occurrence of scratches + : A little scratch occurs - : A large amount of scratches occur

[0226] [Pencil Hardness] The pencil hardness was measured by a test method conforming to JIS K5600-5-4. The hardness with no occurrence of scratches on the surface was defined as the pencil hardness

[0227] [Folding Whitening] The decorative sheet was cut into 10 cm × 10 cm to prepare a test piece. The test piece was rapidly bent 180 degrees in two directions (both vertically and horizontally) so that the surface protection layer side became the peak, and evaluated according to the following evaluation criteria. Note that the vertical direction of the decorative sheet is the winding direction of the original roll of the decorative sheet (MD direction in the manufacturing apparatus), and the horizontal direction of the decorative sheet is the width direction of the original roll of the decorative sheet (TD direction in the manufacturing apparatus). Evaluation Criteria ++: Not whitened at all + : Partially whitened but not noticeable - : Whitened and noticeable

[0228] [Weather Resistance Adhesion (Adhesion after Weather Resistance Test)] The weather resistance adhesion (adhesion after weather resistance test) of the decorative material (exterior member) was evaluated. Specifically, for the decorative material, an accelerated weather resistance test using a metal halide lamp (MWOM) (a test in which ultraviolet rays are irradiated for 20 hours under the following irradiation conditions and then dew condensation is performed for 4 hours under the following dew condensation conditions, with one cycle being defined as the above process and the above cycle being repeated) was carried out for 600 hours

[0229] [Conditions of Accelerated Weather Resistance Test] (Test Apparatus) Manufactured by Dipla·Wintec Co., Ltd., product name "Dipla·Metal Weather" (Irradiation Conditions) Illuminance: 65 mW / cm 2 , Black panel temperature: 63 °C, humidity inside the tank: 50%RH, time: 20 hours (Dew Condensation Conditions) Illuminance: 0 mW / cm2 , Humidity inside the tank: 98%RH, Time: 4 hours

[0230] The weather-resistant adhesion of the decorative material that underwent accelerated weathering testing was evaluated by performing the same tests as the adhesion test described above.

[0231] [Weather resistance of the design (design quality after weather resistance testing)] The decorative material (exterior component) was subjected to the same accelerated weathering test as the one used to evaluate weather adhesion described above. The decorative material was visually observed from the side with the protective surface layer before and after the accelerated weathering test, and the aesthetic appeal of the pattern was evaluated based on human perception according to the following evaluation criteria: +: Compared to the pattern before the accelerated weathering test, there was no discoloration of the pattern after the accelerated weathering test, indicating superior aesthetic appeal. -: Compared to the pattern before the accelerated weathering test, the pattern after the accelerated weathering test has discolored, resulting in inferior design quality.

[0232] The results are shown in Table 1.

[0233] [Table 1]

[0234] From the results in Table 1, in Examples 1 and 2, the peak height ratio of A to B was 221 or 116, indicating that they have an appropriate amount of ester bonds. This resulted in an appropriate hardness for the surface protective layer, excellent scratch resistance, pencil hardness, and bending whitening, demonstrating that they possess a combination of these properties. Furthermore, in Examples 1 and 2, the peak height ratio of B to C was 1723 or 5057, indicating an appropriate amount of urethane bonds. As shown in Figure 8, it is thought that hydrogen bonds are formed with the ester bonds in the surface protective layer, resulting in a ++ rating for adhesion. Additionally, hydrolysis is suppressed, leading to a ++ rating for adhesion after environmental testing.

[0235] Furthermore, the results in Table 1 show that in Example 3, the surface protective layer was relatively softer compared to the surface protective layers of Examples 1 and 2. Specifically, the peak height ratio of A to B was larger compared to Examples 1 and 2, indicating fewer ester bonds, resulting in a softer surface protective layer. Although scratch resistance and pencil hardness were slightly inferior compared to Examples 1 and 2, bending whitening was more suppressed. Additionally, in Example 3, the peak height ratio of B to C was larger compared to Examples 1 and 2, indicating fewer urethane bonds, resulting in slightly inferior adhesion compared to Examples 1 and 2. Moreover, it was more susceptible to hydrolysis, resulting in slightly inferior adhesion after environmental testing.

[0236] Furthermore, as shown in Table 1, it was found that in Example 4, the surface protective layer was relatively harder and more brittle compared to the surface protective layers of Examples 1 and 2. Specifically, the peak height ratio of A to B was smaller compared to Examples 1 and 2, indicating a greater number of ester bonds, resulting in a harder surface protective layer. Although the pencil hardness was rated H, the bending whitening was rated +. In addition, in Example 4, the peak height ratio of B to C was smaller compared to Examples 1 and 2, indicating a greater number of urethane bonds. As shown in Figure 8, it is thought that hydrogen bonds were formed between the ester bonds in the surface protective layer, resulting in a ++ adhesion rating. Furthermore, hydrolysis was more suppressed, leading to a ++ adhesion rating after environmental testing.

[0237] In Table 1, in Comparative Example 1, the peak height ratio between A and B was small at 103%, while the peak height ratio between B and C was large at 6500, indicating inferior adhesion to the underlying layer, surface hardness, scratch resistance, and processability. Furthermore, in Comparative Example 1, the weather resistance and design weather resistance were rated as -, indicating that after transferring the decorative sheet from the transfer sheet, the decorative sheet exhibited inferior weather resistance and design weather resistance.

[0238] Example 5 A transfer sheet and decorative material were prepared in the same manner as in Example 1, except that 3 parts by mass of a phosphate-based glass silver-supported compound (PG-711, manufactured by Koa Glass Co., Ltd.) was added as an antiviral agent to 100 parts by mass of an ionizing radiation-curable resin that forms the surface protective layer. The peak height ratios of surface protective layers A and B, and B and C were the same as in Example 1.

[0239] The release film was peeled off the transfer sheets prepared in Example 1 and Example 5 to prepare decorative sheets, and the following evaluations were performed using these decorative sheets.

[0240] [Antiviral] <Evaluation Method> In Examples 1 and 5, the release film was peeled off the transfer sheets to prepare decorative sheets. These decorative sheets were then subjected to antiviral performance tests in accordance with the antiviral test method (ISO 21702), and the antiviral activity value against influenza virus was calculated and evaluated based on the evaluation criteria below. The results are shown in Table 2. A + rating indicates that there are no problems in actual use. In Table 2, the antiviral agent (parts by mass) refers to the amount of antiviral agent used (parts by mass) per 100 parts by mass of ionizing radiation-curable resin. <Evaluation Criteria> +: Antiviral activity value was 2.0 or higher. -: Antiviral activity value was less than 2.0.

[0241] The results are shown in Table 2.

[0242] [Table 2]

[0243] Example 6 A transfer sheet and decorative material were prepared in the same manner as in Example 1, except that the following resin compositions were laminated by heat-melt extrusion to form an 80 μm transparent resin layer as a transparent polypropylene resin (transparent random polypropylene resin). The peak height ratios of surface protective layers A and B, and B and C, were the same as in Example 1. (Resin composition) • Transparent polypropylene resin: 100 parts by mass • Phosphinate metal salt-based flame retardant (product name: Pekoflam STC (manufactured by Arkroma); aluminum phosphinate): 10 parts by mass

[0244] The release film was peeled off the transfer sheets prepared in Examples 1 and 6 to prepare decorative sheets, and the following evaluations were performed using these decorative sheets.

[0245] [Flame retardancy assessment] The decorative panels prepared in Examples 1 and 6 were cut to a size of 9 cm x 30 cm to serve as test specimens. As shown in Figures 9 and 10, a rectangular metal stand 103 was placed on the base 102 of a commercially available household heater 101 (Zaigle Handsome SJ-100 (product name)), and the test specimen 105 was placed inside a metal frame 104 installed on the stand. A test was then conducted to determine the resistance to flame spread under the conditions of a heater angle of 45° and heater output dial 4. In detail, the test specimen was preheated for 2 minutes using the above-mentioned household heater. Then, as shown in Figure 9, the heater-side end 106 of the test specimen in the longitudinal direction was heated with a lighter 107 for 1 minute to ignite it. As shown in Figure 10, the test specimen 105 was allowed to burn in the longitudinal direction. Next, the burning state was observed visually, and the burning distance (L1) and burning duration were evaluated as follows. This allowed for the evaluation of horizontal flammability (resistance to fire spreading).

[0246] (Burning distance (L1)) The test specimen was ignited, and after removing the lighter flame, the distance the flame spread from the initial ignition was measured to determine the burning distance (L1). This was then evaluated according to the following evaluation criteria. A rating of + or higher indicates that the specimen is considered suitable for practical use. ++: L1 is less than 5cm +: L1 is between 5cm and 10cm. -: L1 is 10cm or larger

[0247] (Burning duration) The test specimen was ignited, the lighter flame was removed, and the burning time from initial ignition to self-extinguishing was measured and evaluated according to the following evaluation criteria. A rating of + or higher indicates that there are no problems in actual use. +++: The burning time is less than 100 seconds, or it does not ignite. ++: Burning duration is 100 seconds or more but less than 300 seconds. +: Burning duration is 300 seconds or more but less than 600 seconds. -: The burning time is 600 seconds or more (it does not self-extinguish after 600 seconds).

[0248] The results are shown in Table 3.

[0249] [Table 3]

[0250] Example 7 A transfer sheet and decorative material were prepared in the same manner as in Example 1, except that a resin layer forming unevenness was formed on the surface to which the composition for forming the surface protective layer of the release film was coated by the following method. The peak height ratios of surface protective layers A and B, and B and C were the same as in Example 1.

[0251] <Method for forming a resin layer with uneven surfaces> A 100 μm thick transparent polypropylene (PP) film treated with corona discharge was prepared as a release film, and a two-component curing urethane resin was applied to the corona discharge-treated surface at a drying rate of 1 g / m². 2 A primer layer was formed by applying the material. On the primer layer, a resin layer forming composition for creating unevenness, with the composition described later, was applied at a dry rate of 5 g / m². 2 The coating was applied to form a film.

[0252] First, as part of the irradiation treatment (C), ultraviolet light is irradiated onto the coating film using a UV irradiation device consisting of LEDs (LED-UV irradiation, wavelength 395nm, illuminance 600mW / cm²). 2 , cumulative light intensity 30 mJ / cm 2 The coating was then pre-cured.

[0253] Next, as part of the irradiation process (A), ultraviolet light is irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe2), ultraviolet power density 30 mW / cm²). 2 , cumulative light intensity 30 mJ / cm 2 Random, wrinkle-like irregularities were formed on the surface of the coating film (under a nitrogen atmosphere).

[0254] Next, as part of the irradiation treatment (B), an electron beam was irradiated (acceleration voltage 125kV, irradiation dose 60kGy, nitrogen atmosphere) to form a surface protective layer (thickness 5μm) with irregularities on the outermost surface.

[0255] (Composition for forming an uneven resin layer) • Monofunctional acrylate monomer (monofunctional monomer) 40 parts by mass • 30 parts by mass of bifunctional acrylate monomer (polyfunctional monomer) • Photopolymerization initiator (benzophenone-based) 0.8 parts by mass • Water repellent (silicone-based) 0.5g

[0256] The release film was peeled off the transfer sheets prepared in Examples 1 and 7 to prepare decorative sheets, and the following evaluations were performed using these decorative sheets.

[0257] (i) Ra (arithmetic mean roughness) The surface roughness (Ra) of the protective layer of the decorative sheet was measured according to the measurement method compliant with JIS B0601:2013, under the condition of a cutoff value of 0.8 mm. Measurements were taken at 10 arbitrary locations, and the average value was used as the measured value.

[0258] (ii) RSm (average length of the curve element) The RSm (average length of curved elements) of the surface protective layer of the decorative sheet was measured using a measurement method compliant with JIS B0601:2013, under the condition of a cutoff value of 0.8 mm. Measurements were taken at 10 arbitrary locations, and the average value was used as the measured value.

[0259] [Specular gloss] The specular gloss of the decorative sheet was measured from the surface protective layer side using a 60-degree specular gloss tester (GMX-203 model) manufactured by Murakami Color Technology Laboratory, in accordance with JIS Z 8741:1997.

[0260] The results are shown in Table 4.

[0261] [Table 4] [Explanation of symbols]

[0262] 1: Transfer sheet 10: Release film 11: Decorative sheet 111: Base material sheet 112: Pattern layer 113: Transparent resin layer 114: Surface protective layer 2: Base 101. Household heaters 102. Stand for household heater 103. Rectangular metal stand 104. Metal frame 105. Test specimen 106. End of the test specimen on the heater side in the longitudinal direction 107. Writer L1. Burning distance

Claims

1. A transfer sheet having at least a surface protective layer and a release film, The aforementioned surface protective layer contains a cross-linked curing resin, In the infrared spectroscopic measurement of the surface protective layer, 855–1325 cm⁻¹ －１ Let A be the height of the peak that appears, between 1650 and 1800 cm. －１ When the peak height appearing is B, the peak height ratio of A to B ((A / B) × 100 (%)) is between 105% and 400%. In the infrared spectroscopic measurement of the aforementioned surface protective layer, 3200 to 3500 cm⁻¹ －１ When the peak height appearing is C, the peak height ratio of B to C ((B / C) × 100 (%)) is between 1000% and 6000%. A transfer sheet characterized by the following features.

2. The transfer sheet according to claim 1, wherein the peak height ratio between A and B is 110% or more and 300% or less, and the peak height ratio between B and C is 1300% or more and 5500% or less.

3. The transfer sheet according to claim 1, wherein the cross-linked curable resin includes an ionizing radiation curable resin.

4. The transfer sheet according to claim 3, wherein the ionizing radiation-curable resin includes an acrylic resin having a (meth)acryloyl group.

5. The transfer sheet according to claim 1, wherein the surface protective layer comprises at least one selected from the group consisting of antibacterial agents, antiviral agents, and allergen reducing agents.

6. The transfer sheet according to claim 1, wherein the surface protective layer has a back adhesive layer on the side opposite to the release film.

7. The transfer sheet according to claim 6, further comprising a pattern layer between the surface protective layer and the back adhesive layer.

8. The transfer sheet according to claim 1, wherein the surface protective layer has a ridged shape.

9. The transfer sheet according to claim 8, wherein the surface protective layer has an arithmetic mean roughness Ra of 0.2 μm or more and 3.0 μm or less, an average length RSm of the curved elements of 50.0 μm or more and 100.0 μm or less, and a 60-degree specular gloss of 1 or more and 10 or less as measured in accordance with JIS Z8741:1997.

10. A decorative material having a decorative sheet transferred from a transfer sheet according to any one of claims 1 to 9 on a substrate.

11. An exterior component having at least a surface protective layer and a substrate, The aforementioned surface protective layer contains a cross-linked curing resin, In the infrared spectroscopic measurement of the surface protective layer, 855–1325 cm⁻¹ －１ Let A be the height of the peak that appears, between 1650 and 1800 cm. －１ When the peak height appearing is B, the peak height ratio of A to B ((A / B) × 100 (%)) is between 105% and 400%. In the infrared spectroscopic measurement of the aforementioned surface protective layer, 3200 to 3500 cm⁻¹ －１ When the peak height appearing is C, the peak height ratio of B to C ((B / C) × 100 (%)) is between 1000% and 6000%. An exterior component characterized by the following features.

12. The exterior member according to claim 11, wherein the substrate is an acrylic sheet, a polycarbonate sheet, a non-combustible sheet, a metal sheet, a polyvinyl chloride sheet, a melamine sheet, or a carbon fiber reinforced plastic sheet.

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