Transfer sheet, method for manufacturing transfer sheet, method for manufacturing exterior member, and exterior member

Abstract

The present invention provides a transfer sheet for manufacturing an exterior member, the transfer sheet having a mold release film and a transfer layer disposed on one surface of the mold release film, the transfer layer having a first protective layer and a second protective layer in this order from the mold release film side in the thickness direction, the first protective layer containing a cured product of a first curable resin composition and a weather-resistant agent, and the second protective layer containing a cured product of a second curable resin composition and a weather-resistant agent. The first protective layer contains a cured product of a first curable resin composition and a weather-resistant agent, the second protective layer contains a cured product of a second curable resin composition and a weather-resistant agent, and the cured product of the first curable resin composition and the cured product of the second curable resin composition each contain a (meth) acrylic acid component and a urethane component. The indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less, and the indentation hardness of the cross section of the second protective layer is 2 MPa or more and 50 MPa or less.

Description

Technical Field

[0001] The present invention relates to a transfer sheet, a method for manufacturing the transfer sheet, a method for manufacturing an exterior component, and the exterior component. Background Art

[0002] It is known to decorate a substrate such as a metal component or a resin component by transferring a transfer layer (a layer transferred from a transfer sheet) in a transfer sheet to the substrate. For example, Patent Document 1 discloses a design transfer sheet comprising a release layer and a design transfer layer releasably attached to the release layer. The design transfer layer comprises, in order from the release layer side, a first surface layer capable of heat bonding and a second surface layer capable of heat bonding.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-120643 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] The transfer sheet, for example, has a release film, a first protective layer and a second protective layer in sequence in the thickness direction. In such a transfer sheet, the adhesion of the first protective layer and the second protective layer is likely to be insufficient. The first protective layer is typically produced by curing a first protective layer-forming composition on a release film. Since the second protective layer is formed on the cured first protective layer, the adhesion of the first protective layer and the second protective layer is likely to be insufficient. In addition, since exterior components (outdoor components) are exposed to harsh environments, the first protective layer and the second protective layer constituting the transfer layer in the transfer sheet for manufacturing exterior components are required to have not only good initial adhesion but also good weather-resistant adhesion. In addition, for the transfer sheet, the surface of the transfer layer transferred to the substrate is required to have damage resistance.

[0008] The present invention has been made in view of the above-mentioned actual situation, and its main object is to provide a transfer sheet having a transfer layer with excellent transfer resistance and good weather-resistant adhesion between the first and second protective layers.

[0009] Technical means to solve the problem

[0010] The present invention provides a transfer sheet for use in manufacturing exterior components. The transfer sheet comprises a release film and a transfer layer disposed on one surface of the release film. The transfer layer comprises a first protective layer and a second protective layer in order from the release film side in the thickness direction. The first protective layer comprises a cured product of a first curable resin composition and a weathering agent. The second protective layer comprises a cured product of a second curable resin composition and a weathering agent. The cured products of the first curable resin composition and the second curable resin composition each comprise a (meth)acrylic acid component and a urethane component. When a cross-sectional sample of the transfer sheet is prepared using a resin embedding method and a microtome, the indentation hardness of the cross section of the first protective layer is 150 MPa to 300 MPa, and the indentation hardness of the cross section of the second protective layer is 2 MPa to 50 MPa.

[0011] In addition, the present invention provides a method for manufacturing a transfer sheet, which is the above-mentioned method for manufacturing a transfer sheet, comprising: a first protective layer forming step, in which a first composition comprising the above-mentioned first curable resin composition and the above-mentioned weathering agent is applied to the surface of the above-mentioned release film and cured to form the above-mentioned first protective layer; and a second protective layer forming step, in which a second composition comprising the above-mentioned second curable resin composition and the above-mentioned weathering agent is applied to the surface of the above-mentioned first protective layer opposite to the above-mentioned release film and cured to form the above-mentioned second protective layer.

[0012] The present invention provides a method for manufacturing an exterior member, comprising: a preparation step of preparing the transfer sheet; and a bonding step of placing the second protective layer side of the transfer sheet facing a substrate and bonding them together.

[0013] The present invention provides an exterior component comprising, in order in the thickness direction, a first protective layer, a second protective layer, an adhesive layer, and a substrate, wherein the first protective layer comprises a cured product of a first curable resin composition and a weathering agent, and the second protective layer comprises a cured product of a second curable resin composition and a weathering agent, wherein the cured product of the first curable resin composition and the cured product of the second curable resin composition each comprise a (meth)acrylic component and a urethane component. When a cross-sectional sample piece of the exterior component is prepared using a resin embedding method and a microtome, the indentation hardness of the cross section of the first protective layer is greater than or equal to 150 MPa and less than or equal to 300 MPa, and the indentation hardness of the cross section of the second protective layer is greater than or equal to 2 MPa and less than or equal to 50 MPa.

[0014] Effects of the Invention

[0015] The present invention has the effect of providing a transfer sheet capable of transferring a transfer layer having excellent scratch resistance and good weather-resistant adhesion between the first protective layer and the second protective layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic cross-sectional view illustrating the transfer sheet in the present invention.

[0017] Figure 2 This is a schematic cross-sectional view illustrating the method for producing a transfer sheet in the present invention.

[0018] Figure 3 This is a schematic cross-sectional view illustrating a method for manufacturing an exterior member according to the present invention.

[0019] Figure 4 This is a schematic cross-sectional view showing an example of the exterior member in the present invention. DETAILED DESCRIPTION

[0020] The following describes embodiments with reference to the accompanying drawings. However, the present invention can be implemented in many different ways and is not limited to the following exemplary embodiments. Furthermore, for clarity, the drawings may schematically illustrate the width, thickness, and shape of various components, as compared to their actual form. However, this is merely an example and should not be construed as limiting.

[0021] In this specification, when expressing the manner in which another component is disposed on a certain component, when simply stated as "on..." or "below...", unless otherwise specified, this includes both the manner in which the other component is disposed directly above or directly below the certain component so as to be in contact with the certain component, and the manner in which the other component is disposed above or below the certain component with other components interposed therebetween. Furthermore, in this specification, when expressing the manner in which another component is disposed on the surface of a certain component, when simply stated as "on the surface...", unless otherwise specified, this includes both the manner in which the other component is disposed directly above or directly below the certain component so as to be in contact with the certain component, and the manner in which the other component is disposed above or below the certain component with other components interposed therebetween.

[0022] Hereinafter, the transfer sheet, the method for producing the transfer sheet, the method for producing the exterior member, and the exterior member according to the present invention will be described in detail.

[0023] A. Transfer Sheet

[0024] Figure 1 (a) is a schematic cross-sectional view illustrating the transfer sheet of the present invention. Figure 1 As shown in (a), the transfer sheet 10 includes a release film 1 and a transfer layer X disposed on one side of the release film 1. The transfer layer X extends from the release film 1 side in the thickness direction D. T The first protective layer 2 and the second protective layer 3 are sequentially provided on the substrate. Figure 1 As shown in (b) in FIG. 1 , the transfer sheet 10 may include an adhesive layer 4 on the surface of the second protective layer 3 opposite to the first protective layer 2. Figure 1 As shown in (c) in FIG. 1 , the transfer sheet 10 may have a design layer 5 on the surface of the second protective layer 3 opposite to the first protective layer 2. Figure 1 As shown in (d) , the transfer sheet 10 may include an adhesive layer 4 on the surface of the design layer 5 opposite to the second protective layer 3 .

[0025] The transfer sheet of the present invention comprises a first protective layer 2 comprising a cured product of a specific first curable resin composition and a weathering agent. Cross-sectional samples of the transfer sheet produced by a specific method exhibit an indentation hardness within a specific range. Furthermore, the second protective layer 3 comprises a cured product of a specific second curable resin composition and a weathering agent. Cross-sectional samples of the transfer sheet produced by a specific method exhibit an indentation hardness within a specific range. This invention enables the production of a transfer sheet for exterior components that exhibits excellent weather-resistant adhesion and damage resistance.

[0026] As described above, in the transfer sheet, the adhesion of the first protective layer and the second protective layer is easily insufficient. Here, in the case of a decorative sheet, a design layer is usually formed on the base material layer, and then a second protective layer is formed on the design layer, and then the first protective layer is formed on the second protective layer. Typically, the first protective layer is made by curing the first protective layer-forming composition formed on the second protective layer, so the adhesion of the first protective layer and the second protective layer becomes good. In contrast, in the case of a transfer sheet, the first protective layer is usually formed on a release film, and then a second protective layer is formed on the first protective layer, and then a design layer is formed on the second protective layer. Typically, the first protective layer is made by curing the first protective layer-forming composition on a release film. Since the second protective layer is formed on the cured first protective layer, the adhesion of the first protective layer and the second protective layer is easily insufficient.

[0027] Because the first protective layer is required to have good damage resistance, it is preferable that the first protective layer have low flexibility. Furthermore, the inventors of this application have determined that the second protective layer requires a certain degree of flexibility to achieve close adhesion (initial adhesion and weathering adhesion) with the cured first protective layer. Furthermore, they have determined that in environments subject to repeated temperature fluctuations, such as those caused by daytime and seasonal temperature differences, the first protective layer may not be able to follow the second protective layer, resulting in poor weathering adhesion.

[0028] The present inventors have discovered that the indentation hardness measured on a cross-sectional sample of a transfer sheet produced using a resin embedding method and a microtome can more accurately evaluate the flexibility of a layer than the indentation hardness measured on a cross-sectional sample produced by, for example, mechanical grinding. Furthermore, the present inventors have discovered that, when cross-sectional samples of the transfer sheet are produced using a resin embedding method and a microtome, the indentation hardness of the cross section of the first protective layer is within a specific range, and the indentation hardness of the cross section of the second protective layer is within a specific range. This allows for the production of a transfer sheet having a transfer layer with excellent transferable damage resistance and good weather-resistant adhesion between the first and second protective layers.

[0029] In addition, compared with interior components (indoor components), exterior components (outdoor components) require high weather resistance. For example, when using decorative sheets to manufacture exterior components, there is a case where a transparent resin layer is provided on the decorative sheet in order to improve strength. In this case, since the transparent resin layer is a relatively thick layer, high weather resistance is imparted by, for example, adding a sufficient amount of weathering agent to the transparent resin layer. In contrast, it is technically difficult to impart high weather resistance to a transfer sheet that does not have a layer equivalent to a transparent resin layer. In the present invention, usually both the first protective layer and the second protective layer contain a weathering agent. Thus, high weather resistance can be imparted while maintaining the properties required for the first protective layer (such as surface properties such as damage resistance and wear resistance) and the properties required for the second protective layer (such as adhesion).

[0030] 1. First protection layer

[0031] The transfer sheet of the present invention has a first protective layer. The first protective layer contributes to improving the surface properties of the exterior member (such as scratch resistance and wear resistance). The first protective layer and the release film are preferably placed in direct contact.

[0032] (1) Indentation hardness

[0033] In the present invention, when a cross-sectional sample of the transfer sheet is prepared using a resin embedding method and a microtome, the indentation hardness of the cross section of the first protective layer is generally 150 MPa or more, and may be 180 MPa or more, or 190 MPa or more. If the indentation hardness of the cross section of the first protective layer is low, good damage resistance and wear resistance may not be achieved. On the other hand, the indentation hardness of the cross section of the first protective layer is generally 300 MPa or less, and may be 280 MPa or less, or 250 MPa or less. If the indentation hardness of the cross section of the first protective layer is high, the first protective layer's ability to follow the second protective layer is reduced, and good weather-resistant adhesion may not be achieved.

[0034] The indentation hardness of the cross section of the first protective layer can be adjusted, for example, by adjusting the number of functional groups of the curable resin in the first curable resin composition used to form the first protective layer. For example, by reducing the number of functional groups of the ionizing radiation-curable compound, the number of crosslinking points in the cured product of the first curable resin composition can be reduced, thereby forming a softer structure and reducing the indentation hardness.

[0035] The indentation hardness of the cross section of the first protective layer is a value measured by the following method using a cross-section sample piece prepared using a resin embedding method and a microtome, using the following indentation hardness measurement method.

[0036] (Method for preparing cross-sectional sample piece for measurement)

[0037] The transfer sheet is cut into any size to prepare a cut sample. The cut sample is embedded with a resin (a two-liquid epoxy curing resin at room temperature) and left at room temperature for more than 24 hours to solidify, thereby preparing an embedded sample (resin embedding method) in which the cut sample is embedded with a resin. Using a microtome, the embedded sample is cut vertically to prepare a cross-section sample piece for indentation hardness measurement in which the cross section of the layer to be measured is exposed. Specifically, an ultrathin microtome (Leica EM UC6, manufactured by Leica Microsystems) equipped with a cryo-cutting system (Leica EM FC6, manufactured by Leica Microsystems) and a diamond knife are used to prepare a cross section in which the cross section of the layer to be measured is exposed at -120°C. Compared with the cross section obtained by cutting at room temperature, the cross section roughness can be suppressed and a cross section suitable for indentation test can be obtained. Especially in the case of soft materials, the cross section roughness can be suppressed.

[0038] (Measurement method of indentation hardness)

[0039] The term "indentation hardness" used in this specification is measured using the nanoindentation method. Nanoindentation is a method for calculating mechanical quantities based on a load-displacement curve obtained by continuously measuring the load and displacement during the process of pressing and removing the indenter from the sample surface.

[0040] Specifically, the indentation hardness of the cross section of the first protective layer is measured by vertically pressing a Berkovich indenter (material: diamond triangular pyramid) into the cut surface of the above-mentioned measurement sample using the following nanoindenter. The measuring apparatus and measurement conditions are as follows. Here, the position where the Berkovich indenter is pressed is preferably approximately the center in the thickness direction of the first protective layer. Approximately the center means that when the thickness of the first protective layer is defined as T [μm], the deviation from the center in the thickness direction of the first protective layer is within ±0.1T. In addition, when the layer contains microparticles such as fillers (such as silica), the above-mentioned Berkovich indenter is pressed into a position avoiding the microparticles.

[0041] Device used: Nanoindenter (TI 950 TriboIndenter, manufactured by BRUKER)

[0042] Indenter used: Bosch indenter (Model: TI-0039, manufactured by BRUKER)

[0043] Press-in control method: displacement control method (no lifting action)

[0044] Maximum indentation depth: 100nm

[0045] Pressing speed: 10nm / s

[0046] Load time: 10 seconds (from 0 to 100nm)

[0047] Holding time: 5 seconds (holding 100nm)

[0048] Unloading time: 10 seconds (from 100nm to 0)

[0049] Number of measurements: 5 times

[0050] The indentation hardness of the cross section of the first protective layer can be calculated as follows. First, the indentation depth h (nm) corresponding to the indentation load P (N) is continuously measured and a load-displacement curve is plotted. The plotted load-displacement curve is analyzed to calculate the maximum indentation load P max (N) divided by the projected area A (mm) of contact between the indenter and the cross section of the first protective layer at this time 2 ) is taken as the indentation hardness H IT (Formula (1) below).

[0051] H IT =P max / A ···(1)

[0052] Here, A is the contact projection area obtained by correcting the indenter tip shape using fused quartz, a standard sample, according to the apparatus standard method.

[0053] In this specification, the indentation hardness of the cross-section of the first protective layer is measured five times at offset positions on the same sample, and the arithmetic mean of these measurements is calculated. It should be noted that each measurement was performed with an offset of at least 5 μm. During the measurement, to confirm that the indenter shape is correctly corrected and that there are no problems with the device's operation and measurement, it is preferred to use the device manufacturer's standard sample, fused quartz, and confirm that the measurement is within ±5% of the reference value. The indentation hardness measurement atmosphere is set to a temperature of 23°C ± 5°C and a humidity of 40% to 65%.

[0054] (2) Resin component

[0055] The first protective layer comprises a cured product (cross-linked structure) of the first curable resin composition. In addition, the cured product of the first curable resin composition comprises a (meth) acrylic acid component and a carbamate component. The (meth) acrylic acid component refers to an acrylic acid component or a methacrylic acid component. The carbamate component refers to a carbamate bond. In addition, the proportion of the cured product of the first curable resin composition relative to the total resin components constituting the first protective layer is, for example, 70% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0056] Examples of the first curable resin composition include ionizing radiation curable resin compositions and thermosetting resin compositions. Examples of ionizing radiation curable resin compositions include electron beam curable resin compositions and ultraviolet curable resin compositions. Of these, electron beam curable resin compositions are preferred because they do not require a polymerization initiator, have low odor, and are less likely to discolor.

[0057] An ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as an "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that undergoes cross-linking and curing by irradiation with ionizing radiation. The ionizing radiation curable resin composition preferably contains at least a compound having a (meth)acryloyl group. (Meth)acryloyl refers to an acryloyl group or a methacryloyl group. In addition, in addition to the compound having a (meth)acryloyl group, the ionizing radiation curable resin composition may also contain a compound having a functional group having an olefinic double bond, such as a vinyl group or an allyl group.

[0058] The number of functional groups of the ionizing radiation curable compound is preferably 2 to 20, more preferably 2 to 18, and even more preferably 2 to 15. This is because it facilitates adjustment of the indentation hardness of the first protective layer to the above range.

[0059] Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Examples of ionizing radiation include electron beams (EB) and ultraviolet rays (UV). Other examples of ionizing radiation include electromagnetic waves such as X-rays and gamma rays, alpha rays, and charged particle beams such as ion beams.

[0060] The ionizing radiation curable resin composition preferably contains at least urethane (meth)acrylate as an ionizing radiation curable compound. (Meth)acrylate refers to acrylate or methacrylate. In addition, the ionizing radiation curable resin composition may also contain at least one of epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and acrylic acid (meth)acrylate as an ionizing radiation curable compound in addition to urethane (meth)acrylate.

[0061] The ionizing radiation curable resin composition preferably contains caprolactone urethane (meth) acrylate as the urethane (meth) acrylate. In addition, the ionizing radiation curable resin composition may also contain caprolactone urethane (meth) acrylate and urethane (meth) acrylate that is not modified with caprolactone. In this case, the content of the caprolactone urethane (meth) acrylate contained in the first protective layer is set to M CLUA , the content of urethane (meth) acrylate not modified with caprolactone is set as M UA . M CLUA Relative to M UA and M CLUA The mass ratio of the total amount (M CLUA / (M UA +M CLUA )) is, for example, 10 mass % to 90 mass %, may be 20 mass % to 80 mass %, or may be 30 mass % to 70 mass %.

[0062] When the ionizing radiation-curable compound includes caprolactone-based urethane (meth)acrylate, the number of functional groups of the caprolactone-based urethane (meth)acrylate is preferably 2 or more and 9 or less, and more preferably 2 or more and 5 or less. This is because by setting the number of functional groups of the caprolactone-based urethane (meth)acrylate within the above range, it is easy to adjust the indentation hardness of the cross section of the first protective layer to the above range.

[0063] Caprolactone urethane (meth)acrylates can generally be obtained by reacting caprolactone polyols, organic isocyanates, and hydroxyl-containing (meth)acrylates. For example, the following synthesis method is used: a polycaprolactone polyol is reacted with an organic polyisocyanate to produce a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, which is then reacted with a hydroxyl-containing (meth)acrylate.

[0064] As caprolactone-based polyols, commercially available products can be used, preferably caprolactone-based polyols having two hydroxyl groups and a number average molecular weight of preferably 500 to 3000, more preferably 750 to 2000. In addition, one polyol other than caprolactone-based polyols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., can also be used, or a plurality of polyols other than caprolactone-based polyols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., can be mixed and used in any proportion. As organic polyisocyanates, diisocyanates having two isocyanate groups are preferred. From the perspective of suppressing yellowing, for example, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc. are preferred. As the hydroxyl group-containing (meth)acrylate, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, etc. are preferable.

[0065] When using a caprolactone-based polyol, the caprolactone-based urethane (meth)acrylate is preferably a caprolactone diol-based urethane (meth)acrylate. Caprolactone diol-based urethane (meth)acrylate refers to a caprolactone-based urethane (meth)acrylate terminated with diethylene glycol. By using a caprolactone diol-based urethane (meth)acrylate, cracking and whitening of the first protective layer can be suppressed.

[0066] The number average molecular weight of the ionizing radiation curable compound is, for example, 1000 to 10000, or 2000 to 10000. The number average molecular weight is an average molecular weight measured by GPC (Gel Permeation Chromatography) analysis and converted to standard polystyrene.

[0067] For example, when the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable compound preferably contains at least one of a photopolymerization initiator and a photopolymerization accelerator. Examples of photopolymerization initiators include acetophenone, benzophenone, α-hydroxyalkyl phenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyl oxime ester, acylphosphine oxide, and thioxanthones. Examples of photopolymerization accelerators include isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate.

[0068] The first curable resin composition may be a thermosetting resin composition. Details of the thermosetting resin composition are the same as those described in the following "2. Second Protective Layer".

[0069] (3) Weathering agent

[0070] The first protective layer typically contains a weathering agent. Examples of weathering agents include ultraviolet absorbers and light stabilizers. The first protective layer preferably contains at least one of the ultraviolet absorbers and light stabilizers. The first protective layer may contain one or more ultraviolet absorbers. Similarly, the first protective layer may contain one or more light stabilizers.

[0071] Examples of the UV absorber contained in the first protective layer include organic UV absorbers such as triazine-based UV absorbers, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, oxybenzophenone-based UV absorbers, salicylate-based UV absorbers, and cyano(meth)acrylate-based UV absorbers; and inorganic UV absorbers such as titanium dioxide, cerium oxide, and zinc oxide. Among these, triazine-based UV absorbers are more preferred.

[0072] Examples of the triazine-based ultraviolet absorbers include hydroxyphenyltriazine-based ultraviolet absorbers. Examples of the hydroxyphenyltriazine-based ultraviolet absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0073] The content of the ultraviolet absorber contained in the first protective layer is, for example, 0.5 parts by mass to 10 parts by mass, or 0.8 parts by mass to 8 parts by mass, or 1 part by mass to 5 parts by mass, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the ultraviolet absorber is high, the ultraviolet absorber may bleed out, while if the content of the ultraviolet absorber is low, sufficient ultraviolet absorption performance may not be achieved.

[0074] Examples of the light stabilizer contained in the first protective layer include hindered amine light stabilizers. Examples of the hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, (1,2,2,6,6-pentamethyl-4-piperidinyl)methyl sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamino)-1,3,5-triazine.

[0075] The content of the light stabilizer contained in the first protective layer is, for example, 1 part by mass or more and 10 parts by mass or less, 1.5 parts by mass or more and 8 parts by mass or less, or 2 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the light stabilizer is high, the light stabilizer may bleed out, while if the content of the light stabilizer is low, sufficient light stability may not be achieved.

[0076] (4) Additives

[0077] The first protective layer may contain additives such as silicone compounds, polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropy imparting agents, coupling agents, plasticizers, antifouling agents, defoaming agents, fillers, anti-wear agents, antibacterial agents, antiviral agents, and antifungal agents.

[0078] (5) 1st protective layer

[0079] The thickness of the first protective layer is, for example, 2 μm to 20 μm, or 3 μm to 15 μm, or 4 μm to 10 μm. If the first protective layer is thin, sufficient weather resistance may not be achieved. If the first protective layer is thick, cracks may easily form in the first protective layer, and good adhesion may not be achieved.

[0080] 2. Second protection layer

[0081] The transfer sheet of the present invention has a second protective layer. The second protective layer and the first protective layer may be disposed in direct contact or with another layer interposed therebetween.

[0082] (1) Indentation hardness

[0083] In the present invention, when a cross-sectional sample piece of a transfer sheet is prepared using a resin embedding method and a microtome, the indentation hardness of the cross section of the second protective layer is generally above 2 MPa, and may also be above 5 MPa, or may be above 10 MPa. On the other hand, the indentation hardness of the cross section of the second protective layer is generally below 50 MPa, and may also be below 40 MPa, or may be below 30 MPa. If the indentation hardness of the cross section of the second protective layer is high, the adhesion (especially the initial adhesion) to the first protective layer may be reduced. It should be noted that the method for preparing the cross-sectional sample piece of the transfer sheet and the method for measuring the indentation hardness of the cross section of the second protective layer are the same as the method described above for the first protective layer.

[0084] (2) Resin component

[0085] The second protective layer comprises a cured product (cross-linked structure) of a second curable resin composition. Furthermore, the cured product of the second curable resin composition comprises a (meth) acrylic acid component and a urethane component. Furthermore, the proportion of the cured product of the second curable resin composition relative to the total resin components constituting the second protective layer is, for example, 70% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0086] As the second curable resin composition, for example, a thermosetting resin composition can be cited. A thermosetting resin composition is a composition comprising at least a thermosetting resin, and is a composition that is cured by heating. The thermosetting resin composition preferably comprises at least a carbamate (meth) acrylic resin as a thermosetting resin. In addition to the carbamate (meth) acrylic resin, the second curable resin composition may also comprise at least one of a (meth) acrylic resin, a carbamate resin, a phenolic resin, a urea-melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin as a thermosetting resin. In addition, the thermosetting resin composition may also comprise a curing agent such as an isocyanate curing agent and an epoxy curing agent.

[0087] When the second curable resin composition includes a urethane (meth)acrylic resin, the urethane (meth)acrylic resin is preferably a urethane (meth)acrylic copolymer, and more preferably a polycarbonate urethane (meth)acrylic copolymer. The polycarbonate urethane (meth)acrylic copolymer is a resin obtained by free radical polymerization of a polyurethane polymer obtained by reacting a (meth)acrylic acid monomer with a polycarbonate diol and a (di)isocyanate.

[0088] Examples of the (di)isocyanate include aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 1,5-naphthalene diisocyanate, orthoisocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; and alicyclic isocyanates such as isophorone diisocyanate, hydrogenated xylylenediisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0089] Examples of the (meth)acrylic monomer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate and other alkyl (meth)acrylates.

[0090] In the polycarbonate-based urethane (meth)acrylic acid copolymer, the mass ratio of the urethane component to the total amount of the (meth)acrylic acid component and the urethane component ([urethane component] / ([(meth)acrylic acid component]+[urethane component]) is, for example, 65% by mass or more and 95% by mass or less, or 70% by mass or more and 90% by mass or less. By setting the mass ratio to 65% by mass or more, the proportion of the polycarbonate structure in the polycarbonate-based urethane (meth)acrylic acid copolymer can be increased, thereby making the structure of the polycarbonate-based urethane acrylic acid copolymer more rigid. As a result, the indentation hardness of the cross section of the second protective layer can be adjusted to a specific value or more. In addition, by setting the mass ratio to 95% by mass or less, the indentation hardness of the cross section of the second protective layer can be adjusted to a specific value or less.

[0091] (3) Weathering agent

[0092] The second protective layer typically contains a weathering agent. Examples of weathering agents include ultraviolet absorbers and light stabilizers. The second protective layer preferably contains at least one of these. Preferred types and configurations of weathering agents are the same as those described in "1. First Protective Layer" above and are therefore omitted here. The second protective layer particularly preferably contains a triazine-based ultraviolet absorber. Furthermore, the second protective layer preferably contains a hindered amine-based light stabilizer.

[0093] The content of the ultraviolet absorber contained in the second protective layer is, for example, 0.1 parts by mass or more and 50 parts by mass or less, 3 parts by mass or more and 40 parts by mass or less, or 10 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin component. Furthermore, the content of the ultraviolet absorber contained in the second protective layer (relative to 100 parts by mass of the resin component) may be greater than the content of the ultraviolet absorber contained in the first protective layer (relative to 100 parts by mass of the resin component).

[0094] The content of the light stabilizer contained in the second protective layer is, for example, 0.1 parts by mass or more and 15 parts by mass or less, or 1 part by mass or more and 15 parts by mass or less, or 3 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the resin component. Furthermore, the content of the light stabilizer contained in the second protective layer (relative to 100 parts by mass of the resin component) may be greater than the content of the light stabilizer contained in the first protective layer (relative to 100 parts by mass of the resin component).

[0095] (4) Additives

[0096] The second protective layer may contain additives such as silicone compounds, polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropy imparting agents, coupling agents, plasticizers, antifouling agents, defoaming agents, fillers, and antiblocking agents.

[0097] (5) Second protective layer

[0098] The thickness of the second protective layer is, for example, 2 μm to 10 μm, 3 μm to 8 μm, or 3 μm to 5 μm. If the second protective layer is thin, the adhesion (especially initial adhesion) to the first protective layer may be reduced. On the other hand, if the second protective layer is thick, the movement of the second protective layer may be increased in an environment with repeated temperature changes, and good weather-resistant adhesion may not be achieved.

[0099] 3. Transfer layer

[0100] The transfer sheet in the present invention has a release film and a transfer layer arranged on one side of the release film. The transfer layer has at least the first protective layer and the second protective layer in order from the release film side. The transfer layer may have the first protective layer and the second protective layer, and may also have other layers. As other layers, for example, a design layer and an adhesive layer can be mentioned. The transfer layer may have an adhesive layer on the surface of the second protective layer opposite to the first protective layer. In addition, the transfer layer may have a design layer on the surface of the second protective layer opposite to the first protective layer. In addition, the transfer layer may have the first protective layer, the second protective layer, the design layer and the adhesive layer in order from the release film side.

[0101] The thickness of the transfer layer is, for example, 8 μm or greater, 10 μm or greater, 12 μm or greater, or 14 μm or greater. If the transfer layer is thin, sufficient weather resistance may not be achieved. On the other hand, the thickness of the transfer layer is, for example, 50 μm or less, 40 μm or less, or 30 μm or less.

[0102] (1) Adhesive layer

[0103] The transfer sheet of the present invention may or may not have an adhesive layer on the surface of the second protective layer opposite to the first protective layer. When the transfer sheet of the present invention includes the design layer described below, the design layer may have an adhesive layer on the surface opposite to the second protective layer.

[0104] The adhesive layer is preferably a layer that contacts the substrate among the layers of the transfer layer in the transfer sheet. In this case, the adhesive layer is configured to improve the adhesion between the transfer layer and the substrate. The adhesive layer may contain 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.

[0105] The adhesive layer may be a so-called adhesive layer. The adhesive layer has adhesive properties at room temperature. Examples of the resin contained in the adhesive layer include (meth)acrylic resins, silicone resins, vinyl resins, ester resins, urethane resins, amide resins, epoxy resins, rubber resins, and ionomer resins.

[0106] In addition, the adhesive layer can also be a so-called heat seal layer. The heat seal layer develops adhesiveness by heat. As the resin contained in the heat seal layer, thermoplastic resins can be mentioned. As thermoplastic resins, acrylic resins, polyacrylic polyols, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic acid copolymers, acrylic acid-vinyl acetate copolymers, polyester resins, amide resins, cyanoacrylate resins, epoxy resins, etc. can be mentioned. These can be used alone or in combination. Among these, in order to improve the processability during the manufacture of exterior components and the adhesion between the transfer layer and the substrate, it is preferred to use at least one of acrylic resins, polyacrylic polyols and urethane resins. Acrylic resins are particularly preferred.

[0107] The indentation hardness of the cross section of the adhesive layer when using a resin embedding method and a microtome to prepare a cross-sectional sample of the transfer sheet is not particularly limited, and can be, for example, 100 MPa to 300 MPa, 120 MPa to 270 MPa, or 140 MPa to 250 MPa. If the indentation hardness of the cross section of the adhesive layer is within the above range, good weather-resistant adhesion can be achieved, for example, with the design layer. It should be noted that the method for preparing the cross-sectional sample of the transfer sheet and the method for measuring the indentation hardness of the adhesive layer are the same as those described above for the first protective layer.

[0108] The thickness of the adhesive layer is, for example, 1 μm to 30 μm, 2 μm to 10 μm, 3 μm to 8 μm, or 3 μm to 5 μm. When the thickness of the adhesive layer is within the above range, good adhesion between the adhesive layer and the substrate is easily achieved during manufacture of the exterior component.

[0109] In the present invention, the adhesive layer may contain a colorant. Examples of the colorant include the colorants described below for the design layer. By including a colorant in the adhesive layer, the transfer layer can be given a design feature. In other words, the adhesive layer can share the functions of the design layer described below.

[0110] (2) Design layer

[0111] The transfer sheet of the present invention may or may not include a design layer on the surface of the second protective layer opposite the first protective layer. The design layer enhances the design of the exterior component. The design layer and the second protective layer may be placed in direct contact or with another layer interposed between them.

[0112] Examples of the design layer include a full coat layer (a layer fully coated with ink) and a pattern layer (a layer printed with ink). The transfer sheet may have a pattern layer and a full coat layer as the design layer, in order from the release film side. Examples of the pattern (decorative pattern) of the pattern layer include wood grain, stone grain, sand grain, tile pattern, brickwork pattern, fabric pattern, leather pattern, geometric figures, text, symbols, abstract patterns, and floral patterns.

[0113] The design layer typically contains a colorant and a binder resin. Examples of colorants include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, chrome yellow, titanium yellow, red lead, cadmium red, ultramarine, and cobalt blue; organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black; metallic pigments such as aluminum and brass; and pearlescent pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0114] Examples of the binder resin include urethane resins, acrylic polyol resins, (meth)acrylic resins, ester resins, amide resins, butyraldehyde resins, styrene resins, urethane acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic acid copolymers, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins. Among these, the combined use of an acrylic polyol resin and a urethane resin is more preferred.

[0115] When using a resin embedding method and a microtome to prepare cross-sectional sample pieces of the transfer sheet, the indentation hardness of the cross section of the design layer is not particularly limited. For example, it can be between 100 MPa and 300 MPa, or between 120 MPa and 270 MPa, or between 140 MPa and 250 MPa. If the cross-sectional indentation hardness of the design layer is within the above range, good weather-resistant adhesion can be achieved, for example, with the adhesive layer or the second protective layer. It should be noted that the method for preparing cross-sectional sample pieces of the transfer sheet and the method for measuring the indentation hardness of the design layer are the same as those described above for the first protective layer.

[0116] The design layer may contain additives such as ultraviolet absorbers, light stabilizers, curing agents, plasticizers, catalysts, etc. as needed. The thickness of the design layer may be, for example, 0.5 μm to 20 μm, 1 μm to 10 μm, or 2 μm to 5 μm.

[0117] (3) Second release film

[0118] The transfer sheet of the present invention may have a second release film on the surface of the second protective layer opposite to the first protective layer. For example, when the transfer sheet is wound into a roll, this can prevent blocking. The second release film is typically peeled from the transfer sheet before the following lamination step. Details of the second release film are identical to those described for the first release film, and therefore are omitted here.

[0119] 4. Release film

[0120] The transfer sheet of the present invention has a release film (first release film) on the surface of the first protective layer opposite to the second protective layer. The release film and the first protective layer may be disposed in direct contact or with another layer interposed therebetween.

[0121] The release film preferably includes a resin film. Examples of the resin included in the resin film include ester resins, olefin resins, styrene resins, vinyl resins, (meth)acrylic resins, amide resins, imide resins, and carbonate resins.

[0122] The resin film preferably comprises an ester resin or an olefin resin. Examples of ester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymers. Of these, PET or PBT are preferred, and PET is more preferred, from the perspective of being less susceptible to thermal shrinkage during transfer sheet production and shrinkage due to ionizing radiation exposure.

[0123] Examples of olefin resins include polyethylene, polypropylene, polybutene, ethylene-propylene copolymers, and ethylene-propylene-butene copolymers. Of these, polypropylene is preferred because it is less susceptible to thermal shrinkage during transfer sheet production and shrinkage due to ionizing radiation exposure.

[0124] The resin film may be a stretched film or an unstretched film. The stretch ratio in the machine direction (MD) of the stretched film is, for example, 5 times or more and 30 times or less. The stretch ratio in the width direction (TD) of the stretched film is, for example, 5 times or more and 30 times or less. In addition, the thickness of the release film is, for example, 10 μm or more and 200 μm or less, or 15 μm or more and 150 μm or less, or 20 μm or more and 100 μm or less.

[0125] The release film in the present invention may be a mirror film or a low-gloss film depending on the target surface shape of the first protective layer.

[0126] When the release film is a low-gloss film, the 60° gloss value of the first surface of the release film, located opposite the transfer layer, is, for example, 90 or higher, but may also be 100 or higher, or even 110 or higher. By setting the 60° gloss value of the first surface to be above this value, the design of the transfer sheet is easily visible even without removing the release film. This allows defect inspection without removing the release film, improving workability. Furthermore, since the release film can be used directly as a masking material, the amount of plastic used can be reduced. On the other hand, the 60° gloss value of the first surface of the release film is, for example, 200 or lower, but may also be 160 or lower, or even 140 or lower.

[0127] The 60° gloss value of the first surface of the release film was measured by the following method. The release film, peeled from the transfer sheet, was placed with the first surface facing up on matte black backing paper. The 60° specular gloss was measured using a gloss meter ("micro-TRI-gloss (model name)", manufactured by BYK-Gardner) in accordance with JIS Z 8741:1997, Method 3.

[0128] The 60° gloss value of the second surface of the release film, located on the transfer layer side, can be, for example, 40 or less, 35 or less, or 30 or less. If the 60° gloss value of the second surface of the release film is below this value, the transfer layer exhibits low gloss after the release film is removed. On the other hand, the 60° gloss value of the second surface can be, for example, 3.0 or greater, 5.0 or greater, or 10 or greater. If the 60° gloss value of the second surface is low, the resin of the first protective layer may be trapped in fine matte shapes, making removal difficult. Furthermore, the desired shape may not be achieved.

[0129] The 60° gloss value of the second surface of the release film is a value measured by the following method.

[0130] The release film peeled from the transfer sheet was placed on matte black mount paper with the second surface facing upward, and the 60° specular gloss was measured using a gloss meter ("micro-TRI-gloss (model name)", manufactured by BYK-Gardner) in accordance with Method 3 of JIS Z 8741:1997.

[0131] The maximum height Rz of the first surface is, for example, less than 0.8 μm, or less than 0.6 μm, or less than 0.4 μm. Rz (maximum height) is one of the peak and height parameters of the profile curve specified in JIS B0601:2013, and is the sum of the height of the highest peak and the depth of the deepest valley in the profile curve at the reference length. Therefore, if Rz (maximum height) is within the above range, diffuse reflection of light is suppressed and the visibility of the design is improved. On the other hand, the maximum height Rz of the first surface is, for example, greater than 0.1 μm, or greater than 0.2 μm.

[0132] The maximum height Rz of the first surface of the release film is a value measured using the following measuring apparatus and conditions using a rectangle (1024 μm×768 μm) at an arbitrary position on the first surface of the release film as a measurement area.

[0133] Measurement device: Shape analysis laser microscope (VK-X1000, manufactured by KEYENCE Co., Ltd.)

[0134] Objective lens: 50 times

[0135] ·Measurement mode: Shape measurement mode

[0136] ·Measurement pitch: 12μm

[0137] Measurement quality: High-speed mode

[0138] Scanning mode: laser confocal

[0139] In this specification, Rz (maximum height) is the average value of measured values at any 10 locations.

[0140] The maximum height Rz of the second surface of the release film is, for example, 2.0 μm or more, 3.0 μm or more, or 4.0 μm or more. If the maximum height Rz of the second surface is low, the transfer layer after peeling the release film will not easily exhibit a low gloss. On the other hand, the maximum height Rz of the second surface is, for example, 6.0 μm or less, or 5.0 μm or less. The maximum height Rz of the second surface is a value measured on the second surface of the release film using the same method as the method for measuring the maximum height Rz of the first surface described above.

[0141] The release film in the present invention is not particularly limited and may be a single layer or have a multilayer structure. In the case where the release film is a low-gloss film, the release film preferably comprises, for example, a film layer comprising the first surface and a matte layer disposed on the transfer layer side of the film layer and comprising the second surface.

[0142] (i) Film layer

[0143] The film layer is not particularly limited as long as it has the first surface, and is preferably the resin film.

[0144] (ii) Matting layer

[0145] The matte layer is not particularly limited, as long as it has the above-mentioned second surface, and for example, it contains a resin component and particles as a matting agent. Hereinafter, the matte layer containing a resin component and particles as a matting agent is referred to as the first matte layer. The resin component in the first matte layer is typically a cured product (cross-linked structure) of a curable resin. On the other hand, the resin component may also be a thermoplastic resin. Among them, the first matte layer preferably contains a cured product of a curable resin. By making the first matte layer contain a cured product of a curable resin, the demoulding property with the first protective layer becomes good.

[0146] When the second surface of the release film is the surface of the first matte layer, the 60° gloss value and the maximum height Rz can be adjusted by selecting the type of particles, adjusting the average particle size and content, and the like.

[0147] Examples of the curable resin include ionizing radiation curable resins and thermosetting resins, and examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet curable resins.

[0148] There is no limitation on the ionizing radiation curable resin (ionizing radiation curable compound), as long as it is a material that produces a cross-linking polymerization reaction by irradiation with ionizing radiation and becomes a three-dimensional polymer structure. As the ionizing radiation curable resin, for example, prepolymers, oligomers and monomers having polymerizable unsaturated bonds or epoxy groups that can be cross-linked by irradiation with ionizing radiation can be cited. In the present invention, only one ionizing radiation curable resin can be used, or two or more ionizing radiation curable resins can be used. Among them, it is preferred to use at least one of a multifunctional monomer and an oligomer as the ionizing radiation curable resin.

[0149] Examples of ionizing radiation-curable resins include (meth)acrylate resins such as urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate; silicone resins such as siloxane; ester resins; and epoxy resins. (Meth)acrylate resins refer to acrylate resins or methacrylate resins.

[0150] The weight average molecular weight of the ionizing radiation curable resin is, for example, 500 to 80,000, or 1,000 to 50,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0151] The ionizing radiation curable resin preferably contains at least a polyfunctional monomer or oligomer having a weight average molecular weight of 500 or more. Examples of such polyfunctional monomers or oligomers include (meth)acrylate resins such as dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate.

[0152] On the other hand, examples of thermosetting resins include unsaturated ester resins, urethane resins (including two-component curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine urea co-condensation resins, silicone resins, and siloxane resins.

[0153] Examples of the particles include inorganic particles and synthetic resin particles. Examples of the inorganic particles include silicon dioxide, aluminum oxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin. Examples of the synthetic resin particles include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin waxes (e.g., polypropylene wax and polyethylene wax).

[0154] The average particle size of the particles is preferably 1.0 μm or more and 10 μm or less, and more preferably 2.0 μm or more and 8.0 μm or less.

[0155] The content of the particles in the first matte layer is preferably 3 parts by mass or more and 80 parts by mass or less, and more preferably 5 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the resin component.

[0156] The first matte layer may contain additives such as a release agent, an ultraviolet absorber, an infrared absorber, a light stabilizer, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an antioxidant, a leveling agent, a coupling agent, a plasticizer, a defoaming agent, a filler, a thermal radical generator, and an aluminum chelating agent as needed. The thickness of the first matte layer is not particularly limited, and is, for example, 0.1 μm to 10 μm.

[0157] The first matte layer can be obtained, for example, by applying a matte layer-forming ink containing a curable resin to one side of the film layer and curing the ink.

[0158] As the matte layer, for example, a layer having a concave-convex shape composed of irregular wrinkles on one side (second matte layer) can be used. As the material and formation method of the second matte layer, the material and formation method of the release layer described in Japanese Patent Application Laid-Open No. 2022-149930 can be used.

[0159] The first matte layer and the second matte layer may be formed on the entire surface of one side of the film layer, or may be formed on a partial area of one side of the film layer. The entire surface of one side of the film layer refers to an area of more than 90% of one side of the film layer. The matte layer may be configured to cover more than 95% of one side of the film layer, or may be configured to cover 100% of one side of the film layer. On the other hand, the matte layer may be configured to cover less than 50% of one side of the film layer, may be configured to cover less than 40% of one side of the film layer, or may be configured to cover less than 30% of one side of the film layer.

[0160] Furthermore, the low-gloss film is not limited to the aforementioned configuration comprising a film layer and a matte layer; a single layer may also be used. For example, a matte film kneaded with the particles exemplified for the first matte layer may also be used. In this case, the first surface opposite the transfer layer side and the second surface on the transfer layer side have the same 60° gloss value and Rz.

[0161] B. Method for manufacturing transfer sheet

[0162] Figure 2 1 is a schematic cross-sectional view illustrating a method for manufacturing a transfer sheet according to the present invention. Figure 2 As shown in (a) in FIG. 1 , a release film 1 is prepared. Then, as shown in FIG. Figure 2 As shown in (b) in FIG. 1 , a first composition comprising a first curable resin composition and a weathering agent is applied to the surface of the release film 1 and cured to form a first protective layer 2. Figure 2 As shown in (c), a second composition comprising a second curable resin composition and a weathering agent is applied to the surface of the first protective layer 2 opposite to the release film 1 and cured to form a second protective layer 3. T A transfer sheet 10 having a release film 1, a first protective layer 2 and a second protective layer 3 in this order. Figure 2 In the example, the transfer layer X corresponds to the first protective layer 2 and the second protective layer 3. Furthermore, when a cross-sectional sample of the transfer sheet 10 is prepared using a resin embedding method and a microtome, the indentation hardness of the cross section of the first protective layer 2 is within a specific range, and the indentation hardness of the cross section of the second protective layer 3 is within a specific range.

[0163] According to the present invention, for the reasons described above, a transfer sheet for an exterior member having excellent weather-resistant adhesion and scratch resistance can be obtained.

[0164] 1. First protective layer formation step

[0165] The first protective layer forming step in the present invention is a step of applying a first composition comprising the first curable resin composition and a weathering agent to the surface of the release film and curing the composition to form the first protective layer. The first composition is a first protective layer-forming composition. The first curable resin composition and weathering agent are the same as those described in "A. Transfer Sheet" above, and therefore, their description is omitted here.

[0166] Examples of methods for applying the first composition include gravure printing, rod coating, roller coating, reverse roll coating, and notch wheel coating. By applying the first composition, a first coating layer is obtained. Examples of methods for curing the first coating layer include irradiation with ionizing radiation such as electron beams and ultraviolet rays, and heating.

[0167] 2. Second protective layer formation step

[0168] The second protective layer forming step in the present invention is a step of applying a second composition comprising the second curable resin composition and a weathering agent to the surface of the first protective layer opposite the release film and curing the composition to form the second protective layer. The second composition is a second protective layer-forming composition. The second curable resin composition and weathering agent are the same as those described in "A. Transfer Sheet" above, and therefore, their description is omitted here.

[0169] As a method for applying the second composition, for example, gravure printing, rod coating, roller coating, reverse roll coating, and notch wheel coating can be mentioned. By applying the second composition, a second coating layer is obtained. As a method for curing the second coating layer, for example, a heating method can be mentioned.

[0170] 3. Other processes

[0171] The method for manufacturing the transfer sheet of the present invention may also include a step of forming a layer belonging to the above-mentioned transfer layer in addition to the first protective layer forming step and the second protective layer forming step. For example, the method for manufacturing the transfer sheet of the present invention may include an adhesive layer forming step of forming an adhesive layer on the surface of the second protective layer opposite to the first protective layer. As a method for forming the adhesive layer, a composition for forming an adhesive layer can be applied by a known method such as gravure printing, rod coating, roller coating, reverse roll coating, or notch wheel coating, and then dried and cured as needed to form the adhesive layer. For example, the method for manufacturing the transfer sheet of the present invention may include a design layer forming step of forming a design layer on the surface of the second protective layer opposite to the first protective layer. As a method for forming the design layer, for example, a method of applying an ink containing a colorant, a binder resin, and a solvent to the surface of the second protective layer opposite to the first protective layer can be cited. In addition, the transfer sheet obtained by the above-mentioned steps is the same as that described in the above-mentioned "A. Transfer Sheet", so the description is omitted here.

[0172] C. Manufacturing method of exterior components

[0173] Figure 3 This is a schematic cross-sectional view illustrating a method for manufacturing an exterior component according to the present invention. Figure 3 As shown in (a) in FIG. 1 , a transfer sheet 10 is prepared. Figure 3 The transfer sheet 10 shown in (a) is in the thickness direction D T The mold release film 1, the first protective layer 2, the second protective layer 3 and the adhesive layer 4 are sequentially provided on the mold release film 1. Figure 3 As shown in (b), the surface of the transfer sheet 10 on the second protective layer 3 side is facing the base 20, and the two are closely attached. The "surface of the transfer sheet 10 on the second protective layer 3 side" refers to the surface of the transfer sheet 10 located on the second protective layer 3 side when the release film 1 is used as a reference. Figure 3 Since the transfer sheet 10 shown in (a) has the adhesive layer 4, the "surface of the transfer sheet 10 on the second protective layer 3 side" corresponds to the surface of the adhesive layer 4. Then, as Figure 3 As shown in (c) in FIG. 1 , the release film 1 is peeled off from the transfer sheet 10. Thus, a film having a thickness in the direction D is obtained. T The exterior member 100 has a first protective layer 2, a second protective layer 3, an adhesive layer 4 and a base 20 thereon in this order.

[0174] According to the present invention, by using the transfer sheet, an exterior member having excellent weather-resistant adhesion and damage resistance can be obtained.

[0175] 1. Preparation process

[0176] The preparation step in the present invention is a step of preparing the transfer sheet. Since the transfer sheet is the same as that described in the above-mentioned "A. Transfer Sheet", the description thereof is omitted here.

[0177] 2. Sealing process

[0178] The bonding step in the present invention is a step of placing the second protective layer-side surface of the transfer sheet facing the substrate and bonding the two. When the transfer sheet and substrate are placed facing each other, they may be placed in direct contact or with another layer interposed between them. For example, if the transfer sheet does not have an adhesive layer, an adhesive layer may be provided.

[0179] The material of the substrate in the present invention is not particularly limited, and resin, wood, metal, non-metallic inorganic material, paper, nonwoven fabric, woven fabric, etc. can be appropriately selected according to the intended use.

[0180] As an example of the matrix in the present invention, a resin component can be cited. As the resin used for the resin component, for example, vinyl chloride resin, (meth) acrylic resin, ester resin, styrene resin, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), phenol resin, cellulose resin, rubber, polycarbonate resin, melamine resin can be cited. The resin component may contain fibers such as carbon fiber, glass fiber, aromatic polyamide fiber, Zylon fiber, boron fiber, polyethylene fiber, etc. By including fibers, the strength of the resin component can be improved. In addition, as another example of the matrix, a wooden component can be cited. As the wooden component, for example, a wooden veneer, a wooden plywood, a plastic plywood, and a wooden fiberboard can be cited. As the wood used for the wooden component, for example, fir, cypress, pine, and lauan can be cited.

[0181] Another example of a substrate includes a metal component. Examples of metals used for metal components include iron and aluminum. Another example of a substrate includes a ceramic component. The ceramic component can be made of ceramics such as glass and ceramic, non-cement ceramic materials such as gypsum, or non-ceramic ceramic materials such as ALC (Autoclaved Lightweight Concrete). Calcium silicate boards can also be used as ceramic components.

[0182] To improve adhesion to the transfer sheet, the substrate may be surface treated. For example, if the substrate is an aluminum component, surface treatments include aluminum oxide treatment, chemical treatment, plating, painting, sandblasting, and polishing. For example, if the substrate is a ceramic component, UV protection coating and painting are examples.

[0183] The shape of the base is not particularly limited, and examples thereof include plate, sheet, and three-dimensional shapes. Furthermore, the base may have a flat portion, a curved portion, or both. Furthermore, the base may have at least one of a convex portion, a concave portion, a convex stripe portion, a concave stripe portion, and a through portion.

[0184] As the substrate in the present invention, acrylic board, polycarbonate board, non-combustible board, metal board, vinyl chloride board, melamine board or carbon fiber reinforced plastic board are preferred. As the non-combustible board, for example, fiber reinforced cement board can be mentioned, among which calcium silicate board is preferred.

[0185] In the bonding process, the surface of the transfer sheet on the second protective layer side is made to face the base, and the two are bonded together. As a method for bonding the two together, for example, a lamination method can be cited. In the lamination method, for example, the laminate of the transfer sheet and the base is heated and pressurized from the transfer sheet side. As a method for heating and pressurizing, for example, a method using a roller transfer device can be cited. The roller temperature of the roller transfer device is, for example, below 200°C, or below 180°C. If the roller temperature is high, the transfer sheet may soften to a higher temperature than required. On the other hand, the roller temperature of the roller transfer device is, for example, above 100°C, or above 110°C, or above 120°C. In addition, the method for manufacturing the exterior component of the present invention may have a peeling step of peeling off the release film from the first protective layer after the bonding process.

[0186] 3. Exterior components

[0187] The exterior component of the present invention comprises, in this order along the thickness direction, a first protective layer, a second protective layer, an adhesive layer, and a base. Furthermore, the exterior component may be a release film-attached exterior component, wherein a release film is provided on the surface of the first protective layer opposite to the second protective layer, or may be an exterior component without a release film.

[0188] The exterior components of the present invention are, for example, building materials (exterior components of building structures). Building materials are used in, for example, residences, offices, shops, hospitals, clinics, general roads and highways, agricultural greenhouses, etc. Examples of uses of exterior components include exterior walls, roofs, arches, rainproof window frames, window frames, doors, door frames, handrails, fences, and terraces. Specific uses of exterior components include soundproof walls or windbreaks on general roads and highways, partitions for balconies, fences, roof components for platforms or garages, and transparent components that constitute agricultural greenhouses.

[0189] In addition, the exterior components of the present invention are used as exterior components for vehicles, ships, and aircraft, exterior components for industrial machinery, and exterior components for various lenses, in addition to building materials (exterior components for architectural structures). Examples of exterior components for vehicles include: window materials such as side windows, rear windows, sunroofs, front windows, and triangular windows; headlight covers, turn signal lenses, reflectors; and pillars. Examples of vehicles include automobiles, railway vehicles, construction machinery, and light vehicles such as golf carts. Examples of exterior materials for industrial machinery include visual windows for machine tools. Examples of lenses include lenses for traffic lights.

[0190] D.Exterior components

[0191] Figure 4 : is a schematic cross-sectional view illustrating an exterior component in the present invention. Figure 4 As shown in (a) in the figure, the exterior component 100 of the present invention has a first protective layer 2, a second protective layer 3, an adhesive layer 4 and a base 20 in the thickness direction, the first protective layer 2 contains a cured product of a first curable resin composition and a weathering agent, the second protective layer 3 contains a cured product of a second curable resin composition and a weathering agent, and the cured product of the first curable resin composition and the cured product of the second curable resin composition each contain a (meth) acrylic component and a urethane component. In addition, when a cross-sectional sample piece of the exterior component 100 is made using a resin embedding method and a slicer, the indentation hardness of the cross section of the first protective layer 2 is greater than 150 MPa and less than 300 MPa, and the indentation hardness of the cross section of the second protective layer 3 is greater than 2 MPa and less than 50 MPa. Here, the adhesive layer 4 may also have the function of a design layer. Furthermore, as Figure 4 As shown in (b) , the exterior member 100 may include a design layer 5 between the second protective layer 3 and the adhesive layer 4 .

[0192] According to the present invention, since the first protective layer contains a cured product of a specific first curable resin composition and a weathering agent, and the indentation hardness of the cross section is within a specific range, and the second protective layer contains a cured product of a specific second curable resin composition and a weathering agent, and the indentation hardness of the cross section is within a specific range, an exterior component can be formed that has excellent damage resistance and good weather-resistant adhesion between the first and second protective layers.

[0193] 1. First protection layer

[0194] The exterior member of the present invention has a first protective layer. The first protective layer contributes to improving the surface properties (such as scratch resistance and wear resistance) of the exterior member. The first protective layer may be the outermost layer of the exterior member.

[0195] In the present invention, when a cross-sectional sample piece of an exterior component is produced using a resin embedding method and a microtome, the indentation hardness of the cross section of the first protective layer is generally 150 MPa or more, and may be 180 MPa or more, or 190 MPa or more. If the indentation hardness of the cross section of the first protective layer is low, good damage resistance and wear resistance may not be obtained. On the other hand, when a cross-sectional sample piece of an exterior component is produced using a resin embedding method and a microtome, the indentation hardness of the cross section of the first protective layer is generally 300 MPa or less, and may be 280 MPa or less, or 250 MPa or less. If the indentation hardness of the cross section of the first protective layer is high, the followability of the first protective layer to the second protective layer is reduced, and good weather-resistant adhesion may not be obtained.

[0196] The method for adjusting the indentation hardness of the cross section of the first protective layer is the same as the method described in the above-mentioned "A. Transfer Sheet".

[0197] The indentation hardness of the first protective layer in the exterior member is a value measured by the following method using a cross-sectional sample piece prepared using a resin embedding method and a microtome.

[0198] (Method for preparing cross-sectional sample piece for measurement)

[0199] Cut the exterior component into any size to create a cut sample. Embed the cut sample in resin (room-temperature curing epoxy two-component resin) and allow it to cure at room temperature for at least 24 hours to create an embedded sample (resin embedding method). Use a microtome to vertically cut the embedded sample to create a cross-sectional sample sheet for indentation hardness measurement, exposing the cross section of the layer being measured. The embedded sample cutting method is the same as described in "A. Transfer Sheet" above.

[0200] The method for measuring the indentation hardness is the same as the method described in the above-mentioned "A. Transfer Sheet".

[0201] The resin component, weathering agent, additives, and thickness of the first protective layer are the same as those described in the above-mentioned "A. Transfer Sheet".

[0202] 2. Second protection layer

[0203] The exterior member of the present invention has a second protective layer. The second protective layer and the first protective layer may be disposed in direct contact or with another layer interposed therebetween.

[0204] When using a resin embedding method and a microtome to prepare cross-sectional sample pieces of exterior components, the indentation hardness of the cross section of the second protective layer is usually above 2 MPa, and may also be above 5 MPa, may be above 10 MPa, may be above 15 MPa, and may be above 20 MPa. On the other hand, the indentation hardness of the cross section of the second protective layer is usually below 50 MPa, and may also be below 40 MPa, and may be below 30 MPa. If the indentation hardness of the cross section of the second protective layer is high, the adhesion (especially the initial adhesion) with the first protective layer may be reduced. It should be noted that the method for preparing cross-sectional sample pieces of exterior components and the method for measuring the indentation hardness of the cross section of the second protective layer are the same as the method described above for the first protective layer.

[0205] The indentation hardness of the cross section of the second protective layer in the exterior member may be greater than the indentation hardness of the cross section of the second protective layer in the transfer sheet because the second protective layer is compressed by transfer.

[0206] The resin component, weathering agent, additives, and thickness of the second protective layer are the same as those described in the above-mentioned "A. Transfer Sheet".

[0207] 3. Adhesive layer

[0208] The exterior component of the present invention has an adhesive layer. Examples of the adhesive layer include the same adhesive layer described in "A. Transfer Sheet" above. Furthermore, the indentation hardness of the cross-section of the adhesive layer in the exterior component may be greater than the indentation hardness of the cross-section of the adhesive layer in the transfer sheet. This is due to compression during transfer. If the transfer sheet described above does not have an adhesive layer, the adhesive layer of the exterior component of the present invention may be an adhesive layer disposed between the transfer sheet and the substrate.

[0209] 4. Design layer

[0210] The exterior component of the present invention may include a design layer. Examples of the design layer include those described in "A. Transfer Sheet" above. The indentation hardness of the cross-section of the design layer in the exterior component may be greater than the indentation hardness of the cross-section of the design layer in the transfer sheet. This is due to compression during transfer.

[0211] 5. Matrix

[0212] The base body in the present invention is the same as that described in the above-mentioned "C. Method for producing exterior member", and therefore description thereof is omitted here.

[0213] 6.Exterior components

[0214] The exterior member in the present invention is the same as that described in the above-mentioned "C. Method for producing exterior member", and therefore description thereof is omitted here.

[0215] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any other embodiment having substantially the same configuration and exhibiting the same effects as the technical concept described in the claims of the present invention is encompassed within the technical scope of the present invention.

[0216] Example

[0217] [Example 1]

[0218] On one side of a release film 1 (mirror-finished PET film E5001, manufactured by Toyobo Co., Ltd.), a coating amount of 5 g / m2 was applied after drying. 2 The first protective layer-forming composition 1 described below was applied in a manner and dried. Thereafter, electron beam irradiation (applied voltage: 90 kV, 5 Mrad (50 kGy)) was performed to form a first protective layer having a thickness of 5 μm.

[0219] <First protective layer-forming composition 1>

[0220] Ionizing radiation curable resin composition: 100 parts by mass

[0221] (Caprolactone-based urethane acrylate: 30 parts by mass)

[0222] (Pentaerythritol triacrylate (hydroxyl group-containing acrylate): 50 parts by mass)

[0223] (Acrylate: 20 parts by mass)

[0224] Triazine-based UV absorber: 2 parts by mass

[0225] (Hydroxyphenyltriazine-based UV absorber (trade name: TINUVIN 479, BASF))

[0226] Light stabilizer with reactive functional groups: 2 parts by mass

[0227] (Trade name: SANOL LS-3410, Nippon Emulsifier Co., Ltd.)

[0228] Solvent: appropriate amount

[0229] Then, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the following second protective layer-forming composition 1 was applied and dried to form a second protective layer having a thickness of 5 μm.

[0230] <Second protective layer forming composition 1>

[0231] Polycarbonate-based urethane acrylic copolymer: 100 parts by mass (ratio of urethane to acrylic acid is 9:1)

[0232] Hydroxyphenyltriazine-based ultraviolet absorber: 17 parts by mass (trade name: TINUVIN 400, BASF)

[0233] Hydroxyphenyltriazine-based ultraviolet absorber: 13 parts by mass (trade name: TINUVIN 479, BASF)

[0234] Hindered amine light stabilizer: 8 parts by mass (trade name: TINUVIN 123, BASF)

[0235] Anti-blocking agent: 9 parts by mass (silicon dioxide particles, average particle size 3 μm)

[0236] Curing agent: 25 parts by mass (hexamethylene diisocyanate)

[0237] Solvent: appropriate amount

[0238] A heat sealant containing an acrylic resin (polymethyl methacrylate) was then applied to the surface of the resulting second protective layer and dried to form a 5 μm thick adhesive layer. This yielded a transfer sheet having, in this order in the thickness direction, a release film, a first protective layer, a second protective layer, and an adhesive layer (heat seal layer).

[0239] [Example 2]

[0240] On one side of the release film 2 prepared by the following method, the coating amount after drying was 5 g / m 2 The first protective layer-forming composition 2 described below was applied in a manner and dried. Thereafter, electron beam irradiation (applied voltage: 90 kV, 5 Mrad (50 kGy)) was performed to form a first protective layer having a thickness of 5 μm.

[0241] <Preparation of Release Film 2>

[0242] The corona-treated surface of a 50 μm thick PET film (E5101, Toyobo Co., Ltd.) was coated with a coating weight of 3 g / m after drying. 2 The following thermosetting resin composition was applied in a manner of , and cured in an oven at 40° C. for 5 days. Thus, a release film having a film layer and a matte layer was obtained.

[0243] <Thermosetting resin composition>

[0244] Polyester polyol resin: 100 parts by mass

[0245] Curing agent: 15 parts by mass (hexamethylene diisocyanate)

[0246] Matting agent: 15 parts by mass (silicon dioxide particles, average particle size 3 μm)

[0247] Solvent: appropriate amount

[0248] <First protective layer-forming composition 2>

[0249] Ionizing radiation curable resin composition: 100 parts by mass

[0250] (Caprolactone-based urethane acrylate: 30 parts by mass)

[0251] (Pentaerythritol triacrylate (hydroxyl group-containing acrylate): 70 parts by mass)

[0252] Triazine-based UV absorber: 2 parts by mass

[0253] (Hydroxyphenyltriazine-based UV absorber (trade name: TINUVIN 479, BASF))

[0254] Light stabilizer with reactive functional groups: 2 parts by mass

[0255] (Trade name: SANOL LS-3410, Nippon Emulsifier Co., Ltd.)

[0256] Solvent: appropriate amount

[0257] Then, the surface of the obtained first protective layer was subjected to corona discharge treatment, and then the above-mentioned second protective layer-forming composition 1 was applied thereto and dried to form a second protective layer having a thickness of 5 μm.

[0258] Next, the following ink composition 1, containing a resin component and a pigment, was applied to the surface of the resulting second protective layer by gravure coating and dried to form a design layer with a thickness of 3 to 5 μm, comprising a pattern layer and a solid coating. An adhesive composition 1, containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a 6:4 (mass ratio) was applied to the surface of the resulting design layer by gravure coating and dried to form a 2 μm thick adhesive layer. This yielded a transfer sheet having, in this order, a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in the thickness direction.

[0259] <Ink composition 1>

[0260] Ink resin component (mixed resin of urethane resin and polyacrylic polyol (mass ratio 20:80))

[0261] Pigments (organic and inorganic)

[0262] [Example 3]

[0263] On one side of a release film 3 (PET film with a thickness of 50 μm, haze (Hz): 83%, total light transmittance (Tt): 68%, 60 degree specular gloss: 16%) mixed with a matting agent, the coating amount after drying was 5 g / m2 The first protective layer-forming composition 3 described below was applied in a manner of , and dried. Thereafter, electron beam irradiation (applied voltage: 90 kV, 5 Mrad (50 kGy)) was performed to form a first protective layer having a thickness of 5 μm.

[0264] <First protective layer-forming composition 3>

[0265] Ionizing radiation curable resin composition: 100 parts by mass

[0266] (Caprolactone-based urethane acrylate: 60 parts by mass)

[0267] (Urethane acrylate: 40 parts by mass)

[0268] Triazine-based UV absorber: 2 parts by mass

[0269] (Hydroxyphenyltriazine-based UV absorber (trade name: TINUVIN 479, BASF))

[0270] Light stabilizer with reactive functional groups: 2 parts by mass

[0271] (Trade name: SANOL LS-3410, Nippon Emulsifier Co., Ltd.)

[0272] Solvent: appropriate amount

[0273] Then, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the following second protective layer-forming composition 2 was applied and dried to form a second protective layer having a thickness of 5 μm.

[0274] <Second protective layer forming composition 2>

[0275] Polycarbonate-based urethane acrylic copolymer: 95 parts by mass (the ratio of urethane to acrylic acid is 9:1)

[0276] Acrylic polyol: 5 parts by mass

[0277] Hydroxyphenyltriazine-based ultraviolet absorber: 17 parts by mass (trade name: TINUVIN 400, BASF)

[0278] Hydroxyphenyltriazine-based ultraviolet absorber: 13 parts by mass (trade name: TINUVIN 479, BASF)

[0279] Hindered amine light stabilizer: 8 parts by mass (trade name: TINUVIN 123, BASF)

[0280] Anti-blocking agent: 9 parts by mass (silicon dioxide particles, average particle size 3 μm)

[0281] Curing agent: 25 parts by mass (hexamethylene diisocyanate)

[0282] Solvent: appropriate amount

[0283] Next, the ink composition 1 described above, containing a resin component and a pigment, was applied to the surface of the resulting second protective layer by gravure coating and dried to form a design layer with a thickness of 3 to 5 μm, comprising a pattern layer and a solid coating. An adhesive composition 1 containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a 6:4 (mass ratio) was applied to the surface of the resulting design layer by gravure coating and dried to form a 2 μm thick adhesive layer. This yielded a transfer sheet having, in this order, a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in the thickness direction.

[0284] [Example 4]

[0285] On one side of the release film 3, the coating amount after drying was 5 g / m 2 The first protective layer-forming composition 2 was applied in a manner of 90°C and dried. Thereafter, electron beam irradiation (applied voltage: 90 kV, 5 Mrad (50 kGy)) was performed to form a first protective layer having a thickness of 5 μm.

[0286] Then, the surface of the obtained first protective layer was subjected to corona discharge treatment, and then the following second protective layer-forming composition 3 was applied and dried to form a second protective layer having a thickness of 5 μm.

[0287] <Second protective layer forming composition 3>

[0288] Polycarbonate-based urethane acrylic copolymer: 98 parts by mass (ratio of urethane to acrylic acid is 9:1)

[0289] Acrylic polyol: 2 parts by mass

[0290] Hydroxyphenyltriazine-based ultraviolet absorber: 17 parts by mass (trade name: TINUVIN 400, BASF)

[0291] Hydroxyphenyltriazine-based ultraviolet absorber: 13 parts by mass (trade name: TINUVIN 479, BASF)

[0292] Hindered amine light stabilizer: 8 parts by mass (trade name: TINUVIN 123, BASF)

[0293] Anti-blocking agent: 9 parts by mass (silicon dioxide particles, average particle size 3 μm)

[0294] Curing agent: 25 parts by mass (hexamethylene diisocyanate)

[0295] Next, the ink composition 1 described above, containing a resin component and a pigment, was applied to the surface of the resulting second protective layer by gravure coating and dried to form a design layer with a thickness of 3 to 5 μm, comprising a pattern layer and a solid coating. An adhesive composition 1 containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a 6:4 (mass ratio) was applied to the surface of the resulting design layer by gravure coating and dried to form a 2 μm thick adhesive layer. This yielded a transfer sheet having, in this order, a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in the thickness direction.

[0296] [Example 5]

[0297] (Manufacturing of exterior components)

[0298] The adhesive layer side of the transfer sheet obtained in Example 1 was laminated facing one side of a substrate (a 2 mm thick acrylic plate ("COMOGLAS" manufactured by Kuraray Co., Ltd.). Using a laminator, heat and pressure were applied from the transfer sheet side to achieve close contact at a laminating roll temperature of 170°C and a conveyance speed of 2 m / min. The release film was peeled from the bonded transfer sheet to obtain an exterior component.

[0299] [Example 6]

[0300] (Production of transfer sheets)

[0301] On one side of the release film 3, the coating amount after drying was 5 g / m 2 The first protective layer-forming composition 2 was applied in a manner of 90°C and dried. Thereafter, electron beam irradiation (applied voltage: 90 kV, 5 Mrad (50 kGy)) was performed to form a first protective layer having a thickness of 5 μm.

[0302] Then, the surface of the obtained first protective layer was subjected to corona discharge treatment, and then the second protective layer-forming composition 2 was applied thereto and dried to form a second protective layer having a thickness of 5 μm.

[0303] Next, the ink composition 1 described above, containing a resin component and a pigment, was applied to the surface of the resulting second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm, including a pattern layer and a solid coating. This produced a transfer sheet having, in this order in the thickness direction, a release film, a first protective layer, a second protective layer, and a design layer.

[0304] (Manufacturing of exterior components)

[0305] Prepare a 10mm thick non-combustible board (fiber reinforced cement board) with an epoxy resin sealant applied to the transfer surface as a substrate. Then, apply a hot melt adhesive to the design layer side of the transfer sheet obtained above and let it dry. The surface of the substrate treated with the epoxy resin sealant and the surface of the transfer sheet coated with the adhesive are stacked facing each other. Using a laminator, heat and pressurize the transfer sheet side to make it adhere tightly under the conditions of a laminating roller temperature of 170°C and a conveying speed of 2m / min. Peel off the release film from the adhered transfer sheet to obtain an exterior component.

[0306] [Comparative Example 1]

[0307] On one side of the release film 3, the coating amount after drying was 5 g / m 2 The first protective layer-forming composition 2 was applied in a manner of 90°C and dried. Thereafter, electron beam irradiation (applied voltage: 90 kV, 5 Mrad (50 kGy)) was performed to form a first protective layer having a thickness of 5 μm.

[0308] Then, the surface of the obtained first protective layer was subjected to corona discharge treatment, and then the following second protective layer-forming composition 4 was applied and dried to form a second protective layer having a thickness of 5 μm.

[0309] <Second protective layer-forming composition 4>

[0310] Acrylic polyol: 100 parts by mass

[0311] Hydroxyphenyltriazine-based ultraviolet absorber: 17 parts by mass (trade name: TINUVIN 400, BASF)

[0312] Hydroxyphenyltriazine-based ultraviolet absorber: 13 parts by mass (trade name: TINUVIN 479, BASF)

[0313] Hindered amine light stabilizer: 8 parts by mass (trade name: TINUVIN 123, BASF)

[0314] Anti-blocking agent: 9 parts by mass (silicon dioxide particles, average particle size 3 μm)

[0315] Curing agent: 25 parts by mass (hexamethylene diisocyanate)

[0316] Next, the ink composition 1 described above, containing a resin component and a pigment, was applied to the surface of the resulting second protective layer by gravure coating and dried to form a design layer with a thickness of 3 to 5 μm, comprising a pattern layer and a solid coating. An adhesive composition 1 containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a 6:4 (mass ratio) was applied to the surface of the resulting design layer by gravure coating and dried to form a 2 μm thick adhesive layer. This yielded a transfer sheet having, in this order, a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in the thickness direction.

[0317] [Comparative Example 2]

[0318] On one side of a release film 1 (mirror-finished PET film E5001, manufactured by Toyobo Co., Ltd.), a coating amount of 5 g / m2 was applied after drying. 2 The first protective layer-forming composition 4 described below was applied in a manner of , and dried. Thereafter, electron beam irradiation (applied voltage: 90 kV, 5 Mrad (50 kGy)) was performed to form a first protective layer having a thickness of 5 μm.

[0319] <First protective layer-forming composition 4>

[0320] Ionizing radiation curable resin composition: 100 parts by mass

[0321] (Caprolactone-based urethane acrylate: 100 parts by mass)

[0322] Hydroxyphenyltriazine-based UV absorber: 2 parts by mass (trade name: TINUVIN 479, BASF)

[0323] Light stabilizer with a reactive functional group: 2 parts by mass (trade name: SANOL LS-3410, Nippon Emulsifier Co., Ltd.)

[0324] Then, the surface of the obtained first protective layer was subjected to corona discharge treatment, and then the above-mentioned second protective layer-forming composition 1 was applied thereto and dried to form a second protective layer having a thickness of 5 μm.

[0325] Next, the ink composition 1 described above, containing a resin component and a pigment, was applied to the surface of the resulting second protective layer by gravure coating and dried to form a design layer with a thickness of 3 to 5 μm, comprising a pattern layer and a solid coating. An adhesive composition 1 containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a 6:4 (mass ratio) was applied to the surface of the resulting design layer by gravure coating and dried to form a 2 μm thick adhesive layer. This yielded a transfer sheet having, in this order, a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in the thickness direction.

[0326] [Measurement of indentation hardness]

[0327] The first protective layer, second protective layer, and heat seal layer (Example 1) or design layer (Examples 2 to 4, Comparative Examples 1 and 2) of the transfer sheets obtained in Examples 1 to 4, Comparative Examples 1, and 2 were measured for indentation hardness by the above method. The results are shown in Table 1.

[0328] The indentation hardness of the first protective layer, the second protective layer, and the heat seal layer or the design layer of the exterior members obtained in Examples 5 and 6 was measured by the above-mentioned method. The results are shown in Table 1.

[0329] It should be noted that the indentation hardness value of Example 6 is the indentation hardness of the first protective layer, the second protective layer, and the design layer in the exterior component measured when a 2 mm thick acrylic plate ("COMOGLAS", manufactured by Kuraray Co., Ltd.) is used as the base instead of the non-combustible plate.

[0330] [Evaluation of Adhesion (Initial)]

[0331] The adhesive layer (design layer) side of the transfer sheet obtained in Examples 1 to 4, Comparative Examples 1 and 2 was stacked facing each other on one side of a substrate (an acrylic plate with a thickness of 2 mm ("COMOGLAS", manufactured by Kuraray Co., Ltd.)). Using a laminator, heat and pressurize the transfer sheet from the side to achieve close contact at a laminating roller temperature of 170°C and a conveying speed of 2 m / min. The release film was peeled off from the closely contacted transfer sheet to obtain an exterior component as an evaluation component. The exterior components obtained in Examples 5 and 6 were used as evaluation components as they were.

[0332] An adhesive tape ("Cellotape (registered trademark)" manufactured by Nichiban Co., Ltd.) was applied to an area of 2.5 cm x 2.5 cm, protruding approximately 5 cm from the end of the evaluation member. The protruding portion of the adhesive tape was then pinched and peeled off at a 45-degree angle to the surface of the evaluation member to confirm the interlayer adhesion of the transfer layer. Initial adhesion was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

[0333] <Evaluation Criteria>

[0334] A: No separation occurred between the transfer layers.

[0335] B: Peeling occurred between the transfer layers.

[0336] [Evaluation of Weather-Resistant Adhesion]

[0337] The evaluation member was subjected to the following accelerated weathering test for 700 hours using a metal halide lamp (MWOM) (one cycle consisting of 20 hours of ultraviolet irradiation under the following irradiation conditions followed by 4 hours of condensation under the following condensation conditions, with this cycle repeated). The weathering adhesion was then evaluated as follows. The evaluation results are shown in Table 1.

[0338] <Conditions that promote weathering testing>

[0339] (Test equipment)

[0340] Manufactured by Daipla Winters, trade name "Daipla Metal Weather"

[0341] (irradiation conditions)

[0342] Illumination: 65mW / cm 2 , black panel temperature: 63℃, tank humidity: 50%RH, time: 20 hours

[0343] (Condensation conditions)

[0344] Illumination: 0mW / cm 2 , Humidity in the tank: 98% RH, Time: 4 hours

[0345] An adhesive tape ("Cellotape (registered trademark)" manufactured by Nichiban Co., Ltd.) was applied to an area of 2.5 cm x 2.5 cm so that it protruded approximately 5 cm from the end of the evaluation member undergoing the accelerated weathering test. The protruding portion of the adhesive tape was then pinched and peeled off at a 45-degree angle to the surface of the evaluation member to confirm the weather-resistant adhesion between the transfer layers. The adhesion was evaluated according to the following criteria. The evaluation results are shown in Table 1.

[0346] <Evaluation Criteria>

[0347] A: No separation occurred between the transfer layers.

[0348] B: Peeling occurred between the transfer layers.

[0349] [Evaluation of scratch resistance]

[0350] The evaluation member was subjected to a load of 300 g / cm using steel wool (Bonstar, #0000). 2 The surface of the first protective layer was moved back and forth five times to check the surface condition. The scratch resistance was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

[0351] <Evaluation Criteria>

[0352] A: There is almost no change in appearance.

[0353] B: Clear damage and gloss changes were observed.

[0354] [Table 1]

[0355]

[0356] (* Regarding indentation hardness, the values measured for each layer of the transfer sheet in Examples 1 to 4 and Comparative Examples 1 and 2 are values measured for each layer of the transfer product (exterior member) in Examples 5 and 6.)

[0357] As shown in Table 1, the transfer sheets of Examples 1 to 4 were confirmed to be capable of transferring transfer layers with excellent damage resistance and good weather-resistant adhesion of the first and second protective layers. Similarly, the exterior components of Examples 5 and 6 were confirmed to have good weather-resistant adhesion and excellent damage resistance of the first and second protective layers.

[0358] On the other hand, the transfer sheet of Comparative Example 1 was found to have poor initial adhesion and weathering adhesion due to the excessively high indentation hardness of the second layer. Furthermore, the transfer sheet of Comparative Example 2 was found to have poor scratch resistance due to the excessively low indentation hardness of the first layer.

[0359] Thus, in the present invention, for example, the following inventions are provided. [1]

[0361] A transfer sheet material used for manufacturing exterior components.

[0362] The transfer sheet comprises a release film and a transfer layer disposed on one side of the release film.

[0363] The transfer layer includes a first protective layer and a second protective layer in this order from the release film side in the thickness direction.

[0364] The first protective layer comprises a cured product of a first curable resin composition and a weathering agent.

[0365] The second protective layer comprises a cured product of a second curable resin composition and a weathering agent.

[0366] The cured product of the first curable resin composition and the cured product of the second curable resin composition each contain a (meth)acrylic acid component and a urethane component.

[0367] When a cross-sectional sample of the transfer sheet is prepared using a resin embedding method and a microtome,

[0368] The indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0369] The second protective layer has an indentation hardness of 2 MPa to 50 MPa in a cross section. [2]

[0371] The transfer sheet according to [1], wherein the first curable resin composition is an ionizing radiation curable resin composition. [3]

[0373] The transfer sheet according to [1] or [2], wherein the first curable resin composition is an electron beam curable resin composition. [4]

[0375] The transfer sheet according to any one of [1] to [3], wherein the first curable resin composition contains urethane (meth)acrylate. [5]

[0377] The transfer sheet according to any one of [1] to [4], wherein the second curable resin composition is a thermosetting resin composition. [6]

[0379] The transfer sheet according to any one of [1] to [5], wherein the second curable resin composition contains a urethane (meth)acrylic resin. [7]

[0381] The transfer sheet according to any one of [1] to [6], wherein the second curable resin composition is a thermosetting resin composition containing a polycarbonate-based urethane (meth)acrylic copolymer. [8]

[0383] The transfer sheet according to any one of [1] to [7], wherein the first protective layer contains at least one of an ultraviolet absorber and a light stabilizer as the weathering agent. [9]

[0385] The transfer sheet according to any one of [1] to [8], wherein the first protective layer contains a triazine-based ultraviolet absorber as the weathering agent.

[10]

[0387] The transfer sheet according to any one of [1] to [9], wherein the second protective layer contains at least one of an ultraviolet absorber and a light stabilizer as the weathering agent.

[11]

[0389] The transfer sheet according to any one of [1] to

[10] , wherein the second protective layer contains a triazine-based ultraviolet absorber as the weathering agent.

[12]

[0391] The transfer sheet according to any one of [1] to

[11] , wherein the second protective layer has an adhesive layer on the surface opposite to the first protective layer.

[13]

[0393] The transfer sheet as described in

[12] , wherein the adhesive layer has a colorant.

[14]

[0395] The transfer sheet as described in

[12] or

[13] , wherein the indentation hardness of the cross section of the adhesive layer is 100 MPa or more and 300 MPa or less.

[15]

[0397] The transfer sheet according to any one of [1] to

[14] , wherein the design layer is provided on the surface of the second protective layer opposite to the first protective layer.

[16]

[0399] The transfer sheet as described in

[15] has an adhesive layer on the surface of the design layer opposite to the second protective layer.

[17]

[0401] A method for producing a transfer sheet, which is the method for producing a transfer sheet as described in any one of [1] to

[16] , comprising:

[0402] a first protective layer forming step of applying a first composition comprising the first curable resin composition and the weathering agent on a surface of the release film and curing the composition to form the first protective layer; and

[0403] The second protective layer forming step comprises applying a second composition comprising the second curable resin composition and the weathering agent on the surface of the first protective layer opposite to the release film and curing the composition to form the second protective layer.

[18]

[0405] A method for manufacturing an exterior component, comprising:

[0406] a preparation step of preparing a transfer sheet as described in any one of [1] to

[16] ; and

[0407] In the bonding step, the second protective layer side of the transfer sheet is placed facing the substrate and the substrate is bonded together.

[19]

[0409] An exterior component comprises a first protective layer, a second protective layer, an adhesive layer and a base in this order in the thickness direction.

[0410] The first protective layer comprises a cured product of a first curable resin composition and a weathering agent.

[0411] The second protective layer comprises a cured product of a second curable resin composition and a weathering agent.

[0412] The cured product of the first curable resin composition and the cured product of the second curable resin composition each contain a (meth)acrylic acid component and a urethane component.

[0413] When a cross-sectional sample of the transfer sheet is prepared using a resin embedding method and a microtome,

[0414] The indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0415] The second protective layer has an indentation hardness of 2 MPa to 50 MPa in a cross section.

[20]

[0417] The exterior component as described in

[19] , wherein the above-mentioned 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.

[0418] Description of Reference Numerals

[0419] 1: Release film; 2: First protective layer; 3: Second protective layer; 4: Adhesive layer; 5: Design layer; 10: Transfer sheet; 20: Base; 100: Exterior component.

Claims

1. A transfer sheet for manufacturing exterior components, The transfer sheet comprises a release film and a transfer layer disposed on one side of the release film. The transfer layer includes a first protective layer and a second protective layer in this order from the release film side in the thickness direction. The first protective layer comprises a cured product of a first curable resin composition and a weathering agent. The second protective layer comprises a cured product of a second curable resin composition and a weathering agent. The cured product of the first curable resin composition and the cured product of the second curable resin composition each contain a (meth)acrylic acid component and a urethane component. When a cross-sectional sample of the transfer sheet is prepared using a resin embedding method and a microtome, The indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less. The indentation hardness of a cross section of the second protective layer is 2 MPa or more and 50 MPa or less.

2. The transfer sheet according to claim 1, wherein The first curable resin composition is an ionizing radiation curable resin composition.

3. The transfer sheet according to claim 1, wherein The first curable resin composition is an electron beam curable resin composition.

4. The transfer sheet according to claim 1, wherein The first curable resin composition contains urethane (meth)acrylate.

5. The transfer sheet according to claim 1, wherein The second curable resin composition is a thermosetting resin composition. The transfer sheet according to claim 1 , wherein: The second curable resin composition includes a urethane (meth)acrylic resin.

7. The transfer sheet according to claim 1, wherein The second curable resin composition is a thermosetting resin composition containing a polycarbonate-based urethane (meth)acrylic copolymer.

8. The transfer sheet according to claim 1, wherein The first protective layer includes at least one of an ultraviolet absorber and a light stabilizer as the weathering agent.

9. The transfer sheet according to claim 1, wherein The first protective layer contains a triazine-based ultraviolet absorber as the weathering agent.

10. The transfer sheet according to claim 1, wherein The second protective layer contains at least one of an ultraviolet absorber and a light stabilizer as the weathering agent.

11. The transfer sheet according to claim 1, wherein The second protective layer contains a triazine-based ultraviolet absorber as the weathering agent. 12 . The transfer sheet according to claim 1 , further comprising an adhesive layer on a surface of the second protective layer opposite to the first protective layer.

13. The transfer sheet according to claim 12, wherein The adhesive layer contains a colorant.

14. The transfer sheet according to claim 12, wherein The indentation hardness of a cross section of the adhesive layer is 100 MPa or more and 300 MPa or less. 15 . The transfer sheet according to claim 1 , further comprising a design layer on a surface of the second protective layer opposite to the first protective layer. 16 . The transfer sheet according to claim 15 , further comprising an adhesive layer on a surface of the design layer opposite to the second protective layer.

17. A method for manufacturing a transfer sheet, which is the method for manufacturing a transfer sheet according to any one of claims 1 to 16, comprising: a first protective layer forming step of applying a first composition comprising the first curable resin composition and the weathering agent on a surface of the release film and curing the composition to form the first protective layer; and The second protective layer forming step comprises applying a second composition comprising the second curable resin composition and the weathering agent on the surface of the first protective layer opposite to the release film and curing the composition to form the second protective layer.

18. A method for manufacturing an exterior component, comprising: a preparation step of preparing the transfer sheet according to any one of claims 1 to 16; and In the bonding step, the second protective layer side surface of the transfer sheet is placed facing the substrate and the substrate is bonded to each other.

19. An exterior component comprising, in order in the thickness direction, a first protective layer, a second protective layer, an adhesive layer, and a base. The first protective layer comprises a cured product of a first curable resin composition and a weathering agent. The second protective layer comprises a cured product of a second curable resin composition and a weathering agent. The cured product of the first curable resin composition and the cured product of the second curable resin composition each contain a (meth)acrylic acid component and a urethane component. When a cross-sectional sample piece of the exterior component is prepared using a resin embedding method and a microtome, The indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less. The indentation hardness of a cross section of the second protective layer is 2 MPa or more and 50 MPa or less.

20. The exterior component according to claim 19, wherein The substrate is an acrylic board, a polycarbonate board, a non-combustible board, a metal board, a vinyl chloride board, a melamine board or a carbon fiber reinforced plastic board.

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