Cured product layer, curable resin composition, transfer film, hard coat film, and laminate

Abstract

The present disclosure provides a cured product layer of a curable resin composition containing a carbonate-based urethane (meth)acrylate. The cured product layer has a difference ΔH in haze value before and after testing in a Taber abrasion test, performed under conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 rpm, of 14% or less and a urethane bond retention rate of 70% or more in a 1000-hour weather resistance test by xenon lamp irradiation at an illuminance of 180 W / m2.

Description

Cured product layer, curable resin composition, transfer film, hard coat film and laminate

[0001] The present disclosure relates to a cured product layer, a curable resin composition, a transfer film, a hard coat film, and a laminate.

[0002] Curable resin compositions that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams are known. When the curable resin composition is cured, a cured product having good functionality such as scratch resistance and chemical resistance is formed. Therefore, the cured product is used as a surface protection layer that protects the surface of a substrate such as wood, metal, glass, or a resin molded product.

[0003] Patent Document 1 describes a decorative sheet having at least a surface protective layer on a substrate, the surface protective layer comprising a cured product of an ionizing radiation-curable resin composition containing a urethane (meth)acrylate (A) having a difunctional to hexafunctional polycarbonate skeleton and a polyfunctional (meth)acrylate (B), the mass ratio ((A) / (B)) of the urethane (meth)acrylate (A) to the polyfunctional (meth)acrylate (B) being within a specific range, and the polyfunctional (meth)acrylate (B) being a silicone-modified urethane (meth)acrylate.

[0004] Patent Document 2 discloses a method for producing a cured film, which comprises a step of applying a curable composition having a predetermined solids concentration onto a substrate, the curable composition comprising a urethane (meth)acrylate ligomer having a predetermined weight average molecular weight (Mw) and a predetermined urethane bond amount and (meth)acryloyl group amount, which is obtained by reacting at least polyisocyanate (A), a chain aliphatic diol having 2 to 5 carbon atoms (B), and a polyfunctional (meth)acrylate (C) having a hydroxyl group, and an organic solvent having a predetermined solubility parameter; a step of irradiating the cured composition with active energy rays to obtain a cured product; and a step of stretching the cured product.

[0005] Patent No. 5962814 Patent No. 6816790

[0006] When a curable resin composition containing urethane (meth)acrylate is cured, a cured layer with high hardness is formed due to an increase in crosslink density. Therefore, such a cured layer has high scratch resistance and is useful, for example, as a surface protective layer (hard coat layer). On the other hand, while the cured layer has high hardness, it has low elongation. Therefore, when a film having the cured layer is used, for example, in in-mold molding or insert molding, good molding processing may not be possible. Scratch resistance and elongation are in a trade-off relationship, and it is desirable to achieve both. Furthermore, since the cured layer is used as a surface protective layer, it is required to have high weather resistance in addition to the above-mentioned scratch resistance and elongation.

[0007] The present disclosure has been made in view of the above circumstances, and a main object of the present disclosure is to provide a cured product layer that has high scratch resistance, high weather resistance, and high elongation under high temperature conditions.

[0008] In the present disclosure, the cured layer is a curable resin composition containing a carbonate-based urethane (meth)acrylate, and the cured layer has a difference in haze value ΔH of 14% or less before and after a Taber abrasion test performed under conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 rpm, and an illuminance of 180 W / m ２ The present invention provides a cured product layer having a urethane bond retention rate of 70% or more after 1000 hours of weather resistance testing using xenon lamp irradiation at 1000°C.

[0009] The present disclosure provides a curable resin composition used to produce the above-described cured material layer, the curable resin composition including a carbonate-based urethane (meth)acrylate.

[0010] The present disclosure provides a transfer film having a release substrate and a transfer layer, wherein the transfer layer has, from the release substrate side, a hard coat layer and an adhesive layer in this order, and the hard coat layer is the above-mentioned cured product layer.

[0011] The present disclosure provides a hard coat film having a supporting substrate and a hard coat layer, wherein the hard coat layer is the above-described cured product layer.

[0012] The present disclosure provides a laminate having a substrate and a hard coat layer laminated on the substrate, wherein the hard coat layer is the cured product layer described above.

[0013] The present disclosure can provide a cured product layer that has high scratch resistance, high weather resistance, and high elongation under high temperature conditions.

[0014] FIG. 1 is a schematic cross-sectional view illustrating a transfer film according to the present disclosure. FIG. 2 is a schematic cross-sectional view illustrating a transfer film according to the present disclosure. FIG. 3 is a schematic cross-sectional view illustrating a hard coat film according to the present disclosure. FIG. 4 is a schematic cross-sectional view illustrating a hard coat film according to the present disclosure. FIG. 5 is a schematic cross-sectional view illustrating a laminate according to the present disclosure. FIG. 6 is a schematic cross-sectional view illustrating each test sample.

[0015] Hereinafter, embodiments will be described with reference to the drawings. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. Furthermore, in order to clarify the description, the drawings may schematically show the width, thickness, and shape of each part compared to the actual form, but this is merely an example and should not be interpreted as limiting.

[0016] In this specification, when describing a mode in which another component is placed on a certain component, the term "above" or "below" is used, unless otherwise specified, to include both a case in which another component is placed directly above or below a certain component so as to be in contact with the component, and a case in which another component is placed above or below a certain component with another component interposed therebetween. Also, in this specification, when describing a mode in which another component is placed on the surface of a certain component, the term "on the surface" or "on the surface side" is used, unless otherwise specified, to include both a case in which another component is placed directly above or below a certain component so as to be in contact with the component, and a case in which another component is placed above or below a certain component with another component interposed therebetween.

[0017] The cured product layer, the curable resin composition, the transfer film, the hard coat film, and the laminate according to the present disclosure will be described in detail below.

[0018] A. Cured Material Layer The cured material layer in the present disclosure is a cured material layer of a curable resin composition containing a carbonate-based urethane (meth)acrylate, and in a Taber abrasion test performed under conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 rpm, the difference in haze value ΔH before and after the test is 14% or less, and the illuminance is 180 W / m ２ After 1000 hours of weather resistance testing using a xenon lamp at 1000°C, the urethane bond retention is 70% or more.

[0019] The cured product layer of the present disclosure has excellent scratch resistance because the difference in haze value before and after the Taber abrasion test is a predetermined value or less, and further has excellent weather resistance because the urethane bond retention rate after the weathering test is a predetermined value or more.

[0020] 1. Physical Properties (1) Elongation The cured product layer of the present disclosure may have a high elongation when cracks occur in a thermal tensile test at 180°C. A cured product layer with a high elongation exhibits high elongation under high-temperature conditions. Therefore, it is suitable for applications requiring elongation under high-temperature conditions during production or use, particularly as a hard coat layer in films for molding applications such as in-mold molding and insert molding. The elongation is not particularly limited, but may be, for example, 3% or more, 5% or more, 10% or more, 20% or more, 25% or more, 30% or more, 40% or more, 50% or more, 60% or more, or 70% or more. Meanwhile, the elongation may be, for example, 220% or less, 170% or less, 120% or less, or 90% or less.

[0021] In the present disclosure, the elongation of the cured material layer is a value measured by the following method using test sample 1. Schematic cross-sectional views of the test samples used in each test measurement in the present disclosure are shown in Figures 8(a) to 8(c). As shown in Figure 8(a), test sample 1 has a polyethylene terephthalate (PET) film 61 and a cured material layer 62, which have a higher elongation than the cured material layer. A tensile test is performed on this test sample 1 at 180°C using a tensile tester with a chuck distance of 5 cm and a tensile speed of 100 mm / min. The elongation length when cracks begin to appear in the cured material layer is measured, and the elongation is determined as follows. An AUTOGRAPH AG-Xplus manufactured by Shimadzu Corporation can be used as the tensile tester. Elongation = {(length of elongation when cracks begin to appear in the cured layer) / (distance between chucks before test: 5 cm)} x 100 (%). Note that 180°C is the temperature of molten resin in injection molding or the temperature required when hot bending polycarbonate plates, etc.

[0022] The elongation of the cured product layer can be adjusted, for example, by the value of the number average molecular weight / number of functional groups of the carbonate-based urethane (meth)acrylate. The larger the number average molecular weight / number of functional groups, the greater the elongation tends to be. The number average molecular weight / number of functional groups is, for example, 900 or more, or may be 1000 or more, or may be 1200 or more. A small number average molecular weight / number of functional groups results in a high crosslinking density, making molecular chains more susceptible to breakage due to stress, resulting in a decrease in elongation. On the other hand, the number average molecular weight / number of functional groups is, for example, 3500 or less, or may be 2500 or less, or may be 1500 or less. The number of functional groups of a carbonate-based urethane (meth)acrylate refers to the number of (meth)acryloyl groups in one molecule.

[0023] (2) Taber Abrasion Test In the cured product layer of the present disclosure, a Taber abrasion test is performed in accordance with JIS K5600-5-9 (1999) using a CS-10F abrasion wheel, a load of 500 g, and a rotation speed of 500 rpm. The difference in haze value ΔH before and after the test is 14% or less, or may be 13% or less, 12% or less, 11% or less, or 10% or less. ΔH is the haze value after the Taber abrasion test minus the haze value before the Taber abrasion test. The Taber abrasion test is performed on test sample 2. As shown in FIG. 8(b), test sample 2 has a resin base 63, an adhesive layer 64, a primer layer 65, and a cured product layer 62, in this order. When ΔH is within the above range, the cured product layer has high abrasion resistance. On the other hand, the ΔH is, for example, 0.1% or more, or may be 1% or more, 3% or more, or 5% or more. The haze value is measured in accordance with JIS K7136:2000.

[0024] The above ΔH can be adjusted by the ratio of the soft segment and the ratio of the hard segment in the carbonate-based urethane (meth)acrylate.

[0025] As described below, carbonate-based urethane (meth)acrylates have, for example, a structural unit a derived from a carbonate polyol compound (A) having a terminal hydroxyl group, a structural unit b derived from an alkyl alcohol compound (B), a structural unit c derived from a polyisocyanate compound (C), and a structural unit d derived from a hydroxyl group-containing (meth)acrylate compound (D). In this case, the ΔH can be adjusted by the ratio of the structural unit a, which is the soft segment, to the structural unit b, which is the hard segment, in the molecule.

[0026] Specifically, the total amount M of the structural unit a as a soft segment contained in one molecule of the carbonate-based urethane (meth)acrylate relative to the number average molecular weight (Mn) of the carbonate-based urethane (meth)acrylate is Ｓ The ratio (M Ｓ / Mn) is 30% or more and 50% or less, and the total amount M of the structural unit b as a hard segment contained in one molecule of the carbonate-based urethane (meth)acrylate relative to the number average molecular weight (Mn) of the carbonate-based urethane (meth)acrylate is Ｈ The ratio (M Ｈ By setting the ratio of Mn to Mn in the range of 4% to 15%, the self-repairing performance of the cured layer is improved, and ΔH can be adjusted to fall within the above range.

[0027] M Ｈ / Mn is preferably 4% or more and 15% or less, and more preferably 7% or more and 12% or less. Ｈ The larger the value of / Mn, the more the urethane bonds are aggregated. Ｈ When / Mn is equal to or greater than the above value, the density of the cured layer increases, resulting in high hardness and scratch resistance. In addition, urethane bonds have high crystallinity and interaction, and therefore act to bind molecules together, bundling the structural unit a that ensures flexibility, thereby achieving self-repairing properties. Ｈ If / Mn exceeds the upper limit, the hardness becomes too high, resulting in a cured product layer that does not have self-repairing properties.

[0028] M Ｓ / Mn is preferably 30% or more and 50% or less, more preferably 33% or more and 41% or less, and even more preferably 35% or more and 39% or less. Ｓ The larger the / Mn, the more flexible the cured layer becomes, and the more improved the self-repairing property. Ｓ If / Mn exceeds the upper limit, the change in resistance to an external force becomes large, and the cured layer becomes more susceptible to destruction.

[0029] Therefore, M Ｈ / Mn and M Ｓ When / Mn is in the above-mentioned range, ΔH can be adjusted to the above-mentioned range.

[0030] In the present disclosure, the above M Ｈ / Mn and the above M Ｓ The calculation method for / Mn is as follows: Ｈ / Mn={(number of functional groups in one molecule of urethane (meth)acrylate) / (number of functional groups of compound (D))}×{(number of moles of compound (B)) / (number of moles of compound (D))}×{(molecular weight of compound (B)) / (Mn)} M Ｓ / Mn={(number of functional groups in one molecule of urethane (meth)acrylate) / (number of functional groups of compound (D))}×{(number of moles of compound (A)) / (number of moles of compound (D))}×{(number average molecular weight of compound (A)) / (Mn)}

[0031] (3) Urethane bond retention rate The cured product layer in the present disclosure is cured at an illuminance of 180 W / m ２ The urethane bond retention rate after 1000 hours of weather resistance testing using a xenon lamp at 1000°C is 70% or more, and preferably 80% or more. When the urethane bond retention rate is within the above range, a cured product layer having high weather resistance is obtained. On the other hand, the urethane bond retention rate is, for example, 100% or less.

[0032] In the present disclosure, a weather resistance test is conducted under the following conditions, and the urethane bond retention rate after 1000 hours of weather resistance test is a value calculated by the following method. [Weather resistance test: Xenon irradiation test] A weather resistance test is conducted using the above-mentioned test sample 2. As a weather resistance test, a xenon irradiation test is conducted on test sample 2 using a xenon weather meter (Suga Test Instruments Co., Ltd., 7.5 kW Super Xenon Weather Meter SX75) under the following conditions (1) and (2) in a repeated cycle. <Condition (1): Irradiation> Irradiance: 180 W / m ２ Black panel temperature (BPT): 63°C Humidity: 50% Water spray: None Time: 102 minutes <Condition (2): Irradiation + Rainfall> Irradiance: 180 W / m ２ Black panel temperature (BPT): 28°C Humidity: 95% Water spray: Yes Duration: 18 minutes

[0033] Every 100 hours, the surface condition of the hard coat layer is visually observed to check for the occurrence of cracks. After 1000 hours of weather resistance testing, the urethane bond retention rate is calculated using the following method.

[0034] <Method for calculating urethane bond retention rate> The infrared absorption spectrum (IR spectrum) of the hard coat layer is measured by an attenuated total reflection measurement method (ATR measurement method) using an infrared spectrophotometer (JASCO FT / IR-6100, manufactured by JASCO Corporation). －１ In the IR spectrum, where the vertical axis is the absorption intensity, the absorption intensity of each peak is calculated by the tangent method as follows: (1) 1480 to 1580 cm －１ The valleys on both sides of the peak observed at 1480 cm －１ The minimum value of the nearby valley is 1580 cm －１ The baseline was set by connecting the points (minimum value of the valley nearby) with a straight line, and the distance from the baseline to the －１ The top height of the peak observed in the vicinity is the absorption intensity A1520. The absorption intensity A1520 is the absorption intensity of the absorption spectrum derived from the urethane group. (2) 1600 to 1800 cm －１ The valleys on both sides of the peak observed at －１ The minimum value of the nearby valley and 1800 cm －１ A baseline was set by connecting the points (minimum value of the valley in the vicinity) with a straight line, and a distance of 1720 cm from the baseline was set. －１ The top height of the peak observed nearby is taken as the absorption intensity A1720. The absorption intensity A1720 is the absorption intensity of the absorption spectrum derived from the ester group. In the above (1) and (2), if there is no valley on one or both sides of the peak, the base line may be used to draw the baseline. (3) The absorption intensity A1520 and the absorption intensity A1720 values ​​before and after 1000 hours of weather resistance testing are used to calculate the urethane bond retention rate as follows: Urethane bond retention rate = {(A1520 after weather resistance testing / A1720 after weather resistance testing) / (A1520 before weather resistance testing / A1720 before weather resistance testing)} x 100 (%)

[0035] The urethane bond retention rate can be adjusted by the type of resin and the type and amount of weather resistance agent added.

[0036] In the present disclosure, by using a carbonate-based urethane acrylate as the polymerizable compound, it is possible to obtain a urethane bond retention rate within the above range. By having a carbonate bond in the molecule, the scratch resistance and weather resistance are superior to those of, for example, an ester-based urethane acrylate having an ester structure as the main skeleton.

[0037] In the present disclosure, the retention rate of urethane bonds can be improved by increasing the thickness of the cured product layer.

[0038] Furthermore, the cured product layer can further improve the urethane bond retention rate by including a weathering agent, which will be described later. Examples of weathering agents include an ultraviolet absorber and a light stabilizer, which will be described later. The cured product layer preferably includes at least one of an ultraviolet absorber and a light stabilizer, but from the viewpoint of improving the urethane bond retention rate, it is preferable to use an ultraviolet absorber and a light stabilizer in combination. Furthermore, it is preferable that at least one of the ultraviolet absorber and the light stabilizer has an ethylenically unsaturated bond-containing group. The urethane bond retention rate can be further improved by using at least one of an ultraviolet absorber having an ethylenically unsaturated bond-containing group and a light stabilizer having an ethylenically unsaturated bond-containing group. The ultraviolet absorber and the light stabilizer will be described in detail below.

[0039] (4) Ratio of Silicon Atoms and Fluorine Atoms In the cured material layer according to the present disclosure, the ratio of silicon atoms derived from organosilicon to atoms having an atomic number of Li or more, as detected by X-ray photoelectron spectroscopy, on the surface is preferably 0.3 at% or less, and the ratio of fluorine atoms is preferably 0.3 at% or less.

[0040] When the cured material layer of the present disclosure is used as a hard coat layer of an in-mold transfer film, the transfer film is inserted into an injection mold so that the release substrate contacts the mold, and then molten resin is injected and filled into the cavity. After cooling, the mold is opened, thereby simultaneously performing molding and transfer, and then the release substrate must be peeled off. The peel strength between the release substrate and the hard coat layer must be consistently low over time. That is, the peel strength must be low not only immediately after production, but also after a long period of time. In the present disclosure, when the curable resin composition contains a leveling agent, the content ratio of silicon atoms derived from the organosilicon and the content ratio of fluorine atoms on the surface of the cured material layer are each 0.3 at% or less, thereby achieving stable peel strength over time. Furthermore, in the above-mentioned X-ray photoelectron spectroscopy analysis, it is preferable that the content ratio of silicon atoms derived from the organosilicon and the content ratio of fluorine atoms are below the detection limit.

[0041] The silicon atom content ratio and the fluorine atom content ratio are values ​​measured by X-ray photoelectron spectroscopy performed on the above-mentioned test sample 2 under the following conditions. As the XPS device, a PHI5000VersaProbeIII (a scanning X-ray photoelectron spectroscopy device manufactured by ULVAC-PHI) can be used. <XPS measurement conditions> Incident X-ray: Al Kα (monochromated X-ray, hν=1486.6 eV) X-ray output: 50 W (15 kV, 3.3 mA) X-ray beam diameter: 200 μmφ X-ray scanning: 300 μm × 200 μm Photoelectron acceptance angle: 45 degrees Charge neutralization: low-energy electron irradiation, low-acceleration Ar+ ion irradiation

[0042] The quantitative analysis method for XPS is explained below. In quantitative analysis using XPS, peaks are collected for each element to be measured, and the concentration is calculated from their area ratio. First, the background is subtracted. Techniques such as the Shirley method can be used to calculate the background. Next, to correct for differences in sensitivity due to elements, sensitivity differences are corrected using sensitivity coefficients built into the analysis software. The area ratio is then used to convert to concentration. Note that the quantitative value (atomic %) in XPS (X-ray photoelectron spectroscopy) applies to elements of Li and above. For silicon, waveform separation analysis (curve fitting) is performed on the 2p orbital spectrum to calculate the ratio of that due to organosilicon and that due to silica. The peak appearing around 102 eV corresponds to the C-Si-O bond of organosilicon, and the peak at 103.3 eV corresponds to the SiO ２ For fluorine, photoelectrons from the 1s orbital are observed.

[0043] The waveform separation analysis method will now be explained. Prior to the waveform separation analysis, charge correction is performed on the energy axis (X-axis) of the spectrum. As an example, the reference peak for correction is set to 284.8 to 285.0 eV, which is the peak thought to be caused by a C-C bond in the carbon 1s spectrum. The waveform separation analysis is approximated using a mixed function of a Gaussian function and a Lorentzian function. The peak position (binding energy value), peak full width at half maximum (FWHM), and the mixed ratio of Gaussian function / Lorentzian function (which determines the peak shape) can be fixed, or variable conditions can be set and linked.

[0044] 2. Curable Resin Composition The cured layer in the present disclosure is a cured layer of a curable resin composition containing a carbonate-based urethane (meth)acrylate.

[0045] (1) Carbonate-based urethane (meth)acrylate (a) Structure The curable resin composition of the present disclosure contains a carbonate-based urethane (meth)acrylate as a polymerizable compound. The carbonate-based urethane (meth)acrylate has a carbonate bond and a urethane bond in the molecule and a (meth)acryloyl group at the terminal. In this specification, (meth)acrylate means acrylate or methacrylate, and (meth)acryloyl group means acryloyl group or methacryloyl group.

[0046] As described above, when the curable resin composition contains a carbonate-based urethane (meth)acrylate as the polymerizable compound, it is possible to obtain a urethane bond retention rate within the above range.

[0047] The structure of the carbonate-based urethane (meth)acrylate is not particularly limited as long as it satisfies the physical properties (ΔH and urethane bond retention) of the cured layer described above. Carbonate-based urethane (meth)acrylates are generally reaction products of a carbonate polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate.

[0048] In the present disclosure, the urethane (meth)acrylate is preferably a reaction product of a carbonate polyol compound (A), an alkyl alcohol compound (B) having two or more hydroxyl groups, a polyisocyanate compound (C), and a hydroxyl group-containing (meth)acrylate (D). The use of the alkyl alcohol compound (B) allows the ΔH value to be adjusted. Such a carbonate-based urethane (meth)acrylate preferably has a structural unit a derived from the carbonate polyol compound (A) having a terminal hydroxyl group, a structural unit b derived from the alkyl alcohol compound (B), a structural unit c derived from the polyisocyanate compound (C), and a structural unit d derived from the hydroxyl group-containing (meth)acrylate compound (D), with structural unit d being present at the molecular chain terminal. This carbonate-based urethane (meth)acrylate has a structure in which the structural units a and b are linked to the structural unit c via urethane bonds to form a urethane polymer chain, and the structural unit d is further bonded to the terminal of the urethane polymer chain. The structural unit a has a structure obtained by removing a hydroxyl group from a carbonate polyol compound (A). The structural unit b has a structure obtained by removing a hydroxyl group from an alkyl alcohol compound (B). The structural unit c has a structure obtained by removing an isocyanate group from a polyisocyanate compound (C). The structural unit d has a structure obtained by removing a hydroxyl group from a hydroxyl group-containing (meth)acrylate (D).

[0049] (i) Carbonate polyol compound (A) The carbonate polyol compound (A) has at least one carbonate bond in the molecule, and also includes a polycarbonate polyol compound having two or more carbonate bonds. By having a carbonate bond in the molecule, a cured product layer having excellent scratch resistance, chemical resistance, and weather resistance can be obtained, for example, compared to when an ester polyol compound having an ester structure as the main skeleton is used.

[0050] The carbonate polyol compound (A) has two or more hydroxyl groups, at least one of which is a terminal hydroxyl group. The carbonate polyol compound (A) is preferably a carbonate diol having two hydroxyl groups in total, one at each end, and among these, a carbonate diol represented by the following general formula (1) is preferred. Among these, an aliphatic carbonate diol in which R in the following general formula (1) is a linear or branched divalent hydrocarbon group is preferred.

[0051] (In the formula, R is a divalent hydrocarbon group, and multiple Rs contained in one molecule may be the same or different. n is a number that causes the number average molecular weight of the aliphatic carbonate diol represented by general formula (1) to fall within the range described below.)

[0052] In the above formula (1), R is a divalent hydrocarbon group. In the present disclosure, R is preferably a linear or branched divalent hydrocarbon group, and more preferably a linear or branched divalent saturated hydrocarbon group. By using a carbonate polyol compound in which R is a linear or branched divalent hydrocarbon group, a cured material layer having excellent self-repairing properties and excellent scratch resistance can be obtained. If the carbonate polyol compound has a cyclic skeleton, the cured material layer becomes too hard and has poor self-repairing properties, resulting in low scratch resistance. Note that the cyclic skeleton refers to an alicyclic ring, an aromatic ring, a heterocyclic ring, or a skeleton containing one or more of these. The heterocyclic ring refers to a cyclic structure having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms.

[0053] The number of carbon atoms in R is not particularly limited, but is, for example, 1 or more and 30 or less, and preferably 2 or more and 10 or less. Specific examples of R include ethylene, propylene, butylene, isobutylene, sec-butylene, tert-butylene, 2,2-dimethylpropylene, 2-methylbutylene, 2-methyl-2-butylene, 3-methylbutylene, 3-methyl-2-butylene, pentylene, 2-pentylene, 3-pentylene, 3-dimethyl-2-butylene, 3,3-dimethylbutylene, 3,3-dimethyl-2-butylene, 2-ethylbutylene, hexylene, 2-hexylene, 3-hexylene, 2-methylpentylene, 2-methyl-2-pentylene, 2-methyl-3-pentylene, 3-methylpentylene, 3-methyl-2-pentylene, and 3-methyl-3-pentylene. group, 4-methylpentylene group, 4-methyl-2-pentylene group, 2,2-dimethyl-3-pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6-methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, 2-propylpentylene group, 2,4,4-trimethylpentylene group, nonylene group, and decanylene group. In the general formula (1), the plurality of R's may be of a single type or of two or more types.

[0054] Carbonate polyol compounds are synthesized, for example, by transesterification of a polyhydric alcohol with a carbonate ester. Examples of polyhydric alcohols include polyhydric alcohols having either a linear alkyl structure or a branched alkyl structure. Examples of polyhydric alcohols having a linear alkyl structure include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanodiol, 1,10-dodecanediol, 1,11-undecanediol, and 1,12-dodecanediol. Examples of polyhydric alcohols having a branched alkyl structure include 2-methyl-1,8-octanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol. The polyhydric alcohols may be used alone or in combination of two or more. Examples of carbonate esters include ethylene carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, and dibutyl carbonate. The carbonate esters may be used alone or in combination of two or more.

[0055] The number average molecular weight of the carbonate polyol compound is, for example, 300 or more, or may be 500 or more, or may be 800 or more. If the number average molecular weight is too small, a cured material layer having high elongation cannot be obtained. On the other hand, the number average molecular weight of the carbonate polyol compound is, for example, 3000 or less, or may be 1500 or less, or may be 1300 or less. If the number average molecular weight is too large, the cured material layer becomes too soft and the scratch resistance decreases.

[0056] In this specification, the number average molecular weight (Mn) of a carbonate polyol compound is a calculated value determined from the hydroxyl value, which is measured in accordance with JIS K1557-1.

[0057] (ii) Alkyl Alcohol Compound (B) In the present disclosure, in addition to the carbonate polyol compound (A), it is preferable to use an alkyl alcohol compound (B) having two or more hydroxyl groups. The use of an alkyl alcohol compound (B) having two or more hydroxyl groups allows for the adjustment of the ΔH value. Such an alkyl alcohol compound (B) is not particularly limited as long as it has an alkyl chain and at least two hydroxyl groups. The number of carbon atoms in the alkyl alcohol compound (B) is not particularly limited, but is preferably 20 or less, and alkyl alcohol compounds having 10 or less carbon atoms are particularly preferred. Using an alkyl alcohol compound with such a short carbon chain tends to result in a cured layer with high hardness. The number of carbon atoms in the alkyl alcohol compound is more preferably 4 or more and 8 or less. The alkyl chain in the alkyl alcohol compound (B) may be linear, branched, or cyclic.

[0058] The alkyl alcohol compound may have two or more hydroxyl groups per molecule. Among these, an alkyl diol having two hydroxyl groups is preferred. Examples of alkyl diols include neopentyl glycol, 1,3-butanediol, 1,3-propanediol, cyclohexanedimethanol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. These may be used alone or in combination of two or more.

[0059] (iii) Polyisocyanate Compound (C) The polyisocyanate compound (C) has two or more isocyanate groups in one molecule. Examples of the polyisocyanate compound (C) include aliphatic isocyanates, alicyclic isocyanates, and aromatic isocyanates. The polyisocyanate compound (C) may be a blocked isocyanate compound obtained by addition reaction using a known isocyanate blocking agent by a known, conventional, appropriate method.

[0060] In the present disclosure, alicyclic isocyanate compounds having an alicyclic structure are preferred. This is because a cured layer with good scratch resistance can be obtained. This is because the alicyclic structures interact with each other to form a pseudo-bonding state, thereby increasing hardness. On the other hand, when a linear isocyanate is used, scratch resistance deteriorates. From the viewpoint of weather resistance, the polyisocyanate compound is preferably a non-yellowing polyisocyanate that does not have an aromatic ring.

[0061] Examples of the alicyclic polyisocyanate compound include bis(isocyanatomethyl)cyclohexane (HXDI) such as 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, 2,4-methylcyclohexane diisocyanate, 2,6-methylcyclohexane diisocyanate, cyclohexylene diisocyanate, methyl Examples include alicyclic diisocyanates such as cyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexylene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, dimer acid diisocyanate, bicycloheptane triisocyanate, and hydrogenated xylylene diisocyanate, as well as tri- or higher functional alicyclic polyisocyanates such as their adducts, isocyanurates, and biurets. These may be used alone or in combination of two or more.

[0062] The alicyclic polyisocyanate compound is preferably a diisocyanate compound represented by the following general formula (2).

[0063] (In the formula, Xc is a divalent hydrocarbon group having an alicyclic structure and having 8 to 13 carbon atoms.)

[0064] Examples of the diisocyanate compound represented by the above formula (2) include 1,3-bis(isocyanatomethyl)cyclohexane (HXDI) and 4,4'-dicyclohexylmethane diisocyanate, with 1,3-bis(isocyanatomethyl)cyclohexane (HXDI) being preferred.

[0065] (iv) Hydroxyl Group-Containing (Meth)acrylate (D) The hydroxyl group-containing (meth)acrylate compound (D) is a compound having one or more hydroxyl groups and one or more (meth)acryloyl groups. Examples of the hydroxyl group-containing (meth)acrylate compound (D) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate.

[0066] The number of functional groups (number of (meth)acryloyl groups) of the hydroxyl group-containing (meth)acrylate (D) is preferably one. This is because a good balance between scratch resistance and elongation is achieved. Furthermore, the fewer the number of functional groups (number of (meth)acryloyl groups), the better the weather resistance. On the other hand, the number of functional groups (number of (meth)acryloyl groups) of the hydroxyl group-containing (meth)acrylate may be two or more. The number of hydroxyl groups in the hydroxyl group-containing (meth)acrylate is not particularly limited, but is preferably one. The hydroxyl group-containing (meth)acrylate is preferably a compound having one hydroxyl group and one (meth)acryloyl group. An example of such a hydroxyl group-containing (meth)acrylate is hydroxyethyl (meth)acrylate.

[0067] (b) Others The number average molecular weight (Mn) of the carbonate-based urethane (meth)acrylate is, for example, 1000 or more and may be 1500 or more so that the ΔH falls within the above-mentioned range. On the other hand, the number average molecular weight (Mn) is, for example, 6000 or less and may be 4000 or less.

[0068] In this specification, the number average molecular weight (Mn) of the carbonate-based urethane (meth)acrylate is a value determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0069] From the viewpoint of crosslinking and curing, the number of functional groups n of the carbonate-based urethane (meth)acrylate is, for example, from 2 to 6, or may be from 2 to 4, and is preferably 2 because this makes it easier to obtain the above-mentioned elongation. As mentioned above, the number of functional groups n of the carbonate-based urethane (meth)acrylate means the number of (meth)acryloyl groups in one molecule.

[0070] The carbonate-based urethane (meth)acrylate in the present disclosure has, for example, a structure represented by the following general formula (3): The urethane (meth)acrylate represented by the following general formula (3) is an example of a urethane (meth)acrylate structure when a carbonate diol is used as the component (A), an alkyl diol is used as the component (B), a diisocyanate compound is used as the component (C), and a compound having one hydroxyl group and one (meth)acryloyl group in the molecule is used as the component (D).

[0071] (In the formula, Ra represents the above-mentioned structural unit a, Rb represents the above-mentioned structural unit b, Rc represents the above-mentioned structural unit c, and Rd represents the above-mentioned structural unit d. p and q each represent the average value of the number of repetitions of each repeating unit, p is a number from 1 to 5, and preferably a number from 1 to 2. q is a number from 1 to 10, and preferably a number from 1 to 4. The arrangement order of each repeating unit is not particularly limited, and may be random or block.)

[0072] The content of the carbonate-based urethane (meth)acrylate in the present disclosure relative to a total of 100 parts by mass of the polymerizable compounds contained in the curable resin composition is, for example, 50 parts by mass or more, or may be 80 parts by mass or more, or may be 90 parts by mass or more. This is because the physical properties (ΔH and urethane bond retention rate) of the cured material layer described above are easily obtained. On the other hand, for example, it is 100 parts by mass or less.

[0073] (c) Production Method Carbonate-based urethane (meth)acrylates can be produced according to commonly known methods. For example, the carbonate polyol compound (A), alkyl alcohol compound (B), polyisocyanate compound (C), and hydroxyl group-containing (meth)acrylate (D), as well as a urethane-forming catalyst, polymerization inhibitor, antioxidant, and organic solvent (if necessary), are charged into a reaction vessel, and the mixture is allowed to react while maintaining a predetermined temperature. Alternatively, the carbonate polyol compound (A), alkyl alcohol compound (B), and polyisocyanate compound (C) can be reacted to obtain a urethane prepolymer having an isocyanate group at its terminal, and then the urethane prepolymer can be reacted with the hydroxyl group-containing (meth)acrylate (D). The urethane-forming reaction is typically carried out at a temperature in the range of 60 to 110°C.

[0074] Examples of catalysts include amine compounds such as triethylamine, piperazine, and triethanolamine, and organometallic compounds. Examples of organometallic compounds include organotin compounds such as dibutyltin dilaurate, tin octoate, tin laurate, and dioctyltin dilaurate, organozinc compounds such as zinc 2-ethylhexanoate, organozirconium compounds such as zirconium tetraacetylacetonate, and organobismuth compounds such as bismuth trioctate. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, and p-benzoquinone. In this process, a urethane prepolymer having an isocyanate group at its terminal is obtained.

[0075] The end point of the urethane reaction is 2270 cm, which indicates an isocyanate group. －１ This can be confirmed by determining the disappearance of the infrared absorption spectrum of the compound or by determining the content of isocyanate groups by the method described in JIS K 7301.

[0076] (2) Other Polymerizable Compounds The curable resin composition of the present disclosure may contain other polymerizable compounds in addition to the carbonate-based urethane (meth)acrylate. The content of the other polymerizable compounds relative to a total of 100 parts by mass of the polymerizable compounds contained in the curable resin composition is, for example, 5 parts by mass or more, and may even be 10 parts by mass or more. On the other hand, the content is, for example, 50 parts by mass or less, preferably 25 parts by mass or less, and more preferably 20 parts by mass or less.

[0077] The other polymerizable compound is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond-containing group, and examples thereof include compounds such as polymers (high polymers), oligomers (low polymers), and monomers (monomers), and known compounds can be used as appropriate. The polymerizable compound having an ethylenically unsaturated bond-containing group can be used alone or in combination of two or more.

[0078] In order to obtain chemical resistance to acidic chemicals such as sulfuric acid, the curable resin composition of the present disclosure preferably contains a hydrophobic polymerizable compound as another polymerizable compound. In this specification, a hydrophobic polymerizable compound refers to a compound having a hydrocarbon bond with 4 or more carbon atoms in its skeleton, excluding ethylenically unsaturated bond-containing groups such as (meth)acryloyl groups, and not containing an oxygen atom. Alternatively, the compound has a siloxane bond in the skeleton. The skeleton may have a linear, branched, or cyclic structure. On the other hand, a hydrophilic polymerizable compound refers to a compound having at least one oxygen atom, nitrogen atom, or sulfur atom in its skeleton, excluding ethylenically unsaturated bond-containing groups such as (meth)acryloyl groups. Examples of such functional groups include a hydroxyl group, an amino group, a carboxyl group, a sulfo group, and an ether bond.

[0079] Examples of the hydrophobic polymerizable compound include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples of the hydrophobic polymerizable compound include (meth)acrylates containing a siloxane bond.

[0080] The content of the hydrophobic polymerizable compound relative to a total of 100 parts by mass of the polymerizable compounds contained in the curable resin composition is, for example, 5 parts by mass or more, and may be 10 parts by mass or more. This improves resistance to acidic chemicals such as sulfuric acid. Meanwhile, the content of the hydrophobic polymerizable compound varies depending on the type of hydrophobic polymerizable compound, but is preferably, for example, 25 parts by mass or less, and more preferably 20 parts by mass or less. This is because both the physical properties (ΔH and urethane bond retention rate) of the cured material layer and chemical resistance can be achieved.

[0081] On the other hand, examples of hydrophilic polymerizable compounds include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerin di(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

[0082] (3) Weather Resistant The curable resin composition of the present disclosure preferably contains at least one of an ultraviolet absorber and a light stabilizer as a weather resistance agent. In particular, from the viewpoint of improving the urethane bond retention rate, it is preferable to use an ultraviolet absorber and a light stabilizer in combination. Furthermore, in the present disclosure, it is preferable that at least one of the ultraviolet absorber and the light stabilizer has an ethylenically unsaturated bond-containing group.

[0083] (a) Ultraviolet absorber The curable resin composition of the present disclosure may contain an ultraviolet absorber. By containing an ultraviolet absorber, the curable resin composition of the present disclosure is likely to achieve a high urethane bond retention rate. The ultraviolet absorbers may be used alone or in combination of two or more.

[0084] Examples of the ultraviolet absorber include benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, cyanoacrylate-based compounds, benzoxazinone-based compounds, benzoxazole-based compounds, and merocyanine-based compounds, and benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are more preferred.

[0085] The content of the ultraviolet absorber in the curable resin composition is, for example, 0.5 parts by mass or more and 10 parts by mass or less, or alternatively 0.8 parts by mass or more and 8 parts by mass or less, or 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. If the content of the ultraviolet absorber is too high, bleed-out of the ultraviolet absorber may occur, and if the content of the ultraviolet absorber is too low, sufficient ultraviolet absorption performance may not be obtained.

[0086] As the UV absorber, it is preferable to use a polymerizable UV absorber having an ethylenically unsaturated bond-containing group such as a (meth)acryloyl group, a vinyl group, or an allyl group in the molecule. A curable resin composition containing a UV absorber may result in reduced chemical resistance of the cured layer. The use of a polymerizable UV absorber results in a cured layer with less reduction in chemical resistance than when a non-polymerizable UV absorber without an ethylenically unsaturated bond-containing group is used. Therefore, both chemical resistance and weather resistance can be achieved. In the present disclosure, a polymerizable UV absorber and a non-polymerizable UV absorber may be used in combination. In the present disclosure, the content of the polymerizable UV absorber is preferably 0.1 parts by mass or more per 100 parts by mass of the polymerizable compound. Meanwhile, the content of the polymerizable UV absorber is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less per 100 parts by mass of the polymerizable compound. On the other hand, the content of the non-polymerizable ultraviolet absorber is preferably, for example, 1 part by mass or less relative to 100 parts by mass of the polymerizable compound, from the viewpoint of suppressing a decrease in chemical resistance.

[0087] Examples of the polymerizable ultraviolet absorber include ultraviolet absorbing monomers such as benzotriazole-based ultraviolet absorbing monomers and benzophenone-based ultraviolet absorbing monomers.

[0088] Examples of the benzotriazole-based ultraviolet absorbing monomer include 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, and 2-[2'-hydroxy-5'-(meth)acryloylaminomethyl-5'-tert-octylphenyl]-2H-benzotriazole. azole, 2-[2'-hydroxy-5'-(meth)acryloyloxypropylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy -5'-tert-butyl-3'-(meth)acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(β-(meth)acryloyloxyethylphenyl] [2-(2-hydroxypropyl)-5-(2-benzotriazolyl)-4-hydroxy-5-tert-butyl]phenylpropionate, 2-[2'-hydroxy-5'-(meth)acryloyloxyethoxy]-3'-tert-butylphenyl]-4-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyethylphenyl]-5-nitro-2H-benzotriazole, 3-(meth)acryloyl-2-hydroxypropyl-3-[3-(2-benzotriazolyl)-4-hydroxy-5-tert-butyl]phenylpropionate.

[0089] Examples of benzophenone-based ultraviolet absorbing monomers include 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-[2-hydroxy-3-(meth)acryloyloxy]propoxybenzophenone, 2-hydroxy-4-[2-(meth)acryloyloxy]ethoxybenzophenone, 2-hydroxy-4-[3-(meth)acryloyloxy-2-hydroxypropoxy]benzophenone, 2-hydroxy-3-tert-butyl-4-[2-(meth)acryloyloxy]butoxybenzophenone, and 2,2'-dihydroxy-4-[3-(meth)acryloyloxy-2-hydroxypropoxy]benzophenone.

[0090] (b) Light Stabilizer The curable resin composition of the present disclosure may contain a light stabilizer. By containing a light stabilizer, the curable resin composition of the present disclosure is likely to achieve a high urethane bond retention rate. The light stabilizer may be used alone or in combination of two or more.

[0091] Examples of the light stabilizer include hindered amine light stabilizers, such as 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine).

[0092] The content of the light stabilizer in the curable resin composition is, for example, 0.5 parts by mass or more and 10 parts by mass or less, or alternatively 0.8 parts by mass or more and 8 parts by mass or less, or 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. If the content of the light stabilizer is high, bleed-out of the light stabilizer may occur, and if the content of the light stabilizer is low, sufficient ultraviolet absorption performance may not be obtained.

[0093] As the light stabilizer, a polymerizable light stabilizer having an ethylenically unsaturated bond-containing group such as a (meth)acryloyl group, a vinyl group, or an allyl group in the molecule may be used. A curable resin composition containing a light stabilizer may result in reduced chemical resistance of the cured material layer. The use of a polymerizable light stabilizer results in a cured material layer with reduced chemical resistance compared to the use of a non-polymerizable light stabilizer that does not have an ethylenically unsaturated bond-containing group. Therefore, both chemical resistance and weather resistance can be achieved. In the present disclosure, a polymerizable light stabilizer and a non-polymerizable light stabilizer may be used in combination. In the present disclosure, the content of the polymerizable light stabilizer is preferably 0.1 parts by mass or more per 100 parts by mass of the polymerizable compound. Meanwhile, the content of the polymerizable light stabilizer is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less per 100 parts by mass of the polymerizable compound. On the other hand, the content of the non-polymerizable light stabilizer is preferably, for example, 1 part by mass or less relative to 100 parts by mass of the polymerizable compound, from the viewpoint of suppressing a decrease in chemical resistance.

[0094] Examples of the polymerizable light stabilizer include hindered amine-based polymerizable light-stable monomers, as well as a reaction product of decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide, and octane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, and a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate. Examples of the hindered amine-based polymerizable light-stable monomer include polymerizable compounds having a piperazine skeleton (particularly a 2,2,6,6-tetramethylpiperidine skeleton) (compounds having a piperazine skeleton and a polymerizable group).

[0095] (4) Leveling Agent The curable resin composition of the present disclosure may contain a leveling agent. By including a leveling agent, a smooth surface can be easily obtained when the resin composition is applied to the surface of a support substrate or a release substrate. Furthermore, when the cured product layer is used as a hard coat layer of an in-mold transfer film, the transfer film is inserted into an injection mold so that the release substrate contacts the mold, and then molten resin is injected and filled into the cavity. After cooling, the mold is opened, thereby simultaneously performing molding and transfer, and then the release substrate is peeled off. In the present disclosure, the curable resin composition contains a leveling agent, which facilitates peeling of the release substrate from the cured product layer. Examples of leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine-based leveling agents.

[0096] The leveling agent may be, for example, 0.1 parts by mass or more and 5 parts by mass or less, or 0.5 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the polymerizable compound contained in the curable resin composition.

[0097] Furthermore, in the present disclosure, it is preferable that the leveling agent contains an acrylic leveling agent. By containing an acrylic leveling agent, the peel strength between the release substrate and the hard coat layer is stable over time, making it possible to easily peel the release substrate from the cured material layer over a long period of time. Furthermore, it is preferable that the curable resin composition in the present disclosure does not contain either a silicone leveling agent or a fluorine leveling agent. In this case, the content ratio of silicon atoms derived from organic silicone and the content ratio of fluorine atoms relative to atoms with atomic numbers equal to or greater than Li detected by X-ray photoelectron spectroscopy on the surface of the cured material layer are below the detection limit. Silicone leveling agents and fluorine leveling agents significantly reduce surface tension compared to acrylic leveling agents, so that the state of the molecular chain changes over time, which easily changes the interfacial interaction between the release substrate and the hard coat layer. As a result, the stability of the peel strength over time is reduced. On the other hand, the curable resin composition may contain a silicone-based leveling agent and a fluorine-based leveling agent so that the content ratio of silicon atoms derived from organosilicon to atoms having atomic numbers of Li or more, as detected by X-ray photoelectron spectroscopy, on the surface of the cured material layer is in a range of 0.3 at% or less, and the content ratio of fluorine atoms is in a range of 0.3 at% or less.

[0098] The acrylic leveling agent may be any leveling agent having a (meth)acrylic skeleton. Examples of the (meth)acrylic skeleton include homopolymers and copolymers of (meth)acrylic acid esters. Examples of the (meth)acrylic acid esters include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; (poly)oxyalkylene glycol (meth)acrylates such as diethylene glycol (meth)acrylate, dipropylene glycol (meth)acrylate, and polyoxytetramethylene glycol (meth)acrylate; and polyester (meth)acrylates. These (meth)acrylic acid esters may be used alone or in combination.

[0099] As the acrylic leveling agent, commercially available products can also be used, such as BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, and BYK-392 (all manufactured by BYK Japan), OX-880EF, OX-881, OX-883, OX-883HF, OX-70, OX-77EF, and OX-6 0, OX-710, OX-720, OX-720EF, OX-750HF, LAP-10, LAP-20, LAP-30, 1970, 230, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, LHP-95, LHP-96 (all manufactured by Kusumoto Chemicals Co., Ltd., DISPARLON series), Polyflow No. 3, Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 55, Polyflow No. 64, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. Examples of the solid content include commercially available products such as Polyflow No. S, Polyflow No. 90, Polyflow No. 90D-50, Polyflow No. 95, Polyflow No. 300, Polyflow No. 460, Polyflow WS, Polyflow WS-30, and Polyflow WS-314 (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0100] The content of the acrylic leveling agent relative to 100 parts by mass of the total amount of the leveling agents contained in the curable resin composition is, for example, preferably 80 parts by mass or more and 100 parts by mass or less, and particularly preferably 100 parts by mass.

[0101] (5) Fine particles The curable resin composition according to the present disclosure may contain fine particles from the viewpoint of increasing the hardness of the cured layer or adjusting the refractive index. The fine particles may be inorganic or organic, but inorganic fine particles are preferred from the viewpoint of imparting hardness. Examples of inorganic fine particles include silica (SiO ２), aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like; and metal fluoride fine particles such as magnesium fluoride and sodium fluoride.

[0102] (6) Polymerization Initiator When the curable resin composition of the present disclosure is UV-curable and uses ultraviolet light for curing, it may contain at least one of a photopolymerization initiator, a polymerization accelerator, and a photoinitiation aid to rapidly cure. Examples of photopolymerization initiators include acetophenone-based compounds, benzoin ether-based compounds, benzophenone-based compounds, and thioxanthone-based compounds. The photopolymerization initiators may be used alone or in combination of two or more.

[0103] The content ratio of the photopolymerization initiator is not particularly limited, but may be, for example, 0.1 parts by mass or more and 30 parts by mass or less, and 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable compounds contained in the curable resin composition. Examples of polymerization accelerators and photoinitiation assistants include triethanolamine, methyldiethanolamine, and triisopropanolamine. The content ratio of the polymerization accelerator and photoinitiation assistant is not particularly limited, but may be, for example, 0.01 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the photopolymerization initiator.

[0104] In addition, when using electron beam curing for curing, there is no need to add photopolymerization initiator, polymerization accelerator or photoinitiator assistant.In this case, the content ratio of polymerizable compound in solid content can be increased, and a dense network can be formed, which is preferable because it is easy to improve scratch resistance.In addition, since it can be cured without adding photopolymerization initiator, it can be sufficiently cured even if a large amount of ultraviolet absorber is added, and the weather resistance of the hard coat film can be improved.

[0105] (7) Other Additives The curable resin composition of the present disclosure may further contain various additives, such as antioxidants, plasticizers, flame retardants, surfactants, thermal polymerization inhibitors, antistatic agents, antifogging agents, antibacterial agents, fillers, pigments, dyes, and colorants, as needed.

[0106] (8) Solvent The curable resin composition may contain a solvent to adjust the viscosity of the composition, or to improve the smoothness, uniformity, or adhesion to the substrate of the cured product layer. Known solvents can be used, including, for example, alcohols such as ethanol, propanol, isopropanol, and butanol; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-ethoxypropanol, 2-(2-ethoxyethoxy)ethanol, 1,4-dioxane, and tetrahydrofuran. The solvents may be used alone or in combination of two or more.

[0107] In the curable resin composition, the content ratio of the solvent may be adjusted appropriately depending on the purpose and is not particularly limited, but is preferably 40 parts by mass or more and 300 parts by mass or less, and more preferably 60 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the curable resin composition.

[0108] The curable resin composition of the present disclosure can be obtained by blending a carbonate-based urethane (meth)acrylate, other polymerizable compounds, various additives, and a solvent in predetermined proportions and mixing them uniformly by a conventional method.

[0109] 3. Cured Product Layer The cured product layer can be formed, for example, by applying the above-described curable resin composition to a substrate to a desired thickness, drying the composition to remove the solvent as necessary, and then irradiating the composition with active energy rays to cure the composition.

[0110] The method for applying the curable resin composition to the substrate is not particularly limited, and any known method can be used as appropriate. Examples of the application method include dipping, flow coating, spraying, spin coating, gravure coating, microgravure coating, die coating, slit reverse coating, roll coating, blade coating, air knife coating, offset coating, and bar coating. Imagewise application can also be performed by printing methods such as gravure printing, gravure offset printing, and screen printing.

[0111] When the curable resin composition contains a solvent, drying may be performed after coating to evaporate the solvent. For drying, known methods such as hot air heating, infrared heating, and far-infrared heating can be appropriately adopted. The preferred drying conditions vary depending on the boiling point of the solvent, the material of the release substrate, the coating amount, etc., but for example, the heating temperature is 30°C or higher and 120°C or lower, and the heating time is 1 minute or higher and 30 minutes or lower.

[0112] Examples of active energy rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps; and electron beams, α-rays, β-rays, and γ-rays typically extracted from particle accelerators of 20 to 2000 kV.

[0113] The thickness of the cured material layer varies depending on the application of the cured material layer, but is, for example, 0.1 μm or more, preferably 1 μm or more, and more preferably 4 μm or more, because this improves the urethane bond retention rate. On the other hand, the thickness of the cured material layer is, for example, 200 μm or less, or may be 100 μm or less, or may be 50 μm or less.

[0114] 4. Applications The cured product layer of the present disclosure has excellent elongation and scratch resistance under high-temperature conditions, and therefore can be suitably used in applications where it is used under high-temperature conditions, such as a hard coat layer in a film for molding processing. Furthermore, the cured product layer of the present disclosure has weather resistance, and therefore can be suitably used in applications where it is directly exposed to ultraviolet rays, sunlight, or moisture. The cured product layer of the present disclosure can be suitably used, for example, as a building material and an interior or exterior component of transportation equipment such as automobiles, trains, and airplanes, particularly as a protective layer for the exterior component.

[0115] B. Curable Resin Composition The present disclosure provides a curable resin composition used to produce the above-described cured material layer, the curable resin composition including a carbonate-based urethane (meth)acrylate.

[0116] The curable resin composition of the present disclosure can form a cured product layer having high scratch resistance, high weather resistance, and high elongation under high temperature conditions by irradiation with active energy rays. Therefore, the curable resin composition of the present disclosure can be suitably used as a material for forming a hard coat layer in a film for molding (a sheet for molding). Examples of molding processes include in-mold molding and insert molding.

[0117] The curable resin composition and carbonate-based urethane (meth)acrylate in the present disclosure are similar to the curable resin composition and carbonate-based urethane (meth)acrylate described in detail above in "A. Cured product layer," and therefore will not be described here.

[0118] C. Transfer Film The present disclosure provides a transfer film having a release substrate and a transfer layer, wherein the transfer layer has a hard coat layer and an adhesive layer in this order from the release substrate side, and the hard coat layer is the cured product layer described above.

[0119] 1 and 2 are schematic cross-sectional views illustrating an example of a transfer film according to the present disclosure. As shown in Fig. 1, the transfer film 10 has a release substrate 11 and a transfer layer 12. The transfer layer 12 has, from the release substrate 11 side, a hard coat layer 13 and an adhesive layer 14 in this order, and the hard coat layer 13 is the cured product layer described above. As shown in Fig. 2, the transfer film 10 may have a primer layer 15 between the hard coat layer 13 and the adhesive layer 14.

[0120] The transfer film according to the present disclosure has high scratch resistance and high elongation under high temperature conditions because the hard coat layer is the cured product layer described above, and therefore can be suitably used as an in-mold transfer film.

[0121] According to the transfer film of the present disclosure, as shown in FIG. 6 , when the adhesive layer 14 side is attached to a resin substrate 51 to form a laminate 50, the hard coat layer 13 becomes the outermost layer. The hard coat layer of the present disclosure is the cured product layer described above, and therefore has excellent weather resistance. Therefore, deterioration of layers disposed inside the resin substrate and hard coat layer in the laminate can be suppressed. Furthermore, the adhesive layer 14 and, in some cases, a primer layer are located between the hard coat layer 13 and the resin substrate 51. The thermoplastic resins contained in the adhesive layer and primer layer often have low chemical resistance. Even when such a layer with low chemical resistance is present, the chemical resistance of the laminate can be improved if the hard coat layer, which is a cured product layer of the curable resin composition of the present disclosure, has chemical resistance.

[0122] 1. Transfer Layer In the present disclosure, the transfer layer may have only a hard coat layer and an adhesive layer, or may further have other layers.

[0123] (1) Hard Coat Layer The hard coat layer is the same as that described above in "A. Cured Layer," and therefore, a description thereof will be omitted here. In particular, the hard coat layer of the transfer film in the present disclosure preferably has the silicon atom content ratio and the fluorine atom content ratio described in "A. Cured Layer 1. Physical Properties (4) Silicon Atom and Fluorine Atom Content Ratio."

[0124] (2) Adhesive Layer Any layer can be appropriately selected and used as the adhesive layer, as long as it has the function of adhering the substrate and the transfer layer. The adhesive layer may be present between other layers.

[0125] The adhesive layer is preferably a heat seal layer. The heat seal layer contains a thermoplastic resin that can be welded by heat. The thermoplastic resin is not particularly limited, and examples thereof include acrylic resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, chlorinated polypropylene, chlorinated rubber, urethane resin, epoxy resin, and styrene resin. The above resins may be used alone or in combination of two or more. The thickness of the heat seal layer is not particularly limited, and can be, for example, 1 μm or more and 7 μm or less, and preferably 1 μm or more and 6 μm or less.

[0126] (3) Other Layers As shown in Fig. 2, the transfer layer in the present disclosure may have a primer layer 15 between the hard coat layer 13 and the adhesive layer 14. Although not specifically shown, the transfer layer may further include another layer such as a decorative layer.

[0127] A primer layer may be further provided when the adhesion between the hard coat layer, which is a cured product layer of the curable resin composition, and another layer such as the heat seal layer is insufficient. Materials for the primer layer include, but are not limited to, acrylic resins, urethane resins, vinyl chloride / vinyl acetate copolymer resins, polyester resins, and chlorinated polyolefin resins. The thickness of the primer layer is not particularly limited, but is, for example, 0.1 μm or more and 10 μm or less.

[0128] The decorative layer may be disposed between the hard coat layer and the adhesive layer.

[0129] 2. Release Substrate The release substrate of the transfer film is not particularly limited as long as it can support the hard coat layer so as to be used for transferring the hard coat layer.

[0130] The release substrate has, for example, a resin film. Examples of the resin film include films of polyethylene (PE) resin, polypropylene (PP) resin, polybutadiene resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate resin, polyethylene naphthalate (PEN) resin, triacetyl cellulose (TAC) resin, polymethyl methacrylate (PMMA) resin, polycarbonate (PC) resin, cycloolefin polymer, ethylene vinyl acetate copolymer (EVA) resin, polyvinyl chloride (PVA) resin, ABS resin, and AS resin. Among these, films of polyethylene terephthalate (PET) resin are preferably used in terms of dimensional stability, releasability, and the like.

[0131] The resin film may be subjected to a surface treatment to improve releasability. Such surface treatment is generally carried out by applying a release agent. Examples of the release agent include fluororesin, silicone resin, and long-chain alkyl resin compounds.

[0132] The release substrate may have a resin film and a release layer disposed on the surface of the resin film facing the transfer layer. The release layer may be made of any material having releasability, but examples thereof include silicone resins, organic resin-modified silicone resins, fluororesins, aminoalkyd resins, melamine resins, acrylic resins, and polyester resins. The thickness of the release layer is not particularly limited, but examples thereof include 0.1 μm to 10 μm, and preferably 0.5 μm to 2 μm.

[0133] 3. Manufacturing Method The manufacturing method of the transfer film in the present disclosure is not particularly limited, but for example, a method of forming a hard coat layer on the surface of a release substrate and then forming an adhesive layer on the surface of the hard coat layer opposite to the release substrate can be used. The method of forming the hard coat layer is the same as the method of forming the cured product layer described above.

[0134] 4. Uses The transfer film according to the present disclosure can be suitably used for in-mold transfer because the hard coat layer, which is a cured product of the curable resin composition described above, has excellent elongation under high temperature conditions and excellent scratch resistance.

[0135] In the case of in-mold transfer, the transfer film of the present disclosure is inserted into an injection mold so that the release substrate is in contact with the mold, and then heated and molten resin is injected to fill the cavity, and then cooled and the mold is opened, thereby allowing molding and transfer to be performed simultaneously. By peeling off the release substrate after molding, the cured product of the curable resin composition as a hard coat layer and, in some cases, other layers such as a decorative layer are transferred to the resin molded product.

[0136] In addition to the in-mold transfer, the transfer film of the present disclosure can also be used for lamination transfer. For example, by thermally laminating the transfer film of the present disclosure on a resin plate or metal plate as a substrate, a hard coat layer (and a decorative layer) can be formed on the resin plate or metal plate. Since the hard coat layer of the present disclosure can be molded, after being attached to the resin plate or metal plate as a substrate, the resin plate or metal plate can also be subjected to bending and hot bending.

[0137] D. Hard Coat Film The present disclosure provides a hard coat film having a supporting substrate and a hard coat layer, wherein the hard coat layer is the cured product layer described above. While the transfer film described above is a film used for transferring the cured product layer, the hard coat film is applied in its entirety.

[0138] 3 and 4 are schematic cross-sectional views illustrating hard coat films according to the present disclosure. As shown in Fig. 3, the hard coat film 20 has a supporting substrate 21 and a hard coat layer 22. The hard coat layer 22 is the cured product layer described above. As shown in Fig. 4, the hard coat film 20 may have an adhesive layer 23 on the surface of the supporting substrate 21 opposite to the hard coat layer 22. Furthermore, as shown in Fig. 5, the hard coat film 20 may have a primer layer 24 between the supporting substrate 21 and the hard coat layer 22.

[0139] The hard coat film according to the present disclosure has high scratch resistance and high elongation under high temperature conditions because the hard coat layer is the cured product layer described above, and therefore can be suitably used as a film for insert molding.

[0140] According to the hard coat film of the present disclosure, as shown in FIG. 7 , when the hard coat film 20 is attached to a resin substrate 51 to form a laminate 50, the hard coat layer 22 becomes the outermost layer. The hard coat layer of the present disclosure is the cured product layer described above, and therefore has excellent weather resistance. Therefore, deterioration of layers disposed inside the resin substrate and hard coat layer in the laminate can be suppressed. Furthermore, when the laminate 50 is formed, an adhesive layer 23 and a primer layer may be located between the hard coat layer 22 and the resin substrate 51. The thermoplastic resins contained in the adhesive layer and primer layer often have low chemical resistance. Even when such a layer with low chemical resistance is present, the chemical resistance of the laminate can be improved if the hard coat layer, which is the cured product layer of the present disclosure, has chemical resistance.

[0141] 1. Hard Coat Layer The hard coat layer is the same as that described above in "A. Cured Layer," and therefore, a description thereof will be omitted here.

[0142] 2. Supporting Substrate The supporting substrate in the present disclosure is disposed on the resin substrate together with other components without being peeled off when the hard coat film is attached to the resin substrate. The supporting substrate is not particularly limited, but may be, for example, a resin film such as an acrylic resin film, a polyester resin film, a polyolefin resin film, or a polyvinyl chloride resin film.

[0143] The support substrate may be transparent or opaque. The substrate layer may be a colored substrate layer containing a colorant, or may be colorless. In this embodiment, at least the surface of the support substrate facing the hard coat layer may be subjected to a known surface modification treatment, or may be provided with a coating layer of an easy-adhesion coating agent. This is because the adhesion between the substrate layer and the hard coat layer can be improved.

[0144] The thickness of the support substrate is not particularly limited, but may be, for example, 4 μm or more and 200 μm or less. The support substrate may have a single layer structure or a multi-layer structure. In the case of a multi-layer structure, the thickness of the entire multi-layer structure can be within the above-mentioned range.

[0145] 3. Other Layers (1) Adhesive Layer As shown in Fig. 4, the hard coat film 20 according to the present disclosure may have an adhesive layer 23 on the surface of the supporting substrate 21 opposite to the hard coat layer 22. This allows the hard coat film according to the present disclosure to be attached to a resin substrate via the adhesive layer. On the other hand, for example, when the supporting substrate contains a thermoplastic resin, the supporting substrate may also have an adhesive function.

[0146] In this embodiment, the adhesive layer can be an adhesive layer (adhesive layer) containing a pressure-sensitive adhesive or an adhesive layer (adhesive layer). The resin constituting the adhesive layer or the pressure-sensitive adhesive layer is not particularly limited and can be the same as the resin contained in a general adhesive or pressure-sensitive adhesive used for lamination applications. Examples of the resin include acrylic resins, ester resins, urethane resins, ethylene vinyl acetate resins, latex resins, epoxy resins, polyurethane ester resins, fluorine-based resins such as vinylidene fluoride resins (PVDF) and vinyl fluoride resins (PVF), polyimide resins such as polyimide, polyamideimide, and polyetherimide, and rubber.

[0147] The adhesive layer may be a heat-sealing layer, which is the same as the heat-sealing layer in "C. Transfer film" above, and therefore will not be described here.

[0148] The thickness of the adhesive layer is not particularly limited, but can be appropriately set so as to provide sufficient adhesive strength when the hard coat film of this embodiment is attached to a resin substrate, for example, 1 μm to 7 μm, preferably 1 μm to 6 μm.

[0149] (2) Primer Layer As shown in FIG. 5 , the hard coat film 20 according to the present disclosure may have a primer layer 24 between the supporting substrate 21 and the hard coat layer 22 .

[0150] The primer layer is the same as that in "C. Transfer film" above, and therefore a description thereof will be omitted here.

[0151] (3) Others Known layers can be appropriately selected and used as other layers such as a decorative layer. The decorative layer is disposed, for example, between the hard coat layer and the supporting substrate.

[0152] 4. Manufacturing Method of Hard Coat Film The manufacturing method of the hard coat film in the present disclosure is not particularly limited, but for example, the hard coat film can be obtained by applying a composition for forming a hard coat layer to one surface of a supporting substrate and curing the composition to form a hard coat layer. The method for forming the hard coat layer is the same as the method for forming the cured product layer described above.

[0153] E. Laminate The present disclosure provides a laminate having a substrate and a hard coat layer laminated on the substrate, wherein the hard coat layer is the cured product layer described above.

[0154] The substrate is not particularly limited as long as it can laminate the cured product layer of the present disclosure thereon. The shape of the substrate may be a molded body, a sheet, or a plate. Substrates made of various materials, such as resin, glass, metal, wood, and paper, can be used. Among these, resins are preferred, such as polyethylene (PE) resin, polypropylene (PP) resin, polybutadiene resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate resin, polyethylene naphthalate (PEN) resin, triacetyl cellulose (TAC) resin, polymethyl methacrylate (PMMA) resin, polycarbonate (PC) resin, cycloolefin polymer, ethylene vinyl acetate copolymer (EVA) resin, polyvinyl chloride (PVA) resin, ABS resin, and AS resin.

[0155] When the substrate is a resin substrate, the laminate in the present disclosure is broadly divided into two embodiments depending on the layer structure. Each embodiment of the laminate will be described below.

[0156] 1. First Aspect Figure 6 is a schematic cross-sectional view illustrating a laminate of the first aspect. The laminate 50 of this aspect has a resin base 51, an adhesive layer 14, and a hard coat layer 13, in this order, and the hard coat layer 13 is the cured product layer described above. As described above, other layers such as a primer layer and a decorative layer may be present between the hard coat layer 13 and the adhesive layer 14. According to the laminate of this aspect, the hard coat layer 13 is located as the outermost layer, thereby improving the scratch resistance and weather resistance of the laminate.

[0157] Hereinafter, each component of the laminate of this embodiment will be described. Note that the hard coat layer in the laminate of this embodiment has been described in detail in the above section "A. Cured product layer", so a description thereof will be omitted here. The adhesive layer, primer layer, decorative layer, hard coat layer, etc. in the laminate of this embodiment have been described in detail in the above section "C. Transfer film", so a description thereof will be omitted here.

[0158] The resin substrate to be adhered is not particularly limited, but is preferably a resin molded product that is required to be scratch-resistant and weather-resistant, such as a building material or an interior or exterior member of transportation equipment such as an automobile, train, or airplane, particularly an exterior member.

[0159] As a method for producing the laminate of this embodiment, it is preferable to use an in-mold molding method. In the in-mold molding method, the transfer film of the present disclosure is inserted into an injection mold so that the release substrate is in contact with the mold, and then heated and molten resin is injected and filled into the cavity, and then cooled and the mold is opened, thereby simultaneously molding and transferring the resin substrate. By peeling off the release substrate after molding, the cured product layer of the curable resin composition as a hard coat layer and, in some cases, other layers such as a decorative layer are transferred to the resin molded product.

[0160] 2. Second Aspect The laminate of this aspect is a laminate produced using the hard coat film described above. FIG. 7 is a schematic cross-sectional view showing an example of the laminate of this aspect. This laminate 50 has, in this order, a resin base 51, an adhesive layer 23, a supporting substrate 21, and a hard coat layer 22, and the hard coat layer is a cured product of the curable resin composition described above. As described above, other layers such as a primer layer and a decorative layer may be present between the supporting substrate 21 and the hard coat layer 22. According to the laminate of this aspect, the hard coat layer 22 is located as the outermost layer, thereby improving the scratch resistance and weather resistance of the laminate.

[0161] The resin substrate in the laminate of this embodiment has been described in detail in the first embodiment, and therefore its description will be omitted here. The hard coat layer in the laminate of this embodiment has been described in detail in the above section "A. Cured product layer," and therefore its description will be omitted here. The adhesive layer, primer layer, decorative layer, hard coat layer, etc. in the laminate of this embodiment have been described in detail in the above section "D. Hard coat film," and therefore their description will be omitted here.

[0162] The method for producing the laminate of this embodiment preferably uses an insert molding method. The insert molding method includes at least a molding step of previously molding a hard coat film into the surface shape of an article, an injection step of placing the molded hard coat film in an injection mold, closing the injection mold, and injecting a resin composition in a fluid state into the injection mold, and a solidification step of solidifying the injected resin composition to form a resin base and placing the hard coat film on the surface of the resin base.

[0163] Alternatively, the hard coat film can be attached to a three-dimensional resin molded body prepared in advance by a decoration method such as a vacuum pressure bonding method, for example, a three-dimensional overlay method (TOM method).

[0164] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included within the technical scope of the present disclosure.

[0165] Example 1-1 A main component X1 containing a carbonate-based urethane (meth)acrylate and a solvent (methyl ethyl ketone) was used as a curable resin composition. The carbonate-based urethane (meth)acrylate had a structural unit a derived from an acyclic skeleton-based carbonate polyol (number average molecular weight of 1,000 calculated from the hydroxyl value) having a terminal hydroxyl group, a structural unit b derived from neopentyl glycol, a structural unit c derived from 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), and a structural unit d derived from 2-hydroxyethyl acrylate. The number average molecular weight (Mn), number of functional groups (number of (meth)acryloyl groups, n), number average molecular weight / number of functional groups (Mn / n), and M Ｓ / Mn and M Ｈ / Mn are shown in Table 1. The number average molecular weight (Mn) of the urethane (meth)acrylate is a value determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0166] (Preparation of Test Sample 1) The above curable resin composition was applied to a 50 μm-thick PET film (polyester film Cosmoshine A4160, manufactured by Toyobo Co., Ltd.) in a coating amount of 5 g / m ２ After coating so that the composition satisfies the above formula (1), the coating was dried at 90°C for 60 seconds to form a coating film. The coating film was irradiated with an electron beam at 8 Mrad and 165 kV to form a cured layer (hard coat layer) of the curable resin composition. As a result, test sample 1 having a PET film 61 and a cured layer (hard coat layer) 62 was obtained, as shown in Fig. 8(a) .

[0167] (Preparation of Transfer Film) The following primer layer material was applied to the hard coat layer of the above test sample 1 in an amount of 3 g / m ２and dried at 90°C for 90 seconds to form a primer layer. Next, the following heat seal layer material was applied to the primer layer in a coating amount of 3 g / m ２ and dried at 90°C for 90 seconds to form a heat seal layer (adhesive layer). This resulted in a transfer film. Primer layer material: SG131 (manufactured by DIC Graphics Corporation) A curing agent (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) Heat seal layer material: TMR-600 (acrylic resin, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)

[0168] (Preparation of Test Sample 2 (Laminate)) The transfer film was placed on a 2 mm thick polycarbonate (PC) plate (Carboglass Polish C110C, manufactured by AGC) on a hot plate at 140°C, and then the adhesive layer of the resulting transfer film was placed in contact with the PC plate. The resulting film was then laminated three times with a thermal laminating roll at 180°C to bond the two together. The PET film serving as the release substrate for the transfer film was then peeled off. As a result, as shown in FIG. 8(b), Test Sample 2 (laminate) was obtained, which had a resin base (PC plate) 63, an adhesive layer 64, a primer layer 65, and a cured product layer 62 in this order.

[0169] (Examples 1-2 to 1-8) The content of each of the structural units a to d in Example 1-1 was different, and the number of functional groups n, number average molecular weight / number of functional groups (Mn / n), and M Ｓ / Mn and M Ｈ Test sample 1 and test sample 2 were prepared in the same manner as in Example 1-1, except that main components X2 to X8 containing a urethane (meth)acrylate having / Mn and a solvent (methyl ethyl ketone) were used as the curable resin composition.

[0170] (Example 1-9) A copolymer containing the structural units a to c of Example 1-1 and the structural unit d derived from glycerin diacrylate, having the number of functional groups n, number average molecular weight / number of functional groups (Mn / n), and M Ｓ / Mn and M ＨTest sample 1 and test sample 2 were produced in the same manner as in Example 1-1, except that main component X9 containing a urethane (meth)acrylate having / Mn and a solvent (methyl ethyl ketone) was used as the curable resin composition.

[0171] (Example 1-10) A copolymer containing the structural units a to c of Example 1-1 and the structural unit d derived from pentaerythritol triacrylate, having the number of functional groups n, number average molecular weight / number of functional groups (Mn / n), and M Ｓ / Mn and M Ｈ Test sample 1 and test sample 2 were produced in the same manner as in Example 1-1, except that main component X10 containing a urethane (meth)acrylate having / Mn and a solvent (methyl ethyl ketone) was used as the curable resin composition.

[0172] (Comparative Example 1-1 to Comparative Example 1-8) The content of each of the structural units a to d in Example 1-1 was different, and the number of functional groups n, number average molecular weight / number of functional groups (Mn / n), and M Ｓ / Mn and M Ｈ Test sample 1 and test sample 2 were prepared in the same manner as in Example 1-1, except that main components X11 to X18 containing a urethane (meth)acrylate of / Mn and a solvent (methyl ethyl ketone) were used as the curable resin composition.

[0173] (Comparative Examples 1-9 to 1-12) A laminate was produced in the same manner as in Example 1-1, except that a base resin X19 containing an ester-based urethane (meth)acrylate and a solvent (methyl ethyl ketone) was used as the curable resin composition. The ester-based urethane (meth)acrylate contained a structural unit a derived from an ester polyol compound having a terminal hydroxyl group, a structural unit b derived from an alkyl alcohol compound, a structural unit c derived from a polyisocyanate compound, and a structural unit d derived from a hydroxyl group-containing (meth)acrylate compound. The number average molecular weight (Mn), number of functional groups (n), number average molecular weight / number of functional groups (Mn / n), and M Ｓ / Mn and M Ｈ / Mn are shown in Table 3. Ｓ / Mn and M Ｈ / Mn was calculated using the following formula: M Ｈ / Mn={(number of functional groups in one molecule of urethane (meth)acrylate) / (number of functional groups of compound (D))}×{(number of moles of compound (B)) / (number of moles of compound (D))}×{(molecular weight of compound (B)) / (Mn)} M Ｓ / Mn={(number of functional groups in one molecule of urethane (meth)acrylate) / (number of functional groups of compound (D))}×{(number of moles of compound (A)) / (number of moles of compound (D))}×{(number average molecular weight of compound (A)) / (Mn)}

[0174] Comparative Example 1-13 Test Sample 1 and Test Sample 2 were prepared in the same manner as in Example 1, except that a curable resin composition was used containing a urethane acrylate having a difunctional polycarbonate skeleton and a hexafunctional acrylate in a ratio of 90 / 10, and a solvent (methyl ethyl ketone). The average molecular weight (Mn), number of functional groups (n), number average molecular weight / number of functional groups (Mn / n), and M of each acrylate were measured. Ｓ / Mn and M Ｈ / Mn are shown in Table 3.

[0175] [Elongation under high temperature conditions] Test sample 1 obtained in the examples and comparative examples was cut into a size of 2.5 cm x 10 cm. A tensile test was carried out on this sample using a tensile tester (AUTOGRAPH AG-Xplus manufactured by Shimadzu Corporation) at 180°C, a chuck distance of 5 cm, and a tensile speed of 100 mm / min. The length of elongation when cracks appeared in the cured material layer was measured, and the elongation was calculated as follows: Elongation = {(elongation length when cracks began to appear in the cured material layer) / (5 cm chuck distance before test)} x 100 (%)

[0176] [Evaluation of Scratch Resistance] Test sample 2 obtained in each of the examples and comparative examples was cut into a size of 10 cm x 10 cm, and the sample was subjected to a Taber abrasion test in accordance with JIS K5600 under the conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 rpm, to measure the difference ΔH in haze value before and after the test.

[0177] [Weather resistance] Test sample 2 obtained in the examples and comparative examples was subjected to an irradiation test in which a xenon lamp was irradiated from the cured product layer side under the following conditions using a weather resistance tester xenon weather meter (Suga Test Instruments Co., Ltd., 7.5 kW Super Xenon Weather Meter SX75), and the time until cracks occurred was measured. In addition, the urethane bond retention rate after 1000 hours of xenon lamp irradiation was calculated using the following method. <Conditions> A xenon irradiation test was conducted under the following conditions (1) and (2) in a repeated cycle. <Condition (1): Irradiation> Irradiance: 180 W / m ２ Black panel temperature (BPT): 63°C Humidity: 50% Water spray: No Time: 102 minutes <Condition (2): Irradiation + Rainfall> Irradiance: 180 W / m2 Black panel temperature (BPT): 28°C Humidity: 95% Water spray: Yes Time: 18 minutes

[0178] The surface condition of the hard coat layer was visually observed every 100 hours to check for the occurrence of cracks. After 1000 hours of weather resistance testing, the urethane bond retention rate was calculated by the following method.

[0179] <Method for calculating urethane bond retention rate> The infrared absorption spectrum (IR spectrum) of the hard coat layer was measured by an attenuated total reflection measurement method (ATR measurement method) using an infrared spectrophotometer (JASCO FT / IR-6100, manufactured by JASCO Corporation). The horizontal axis represents wave numbers (cm －１ In the IR spectrum, the vertical axis represents the absorption intensity, and the absorption intensity of each peak was calculated by the tangent method as follows: (1) 1480-1580 cm －１ The valleys on both sides of the peak observed at 1480 cm －１ The minimum value of the nearby valley is 1580 cm －１ The baseline was set by connecting the points (minimum value of the valley nearby) with a straight line, and the distance from the baseline to the －１ The top height of the peak observed in the vicinity is the absorption intensity A1520. The absorption intensity A1520 is the absorption intensity of the absorption spectrum derived from the urethane group. (2) 1600 to 1800 cm －１ The valleys on both sides of the peak observed at －１The minimum value of the nearby valley and 1800 cm －１ A baseline was set by connecting the points (minimum value of the valley in the vicinity) with a straight line, and a distance of 1720 cm from the baseline was set. －１ The top height of the peak observed nearby is taken as the absorption intensity A1720. The absorption intensity A1720 is the absorption intensity of the absorption spectrum derived from the ester group. In the above (1) and (2), if there is no valley on one or both sides of the peak, the base line may be used to draw the baseline. (3) The absorption intensity A1520 and the absorption intensity A1720 values ​​before and after 1000 hours of weather resistance testing were used to calculate the urethane bond retention rate as follows: Urethane bond retention rate = {(A1520 after weather resistance testing / A1720 after weather resistance testing) / (A1520 before weather resistance testing / A1720 before weather resistance testing)} x 100 (%)

[0180] [Coatability] The following primer layer material was applied to the test sample 1 obtained in the examples and comparative examples in an amount of 3 g / m ２ and dried at 90°C for 90 seconds to form a primer layer. The primer layer side of this laminate was visually observed to evaluate whether or not there was any cissing of the primer layer material. Primer layer material SG131 (manufactured by DIC Graphics Corporation) A curing agent (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) <Evaluation criteria> A: No cissing B: Cracks present

[0181] [Evaluation of chemical resistance] Resistance to the chemicals shown in Table 1 was evaluated in accordance with "JIS K5600-6-1 9. Method 3 (Drip Method) Procedure A (Horizontal Method)." Test Sample 2 obtained in the Examples and Comparative Examples was cut into a size of 5 cm x 5 cm, IPA (isopropyl alcohol) was dropped onto the cured layer of the sample with a pipette, the test liquid was covered with a Petri dish, and changes were observed after leaving it at room temperature (23±2°C) for 1 hour and after leaving it for 24 hours. <Evaluation criteria> A: No change in appearance such as wrinkles, swelling, peeling, discoloration, etc. B: Change in appearance such as wrinkles, swelling, peeling, discoloration, etc.

[0182]

[0183]

[0184]

[0185] As shown in Tables 1 to 3, it was confirmed that Examples 1-1 to 1-10 provided cured product layers with excellent elongation, scratch resistance, and weather resistance. Specifically, Comparative Examples 1-9 to 1-12, which used ester-based urethane (meth)acrylate, had a cracking time of 1,000 hours or less. On the other hand, Examples 1-1 to 1-10, which used carbonate-based urethane (meth)acrylate, had a high urethane bond retention rate and a long cracking time of 1,700 hours or more, demonstrating good weather resistance.

[0186] Furthermore, the extensibility was reduced in Comparative Examples 1-11 and 1-12, which used a urethane (meth)acrylate with a number average molecular weight / number of functional groups (Mn / n) ratio of less than 900. On the other hand, it was confirmed that the cured product layers of Examples 1-1 to 1-10, which used a polycarbonate-based urethane (meth)acrylate with a number average molecular weight / number of functional groups (Mn / n) ratio of 900 or more, had excellent extensibility.

[0187] Furthermore, (M Ｓ / Mn) is 30% or more and 50% or less, and (M Ｈ It was confirmed that Examples 1-1 to 1-10, in which the ratio of Mn to Mn was 4% or more and 15% or less, had excellent scratch resistance. Ｓ / Mn) and (M Ｈ / Mn) does not satisfy the above range (Comparative Example 1-1 to Comparative Example 1-8), it was confirmed that the scratch resistance was reduced.

[0188] (Examples 2-1 to 2-6) The main component X3 used in Example 1-3 above was mixed with an ultraviolet absorber and a light stabilizer of the type and amount shown in Table 4 to obtain a curable resin composition. The amounts of the ultraviolet absorber and light stabilizer in Table 4 are the amounts (parts by mass) relative to 100 parts by mass of the urethane (meth)acrylate in the main component X3. Test sample 1 and test sample 2 were prepared in the same manner as in Example 1-1, except that the obtained curable resin composition was used.

[0189] (Comparative Example 2-1) A curable resin composition was obtained by mixing the main agent X19 used in Comparative Example 1-9 above with the ultraviolet absorber and light stabilizer of the types and amounts shown in Table 4. Test sample 1 and test sample 2 were produced in the same manner as in Example 1-1, except that the obtained curable resin composition was used.

[0190] The ultraviolet absorbers and light stabilizers used in Examples 2-1 to 2-6 and Comparative Example 2-1 are as follows. Ultraviolet absorbers Ultraviolet absorber 1: TINUVIN 405 (manufactured by BASF) Ultraviolet absorber 2: TINUVIN 1600 (manufactured by BASF) Ultraviolet absorber 3: RUVA-93 (reactive ultraviolet absorber, manufactured by Otsuka Chemical Co., Ltd.) Ultraviolet absorber 4: TINUVIN 400 (manufactured by BASF) Light stabilizers Light stabilizer 1: LS3410 (reactive light stabilizer, Nippon Nyukazai Co., Ltd.) Light stabilizer 2: TINUVIN 123 (manufactured by BASF) Light stabilizer 3: TINUVIN 152 (manufactured by BASF)

[0191] The above-described tests for elongation and coatability were conducted on Test Sample 1 of Examples 2-1 to 2-6 and Comparative Example 2-1. Test Sample 2 of Examples 2-1 to 2-6 and Comparative Example 2-1 was also tested for scratch resistance, weather resistance, and chemical resistance. The results are shown in Table 4.

[0192]

[0193] As shown in Table 4, in Examples 2-1 to 2-6, it was confirmed that the combined use of an ultraviolet absorber and a light stabilizer further improved weather resistance compared to Example 1-3. On the other hand, in Comparative Example 2-1, weather resistance was poor even when an ultraviolet absorber and a light stabilizer were used in combination. It was also confirmed that chemical resistance decreased when a weathering agent not having an ethylenically unsaturated bond-containing group was contained in an amount of more than 1 part by mass per 100 parts by mass of urethane (meth)acrylate (Examples 2-1, 2-2, 2-5, and 2-6). It was also confirmed that the use of a weathering agent having an ethylenically unsaturated bond-containing group enabled both chemical resistance and weather resistance to be achieved (Examples 2-3 and 2-4).

[0194] (Examples 3-1 to 3-7, Comparative Examples 3-1 to 3-5) A curable resin composition was obtained by mixing the main agent X3 used in Example 1-3 above with the polymerizable compounds 1 to 4, ultraviolet absorber 3, and light stabilizer 1 of the types and amounts shown in Table 5. Test sample 1 and test sample 2 were produced in the same manner as in Example 1-1, except that the obtained curable resin composition was used.

[0195] The polymerizable compounds 1 to 4 used in Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-5 are as follows: Polymerizable compound 1: Light acrylate DCP-A (dimethylol-tricyclodecane diacrylate (hydrophobic polymerizable monomer), manufactured by Kyoeisha Chemical Co., Ltd.) Polymerizable compound 2: Light acrylate 1,9ND-A (1,9-nonanediol diacrylate (hydrophobic polymerizable monomer), manufactured by Kyoeisha Chemical Co., Ltd.) Polymerizable compound 3: Siloxane bond-containing acrylate SQ-250 (hydrophobic polymerizable compound, manufactured by Tokushiki Co., Ltd.) Polymerizable compound 4: Aronix M-240 (hydrophilic polymerizable monomer, manufactured by Toagosei Co., Ltd.)

[0196] Test Sample 1 of Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-5 was subjected to the above-described elongation test, coating suitability test, and the following blocking test. Test Sample 2 of Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-5 was subjected to tests for scratch resistance, weather resistance, and chemical resistance. The results are shown in Table 5. For chemical resistance, a chemical resistance test was performed using IPA (isopropyl alcohol) and sulfuric acid, respectively.

[0197] [Blocking Property Test] Five test samples 1 obtained in each of the examples and comparative examples were stacked and subjected to a load of 2 kg / cm ２ The blocking test was carried out under the conditions of 100°C, room temperature of 20°C, and 24 hours. The stacked films were peeled off, and blocking evaluation was carried out according to the following criteria. <Evaluation criteria> A: The films were easily peeled off, and no blocking occurred. B: When the films were peeled off, noise due to blocking was generated, or the hard coat layer was taken over on the substrate layer side of one of the adjacent films.

[0198]

[0199] As shown in Table 5, it was confirmed that the use of a polymerizable compound other than urethane (meth)acrylate (other polymerizable compound) in combination with urethane (meth)acrylate improved blocking properties. It was also confirmed that the use of a hydrophobic polymerizable compound as the other polymerizable compound improved chemical resistance to sulfuric acid compared to the use of a hydrophilic polymerizable compound (Example 3-7, Comparative Example 3-4, and Comparative Example 3-5). On the other hand, if the blending amount of a polymerizable compound other than the carbonate-based urethane (meth)acrylate of the present disclosure (other polymerizable compound) is too high, elongation, scratch resistance, and weather resistance tend to decrease. Therefore, it was confirmed that the content of the other polymerizable compound, although varying depending on the type of other polymerizable compound, is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

[0200] (Examples 4-1 to 4-10) A release layer having a thickness shown in Table 6 was formed on a substrate layer shown in Table 6 using the following materials. A curable resin composition containing main agent X3 and a leveling agent shown in Table 6 was applied to the release layer in an amount of 5 g / m. ２ After coating so that the curable resin composition was formed, the coating was dried at 90°C for 60 seconds, and then irradiated with an electron beam at 8 Mrad and 165 kV to form a cured layer (hard coat layer) of the curable resin composition. This resulted in test samples 3 of Examples 4-1 to 4-10. As shown in Figure 8(c), test sample 3 has a PET film 61, a release layer 66, and a cured layer 62 in this order in the thickness direction. Release layer materials Material 1: EX-114D Medium (acrylic / melamine-based thermosetting resin, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) Material 2: IMLD Rikei T-kai 1 (EB-cured acrylate resin, manufactured by Showa Ink Industrial Co., Ltd.) Leveling agents LA1: BYK-361N (acrylic-based, manufactured by BYK Japan) LA2: Tego 2100 (silicone-based, manufactured by Shin-Etsu Chemical Co., Ltd.) LA3: F-568 (fluorine-based, manufactured by DIC Corporation)

[0201] Test samples 2 of Examples 4-1 to 4-10 were prepared in the same manner as in Example 1-1, except that a curable resin composition containing main component X3 and a leveling agent shown in Table 6 was used.

[0202] [X-ray Photoelectron Spectroscopy Analysis] For the surface of the hard coat layer of Test Sample 2, the content ratio of silicon atoms derived from organic silicone and the content ratio of fluorine to atoms with atomic numbers equal to or greater than Li detected by X-ray photoelectron spectroscopy analysis were calculated as described above.

[0203] [Peel Test] Test Samples 3 of Examples 4-1 to 4-10 were stored in a constant-temperature oven at 60°C for 0 hours to a maximum of 800 hours, and the peel strength was measured when the coating film was peeled from the PET substrate. Specifically, test samples 3 were first cut into 1.5 cm wide and 8 cm or longer specimens. The substrate layer side of the specimen was fixed to a flat plate with double-sided adhesive tape, and cellophane tape was attached to the surface of the coating film side. Using a tensile tester (AUTOGRAPH AG-Xplus manufactured by Shimadzu Corporation), while the flat plate portion was fixed, the edge of the cellophane tape was pulled in a direction peeling 180° from the flat plate under the following conditions, and the peel strength (N / 15 mm) when the hard coat layer was peeled from the release layer together with the cellophane tape was measured. Distance between chucks: 10 cm, Pulling speed: 300 mm / min, Temperature in thermostatic chamber: 60°C (assuming the substrate peeling temperature at the end of injection molding)

[0204]

[0205] As shown in Table 6, the cured material layers containing an acrylic leveling agent (Examples 4-1 and 4-2) and the cured material layers containing small amounts of silicone-based leveling agent and fluorine-based leveling agent (Examples 4-7 to 4-10) showed a small difference in peel strength from 0 hours (immediately after production of the transfer film) to 800 hours after the lapse of time, but the cured material layers containing a silicone-based leveling agent and a fluorine-based leveling agent and having a content ratio of silicon atoms derived from organosilicon on the surface of the cured material layer of more than 0.3 at% or a content ratio of fluorine atoms of more than 0.3 at% (Examples 4-3 to 4-6) showed an increase in peel strength.

[0206] Thus, the present disclosure provides, for example, the following inventions.

[0207] [1] A cured layer of a curable resin composition containing a carbonate-based urethane (meth)acrylate, wherein the cured layer has a difference ΔH in haze value before and after the Taber abrasion test performed under the conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 rpm of 14% or less, and an illuminance of 180 W / m ２ The cured product layer has a urethane bond retention rate of 70% or more after 1000 hours of weather resistance testing using a xenon lamp at 100°C.

[0208] [2] The cured material layer according to [1], wherein the cured material layer has an elongation of 50% or more when cracks occur in a thermal tensile test at 180°C.

[0209] [3] The cured product layer according to [1] or [2], wherein the carbonate-based urethane (meth)acrylate has a number average molecular weight / number of functional groups of 900 or more.

[0210] [4] The cured product layer according to any one of [1] to [3], wherein the carbonate-based urethane (meth)acrylate has a structural unit a derived from a carbonate polyol compound (A) having a terminal hydroxyl group, a structural unit b derived from an alkyl alcohol compound (B), a structural unit c derived from a polyisocyanate compound (C), and a structural unit d derived from a hydroxyl group-containing (meth)acrylate compound (D), and the structural unit d is located at a molecular chain terminal.

[0211] [5] The total amount (M Ｓ ) ratio (M Ｓ / Mn) is 30% or more and 50% or less, and the total amount (M Ｈ ) ratio (M Ｈ / Mn) is 4% or more and 15% or less.

[0212] [6] The cured product layer according to any one of [1] to [5], wherein the curable resin composition contains at least one of an ultraviolet absorber and a light stabilizer.

[0213] [7] The cured product layer according to [6], wherein at least one of the ultraviolet absorber and the light stabilizer has an ethylenically unsaturated bond-containing group.

[0214] [8] The cured product layer according to any one of [1] to [7], wherein the curable resin composition contains a hydrophobic polymerizable compound.

[0215] [9] The cured material layer according to any one of [1] to [8], wherein the content ratio of silicon atoms derived from organosilicon to atoms having an atomic number of Li or more, as detected by X-ray photoelectron spectroscopy, on the surface of the cured material layer is 0.3 at% or less, and the content ratio of fluorine atoms is 0.3 at% or less.

[0216]

[10] The cured product layer according to any one of [1] to [9], wherein the cured product layer does not contain a silicone-based leveling agent or a fluorine-based leveling agent.

[0217]

[11] The cured material layer according to any one of [1] to

[10] , wherein the content ratio of silicon atoms derived from organosilicon and the content ratio of fluorine atoms relative to atoms having an atomic number of Li or more detected by X-ray photoelectron spectroscopy on the surface of the cured material layer are below the detection limit.

[0218]

[12] The cured product layer according to any one of [1] to

[11] , wherein the cured product layer contains an acrylic leveling agent.

[0219]

[13] A curable resin composition used to prepare the cured material layer according to any one of [1] to

[12] , the curable resin composition comprising a carbonate-based urethane (meth)acrylate.

[0220]

[14] A transfer film having a release substrate and a transfer layer, wherein the transfer layer has a hard coat layer and an adhesive layer in this order from the release substrate side, and the hard coat layer is the cured product layer according to any one of [1] to

[12] .

[0221]

[15] The transfer film according to

[14] , which has a primer layer between the hard coat layer and the adhesive layer.

[0222]

[16] A hard coat film having a supporting substrate and a hard coat layer, wherein the hard coat layer is the cured product layer according to any one of [1] to

[12] .

[0223]

[17] The hard coat film according to

[16] , which has an adhesive layer on the surface of the supporting substrate opposite to the hard coat layer.

[0224]

[18] A laminate having a substrate and a hard coat layer laminated on the substrate, wherein the hard coat layer is the cured product layer according to any one of [1] to

[12] .

[0225] DESCRIPTION OF SYMBOLS 10...Transfer film 11...Release substrate 12...Transfer layer 13...Hard coat layer 14...Adhesive layer 15...Primer layer 20...Hard coat film 21...Support substrate 22...Hard coat layer 23...Adhesive layer 24...Primer layer 50...Laminate 51...Resin substrate 61...PET film 62...Cured product layer 63...Resin substrate 64...Adhesive layer 65...Primer layer 66...Release layer

Claims

1. a cured layer of a curable resin composition containing a carbonate-based urethane (meth)acrylate; The cured material layer is In a Taber abrasion test performed under the conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 rpm, the difference ΔH in haze value before and after the test is 14% or less, Illuminance 180W / m ２ After 1000 hours of weather resistance testing using a xenon lamp at 70°C, the urethane bond retention rate is 70% or more, The cured material layer has an elongation of 20% or more when cracks occur in a heat tensile test at 180°C.

2. The cured material layer according to claim 1 , wherein the cured material layer has an elongation of 50% or more when cracks occur in a thermal tensile test at 180° C.

3. The cured product layer according to claim 1 , wherein the carbonate-based urethane (meth)acrylate has a number average molecular weight / functional group number of 900 or more.

4. 2. The cured material layer according to claim 1, wherein the carbonate-based urethane (meth)acrylate has a structural unit a derived from a carbonate polyol compound (A) having a terminal hydroxyl group, a structural unit b derived from an alkyl alcohol compound (B), a structural unit c derived from a polyisocyanate compound (C), and a structural unit d derived from a hydroxyl group-containing (meth)acrylate compound (D), and the structural unit d is located at a molecular chain terminal.

5. The total amount (M Ｓ ) ratio (M Ｓ / Mn) is 30% or more and 50% or less, The total amount (M Ｈ ) ratio (M Ｈ The cured material layer according to claim 4 , wherein the SiO 2 content is 4% or more and 15% or less.

6. The cured product layer according to claim 1 , wherein the curable resin composition contains at least one of an ultraviolet absorber and a light stabilizer.

7. The cured product layer according to claim 6 , wherein at least one of the ultraviolet absorber and the light stabilizer has an ethylenically unsaturated bond-containing group.

8. The cured product layer according to claim 1 , wherein the curable resin composition contains a hydrophobic polymerizable compound.

9. 2. The cured material layer according to claim 1, wherein the content ratio of silicon atoms derived from organosilicon to atoms having an atomic number of Li or more, as detected by X-ray photoelectron spectroscopy, on the surface of the cured material layer is 0.3 at% or less, and the content ratio of fluorine atoms is 0.3 at% or less.

10. The cured product layer according to claim 9 , wherein the cured product layer does not contain a silicone-based leveling agent or a fluorine-based leveling agent.

11. 10. The cured material layer according to claim 9, wherein the content ratio of silicon atoms derived from the organic silicone and the content ratio of fluorine atoms relative to atoms having an atomic number of Li or more, as detected by X-ray photoelectron spectroscopy, on the surface of the cured material layer are below the detection limit.

12. The cured product layer according to claim 9 , wherein the cured product layer comprises an acrylic leveling agent.

13. A curable resin composition used to produce the cured material layer according to any one of claims 1 to 12, A curable resin composition comprising a carbonate-based urethane (meth)acrylate.

14. A transfer film having a release substrate and a transfer layer, A transfer film, wherein the transfer layer has a hard coat layer and an adhesive layer in this order from the release substrate side, and the hard coat layer is the cured product layer according to any one of claims 1 to 12.

15. The transfer film according to claim 14 , further comprising a primer layer between the hard coat layer and the adhesive layer.

16. A hard coat film having a supporting substrate and a hard coat layer, A hard coat film, wherein the hard coat layer is the cured product layer according to any one of claims 1 to 12.

17. The hard coat film according to claim 16 , further comprising an adhesive layer on the surface of the supporting substrate opposite to the hard coat layer.

18. A laminate having a substrate and a hard coat layer laminated on the substrate, A laminate, wherein the hard coat layer is the cured product layer according to any one of claims 1 to 12.