Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• This disclosure relates to a cured product layer, a curable resin composition, a transfer film, a hard coat film, and a laminate.
• Curable resin compositions that cure when exposed to active energy rays such as ultraviolet rays and electron beams are known. When such curable resin compositions are cured, a cured product with good functionality, such as scratch resistance and chemical resistance, is formed. For this reason, such cured products are used as surface protection layers to protect the surfaces of substrates such as wood, metal, glass, and resin molded bodies.
• Patent Document 1 describes a decorative sheet having at least a surface protective layer on a substrate, wherein the surface protective layer comprises 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 multifunctional (meth)acrylate (B), wherein the mass ratio ((A)/(B)) of the urethane (meth)acrylate (A) to the multifunctional (meth)acrylate (B) is within a specific range, and the multifunctional (meth)acrylate (B) is a silicone-modified urethane (meth)acrylate.
• a urethane (meth)acrylate (A) having a difunctional to hexafunctional polycarbonate skeleton and a multifunctional (meth)acrylate (B) wherein the mass ratio ((A)/(B)) of the urethane (meth)acrylate (A) to the multifunctional
• Patent Document 2 discloses a method for producing a cured film, which includes the steps of applying a curable composition having a predetermined solids concentration onto a substrate, irradiating with active energy rays to obtain a cured product, and stretching the cured product.
• Patent Document 2 discloses a method for producing a cured film, which comprises a urethane (meth)acrylate ligomer having a predetermined weight-average molecular weight (Mw) and a predetermined amount of urethane bonds and (meth)acryloyl groups, obtained by reacting at least polyisocyanate (A), a chain aliphatic diol having 2 to 5 carbon atoms (B), and a polyfunctional (meth)acrylate having a hydroxyl group (C), and an organic solvent having a predetermined solubility parameter.
• Mw weight-average molecular weight
• C polyfunctional (meth)acrylate having a hydroxyl group
• 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 cured product layer described above.
• 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.
• PET polyethylene terephthalate
• 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 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.
• 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.
• ⁇ H is within the above range, the cured product layer has high abrasion resistance.
• the ⁇ H 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.
• M H /Mn is preferably 4% or more and 15% or less, and more preferably 7% or more and 12% or less.
• the larger M H /Mn means that the urethane bonds are more aggregated.
• M H /Mn is equal to or greater than the above value, the density of the cured material layer increases, the hardness increases, and it becomes less susceptible to scratches.
• urethane bonds have high crystallinity and interaction, so they have the effect of bundling molecules, and can bundle the structural unit a that ensures flexibility, thereby achieving self-repairing properties.
• M H /Mn exceeds the above upper limit, the hardness becomes too high, resulting in a cured material layer that does not achieve self-repairing properties.
• Ms /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.
• the larger Ms /Mn the more flexible the cured material layer becomes and the more improved the self-repairing property.
• Ms /Mn exceeds the upper limit, the amount of change in response to an external force increases, making the cured material layer more susceptible to destruction.
• ⁇ H can be adjusted to fall within the above-mentioned range.
• 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) ⁇
• the cured material layer according to the present disclosure has a urethane bond retention rate of 70% or more, preferably 80% or more, after 1000 hours of weather resistance testing using a xenon lamp irradiated at an illuminance of 180 W/m2.
• a urethane bond retention rate within the above range results in a cured material layer with high weather resistance. Meanwhile, the urethane bond retention rate is, for example, 100% or less.
• the weather resistance test was carried out under the following conditions, and the urethane bond retention rate after 1000 hours of the weather resistance test was calculated by the following method.
• the weather resistance test is performed using the above-mentioned test sample 2.
• a xenon irradiation test is performed 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) repeatedly.
• the surface condition of the hard coat layer is visually inspected to check for the occurrence of cracks. Furthermore, at the 1000-hour point of the weather resistance test, the urethane bond retention rate is calculated using the following method.
• a baseline is set by connecting the valleys on both sides of the peak observed between 1480 and 1580 cm with a line (for example, the minimum value of the valley near 1480 cm and the minimum value of the valley near 1580 cm ), and the top height of the peak observed near 1520 cm from the baseline is taken as the absorption intensity A1520.
• the absorption intensity A1520 is the absorption intensity of the absorption spectrum derived from urethane groups.
• a baseline is set by connecting the valleys on both sides of the peak observed between 1600 and 1800 cm with a straight line (for example, the minimum value of the valley near 1600 cm and the minimum value of the valley near 1800 cm ), and the top height of the peak observed near 1720 cm from the baseline 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 drawn using the base line of the peak. (3)
• the above urethane bond retention rate can be adjusted by changing the type of resin and the type and amount of weather resistance agent used.
• the material has superior scratch resistance and weather resistance compared to, for example, an ester-based urethane acrylate that has an ester structure as its main skeleton.
• the retention rate of urethane bonds can be improved by increasing the thickness of the cured product layer.
• the urethane bond retention rate can be further improved.
• weathering agents include an ultraviolet absorber and a light stabilizer, which will be described later.
• the cured material layer preferably includes at least one of an ultraviolet absorber and a light stabilizer, but from the perspective of improving the urethane bond retention rate, it is preferable to use a combination of an ultraviolet absorber and a light stabilizer. 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. UV absorbers and light stabilizers will be described in more detail below.
• 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.
• the transfer film When the cured material layer of the present disclosure is used as the 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 to fill the cavity. After cooling, the mold is opened, and molding and transfer are simultaneously performed, after which the release substrate must be peeled off.
• the peel strength between this 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 over an extended period of time.
• the content ratio of silicon atoms derived from organosilicon and the content ratio of fluorine atoms on the surface of the cured material layer must each be 0.3 at% or less, thereby achieving stable peel strength over time. Furthermore, it is preferable that the content ratio of silicon atoms derived from organosilicon and the content ratio of fluorine atoms be below the detection limit in the above-mentioned X-ray photoelectron spectroscopy analysis.
• XPS quantitative analysis involves collecting peaks for each element to be measured and determining the concentration 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 elemental sensitivity differences, 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 organosilicon-derived and silica-derived components. The peak appearing around 102 eV corresponds to the C-Si-O bond of organosilicon, and the peak at 103.3 eV corresponds to SiO2 . For fluorine, photoelectrons from the 1s orbital are observed.
• the waveform separation analysis method will now be explained.
• a charge correction is performed on the energy axis (X-axis) of the spectrum.
• the reference peak for correction is set to 284.8-285.0 eV, which is the peak in the carbon 1s spectrum that is thought to be caused by a C-C bond.
• 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.
• Carbonate-based urethane (meth)acrylate (a) structure 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.
• (meth)acrylate means acrylate or methacrylate
• (meth)acryloyl group means acryloyl group or methacryloyl group.
• the structure of the carbonate-based urethane (meth)acrylate is not particularly limited as long as it satisfies the physical properties ( ⁇ H and urethane bond retention) of the cured layer described above.
• Carbonate-based urethane (meth)acrylates are generally the reaction product of a carbonate polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate.
• Such a carbonate-based urethane (meth)acrylate contains structural unit a derived from the carbonate polyol compound (A) having a terminal hydroxyl group, structural unit b derived from the alkyl alcohol compound (B), structural unit c derived from the polyisocyanate compound (C), and structural unit d derived from the hydroxyl group-containing (meth)acrylate compound (D), with structural unit d preferably located at the molecular chain end.
• This carbonate-based urethane (meth)acrylate has a urethane polymer chain in which the structural units a and b are linked to structural unit c via urethane bonds, and further has a structure in which the structural unit d is bonded to the end of the urethane polymer chain.
• Structural unit a has a structure obtained by removing a hydroxyl group from carbonate polyol compound (A).
• Structural unit b has a structure obtained by removing a hydroxyl group from alkyl alcohol compound (B).
• Structural unit c has a structure obtained by removing an isocyanate group from polyisocyanate compound (C).
• Structural unit d has a structure obtained by removing a hydroxyl group from hydroxyl group-containing (meth)acrylate (D).
• Carbonate polyol compound (A) has at least one carbonate bond in the molecule, and also includes polycarbonate polyol compounds 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.
• 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 one hydroxyl group at each end, for a total of two hydroxyl groups, and among these, carbonate diols represented by the following general formula (1) are preferred. Of these, aliphatic carbonate diols in which R in the following general formula (1) is a linear or branched divalent hydrocarbon group are preferred.
• 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.
• Carbonate polyol compounds are synthesized, for example, by transesterification of a polyhydric alcohol with a carbonate ester.
• polyhydric alcohols include polyhydric alcohols with either a linear alkyl structure or a branched alkyl structure.
• polyhydric alcohols having a branched alkyl structure examples 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.
• Polyhydric alcohols may be used alone or in combination.
• carbonate esters include ethylene carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, and dibutyl carbonate. Carbonate esters may be used alone or in combination.
• the number average molecular weight of the carbonate polyol compound is, for example, 300 or more, or may be 500 or more, or 800 or more. If the number average molecular weight is too small, a cured layer with 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 1300 or less. If the number average molecular weight is too large, the cured layer will be too soft and will have reduced scratch resistance.
• the number average molecular weight (Mn) of a carbonate polyol compound is a calculated value determined from the hydroxyl value.
• the hydroxyl value of a carbonate polyol compound is measured in accordance with JIS K1557-1.
• Alkyl alcohol compound (B) In the present disclosure, it is preferable to use an alkyl alcohol compound (B) having two or more hydroxyl groups in addition to the carbonate polyol compound (A).
• the use of an alkyl alcohol compound (B) having two or more hydroxyl groups allows the above-mentioned ⁇ H value to be adjusted.
• 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, for example, a carbon number of 20 or less is preferred, and an alkyl alcohol compound having 10 or less carbon atoms is particularly preferred.
• the alkyl alcohol compound may have two or more hydroxyl groups per molecule.
• alkyl diols having two hydroxyl groups are preferred.
• 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.
• 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.
• alicyclic polyisocyanate compounds 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, and methyl
• suitable diisocyanates 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
• a preferred alicyclic polyisocyanate compound is a diisocyanate compound represented by the following general formula (2):
• Xc is a divalent hydrocarbon group having an alicyclic structure and having 8 to 13 carbon atoms.
• diisocyanate compounds 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.
• 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.
• 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 abrasion 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 one is preferred.
• the number average molecular weight (Mn) of carbonate-based urethane (meth)acrylate is a value determined by gel permeation chromatography (GPC) in terms of standard polystyrene.
• the number of functional groups, n, of the carbonate-based urethane (meth)acrylate is, for example, from 2 to 6, or from 2 to 4, from the viewpoint of crosslinking and curing, and is preferably 2, as this makes it easier to achieve the elongation described above.
• the number of functional groups, n, of the carbonate-based urethane (meth)acrylate refers to the number of (meth)acryloyl groups in one molecule.
• the carbonate-based urethane (meth)acrylate in this 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 component (A), an alkyl diol is used as component (B), a diisocyanate compound is used as component (C), and a compound having one hydroxyl group and one (meth)acryloyl group in the molecule is used as component (D).
• Ra represents the above-mentioned structural unit a
• Rb represents the above-mentioned structural unit b
• Rc represents the above-mentioned structural unit c
• 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.
• the solvent content can 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, per 100 parts by mass of the curable resin composition.
• the method for applying the curable resin composition to the substrate is not particularly limited, and any known method can be applied as appropriate. Examples of application methods 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 is also possible using printing methods such as gravure printing, gravure offset printing, and screen printing.
• drying may be performed after coating to evaporate the solvent.
• known methods such as hot air heating, infrared heating, and far-infrared heating can be used as appropriate.
• the preferred drying conditions vary depending on the boiling point of the solvent, the material of the release substrate, the amount of coating, 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.
• 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.
• the curable resin composition of the present disclosure when irradiated with active energy rays, can form a cured layer that has high scratch resistance, high weather resistance, and high elongation under high-temperature conditions. 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 (sheet for molding). Examples of molding processes include in-mold molding and insert molding.
• curable resin composition and carbonate-based urethane (meth)acrylate used in this disclosure are similar to those described in detail in "A. Cured Material Layer” above, and therefore will not be described here.
• FIGS. 1 and 2 are schematic cross-sectional views illustrating an example of a transfer film according to the present disclosure.
• 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.
• the transfer film 10 may have a primer layer 15 between the hard coat layer 13 and the adhesive layer 14.
• the transfer film disclosed herein has a hard coat layer that is the cured product layer described above, which provides high scratch resistance and high elongation under high temperature conditions. Therefore, it can be suitably used as an in-mold transfer film.
• 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. This makes it possible to suppress deterioration of layers in the laminate that are located further inside than the resin substrate and hard coat layer.
• 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 resistance to chemicals. 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.
• the transfer layer may have only a hard coat layer and an adhesive layer, or may further have other layers.
• 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.
• 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.”
• 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.
• the adhesive layer is preferably a heat seal layer.
• the heat seal layer contains a thermoplastic resin that can be welded by heat.
• Thermoplastic resins are not particularly limited, and examples include acrylic resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, chlorinated polypropylene, chlorinated rubber, urethane resins, epoxy resins, and styrene resins. 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, but can be, for example, from 1 ⁇ m to 7 ⁇ m, and preferably from 1 ⁇ m to 6 ⁇ m.
• the transfer layer in the present disclosure may have a primer layer 15 between the hard coat layer 13 and the adhesive layer 14.
• the transfer layer may further include another layer such as a decorative layer.
• a primer layer may be further provided when the adhesion between the hard coat layer, which is a cured layer of the curable resin composition described above, 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, for example, 0.1 ⁇ m or more and 10 ⁇ m or less.
• the release substrate may comprise, for example, a resin film.
• resin films include 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.
• PET polyethylene terephthalate
• PET polypropylene
• PET polybutadiene resin
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• TAC triacetyl cellulose
• PMMA polymethyl methacrylate
• PC polycarbonate
• EVA ethylene vinyl acetate copolymer
• PVC polyvinyl chloride
• 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 that has releasability, but examples include silicone resin, organic resin-modified silicone resin, fluororesin, aminoalkyd resin, melamine resin, acrylic resin, and polyester resin.
• the thickness of the release layer is not particularly limited, but examples include 0.1 ⁇ m to 10 ⁇ m, and preferably 0.5 ⁇ m to 2 ⁇ m.
• 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.
• 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.
• the transfer film disclosed herein is inserted into an injection mold so that the release substrate is in contact with the mold, and then heated, molten resin is injected to fill the cavity, followed by cooling and opening the mold, thereby allowing molding and transfer to occur simultaneously.
• the cured product of the curable resin composition as a hard coat layer, and optionally other layers such as decorative layers are transferred to the molded resin product.
• the transfer film of the present disclosure can also be used for laminate transfer.
• a hard coat layer (and decorative layer) can be formed on the resin plate or metal plate. Because the hard coat layer of the present disclosure is moldable, it is also possible to bend and hot-bend the resin plate or metal plate after bonding it to the resin plate or metal plate as a base.
• 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.
• FIGS. 3 and 4 are schematic cross-sectional views illustrating hard coat films according to the present disclosure.
• 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.
• the hard coat film 20 may have an adhesive layer 23 on the surface of the supporting substrate 21 opposite the hard coat layer 22.
• the hard coat film 20 may have a primer layer 24 between the supporting substrate 21 and the hard coat layer 22.
• the hard coat film of 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. Therefore, it can be suitably used as a film for insert molding.
• 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. This makes it possible to suppress deterioration of layers in the laminate that are located more inward than the resin substrate and hard coat layer.
• 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.
• 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.
• 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.
• the supporting substrate may be transparent or opaque, and the substrate layer may be a colored substrate layer containing a colorant, or may be colorless.
• the surface of the supporting substrate on the side of 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, because this can improve the adhesion between the substrate layer and the hard coat layer.
• the thickness of the support substrate is not particularly limited, but can be, for example, 4 ⁇ m or more and 200 ⁇ m 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 thickness range.
• 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.
• the adhesive layer can be an adhesive layer containing a pressure-sensitive adhesive (adhesive layer) or an adhesive layer containing an adhesive (adhesive layer).
• the resin constituting the adhesive layer or adhesive layer is not particularly limited and can be similar to the resin contained in general adhesives or pressure-sensitive adhesives used in lamination applications.
• 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 resin (PVDF) and polyvinyl fluoride resin (PVF), polyimide resins such as polyimide, polyamideimide, and polyetherimide, and rubber.
• the adhesive layer may be a heat-seal layer.
• the heat-seal layer is similar to the heat-seal layer described above in "C. Transfer Film,” so a detailed explanation will be omitted here.
• the thickness of the adhesive layer is not particularly limited, but can be appropriately set so that sufficient adhesive strength is obtained when the hard coat film of this embodiment is attached to a resin substrate.
• it can be 1 ⁇ m or more and 7 ⁇ m or less, and preferably 1 ⁇ m or more and 6 ⁇ m or less.
• the hard coat film 20 may have a primer layer 24 between the supporting substrate 21 and the hard coat layer 22 .
• the primer layer is the same as that described above in "C. Transfer Film,” so a detailed explanation will be omitted here.
• 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.
• 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.
• 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.
• the substrate is not particularly limited as long as it is capable of laminating the cured material layer of the present disclosure onto the substrate.
• the substrate may be in the form of a molded body, a sheet, or a plate.
• resins are preferred, and examples include 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.
• PE polyethylene
• PP polypropylene
• PET polyethylene terephthalate
• PEN polybutylene terephthalate
• TAC triacetyl cellulose
• PMMA polymethyl methacrylate
• PC polycarbonate
• EVA ethylene vinyl acetate copolymer
• PVA polyvinyl chloride
• ABS resin and AS resin.
• the laminates disclosed herein are broadly divided into two types depending on the layer structure. Each type of laminate is described below.
• the resin substrate that can be used as the adherend, but it is preferably a resin molded product that requires scratch resistance and weather resistance.
• examples include building materials and interior and exterior components for transportation equipment such as automobiles, trains, and airplanes, especially exterior components.
• the preferred method for manufacturing the laminate of this embodiment is in-mold molding.
• in-mold molding 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, followed by cooling and opening the mold, thereby simultaneously molding and transferring the resin substrate.
• the cured layer of the curable resin composition as a hard coat layer, and optionally other layers such as decorative layers are transferred to the molded resin product.
• 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.
• 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.
• the hard coat layer 22 is located as the outermost layer, thereby improving the scratch resistance and weather resistance of the laminate.
• the resin substrate in the laminate of this embodiment was explained in detail in the first embodiment, so its explanation will be omitted here.
• the hard coat layer in the laminate of this embodiment was explained in detail above in the section "A. Cured product layer,” so its explanation will be omitted here.
• the adhesive layer, primer layer, decorative layer, hard coat layer, etc. in the laminate of this embodiment were explained in detail above in the section “D. Hard coat film,” so their explanation will be omitted here.
• the preferred method for manufacturing the laminate of this embodiment is insert molding.
• the insert molding method includes at least a molding step in which a hard coat film is molded into the surface shape of the article, an injection step in which the molded hard coat film is placed in an injection mold, the injection mold is then closed, and a resin composition in a fluid state is injected into the injection mold, and a solidification step in which the injected resin composition is solidified to form a resin base and a hard coat film is placed on the surface of the resin base.
• They can also be manufactured using a decoration method such as vacuum pressure bonding, in which a hard coat film or a molded product thereof is attached to a pre-prepared three-dimensional resin molded product.
• a decoration method such as vacuum pressure bonding, in which a hard coat film or a molded product thereof is attached to a pre-prepared three-dimensional resin molded product.
• vacuum pressure bonding methods include the TOM method (Three Dimension Overlay Method).
• a curable resin composition was prepared using a base compound X1 containing a carbonate-based urethane (meth)acrylate and a solvent (methyl ethyl ketone).
• the carbonate-based urethane (meth)acrylate contained a structural unit a derived from an acyclic skeleton-based carbonate polyol (number-average molecular weight of 1,000 as determined 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), M S /Mn, and M H /Mn of the urethane (meth)acrylate 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.
• test Sample 1 The curable resin composition was applied to a 50 ⁇ m-thick PET film (polyester film Cosmoshine A4160, manufactured by Toyobo Co., Ltd.) at a coating weight of 5 g/ m2 , and then 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.
• test sample 1 having a PET film 61 and a cured layer (hard coat layer) 62 was obtained, as shown in FIG. 8(a).
• the primer layer material described below was applied to the hard coat layer of Test Sample 1 in a coating amount of 3 g/ m2 and dried at 90°C for 90 seconds to form a primer layer.
• the heat seal layer material described below was applied to the primer layer in a coating amount of 3 g/ m2 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 hardener manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.
• Heat seal layer material TMR-600 (acrylic resin, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)
• test sample 2 (Laminate)
• the transfer film was placed on a 2 mm thick polycarbonate (PC) plate (Carboglass Polish C110C, manufactured by AGC) and heated on a hot plate at 140°C.
• the adhesive layer of the resulting transfer film was then placed in contact with the PC plate, and the two plates were laminated three times using a hot laminating roll at 180°C.
• the PET film serving as the release substrate for the transfer film was then peeled off.
• a 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, as shown in Figure 8(b).
• Test sample 1 and test sample 2 were prepared in the same manner as in Example 1-1, except that main agent X9 containing a urethane ( meth )acrylate containing the structural units a to c of Example 1-1 and the structural unit d derived from glycerin diacrylate and having the number of functional groups n, number average molecular weight/number of functional groups (Mn/n), M S /Mn, and M H /Mn shown in Table 1, and a solvent (methyl ethyl ketone) was used as the curable resin composition.
• main agent X9 containing a urethane ( meth )acrylate containing the structural units a to c of Example 1-1 and the structural unit d derived from glycerin diacrylate and having the number of functional groups n, number average molecular weight/number of functional groups (Mn/n), M S /Mn, and M H /Mn shown in Table 1, and a solvent (methyl ethyl ket
• Test sample 1 and test sample 2 were prepared in the same manner as in Example 1-1, except that main agent X10 containing a urethane ( meth )acrylate containing the structural units a to c of Example 1-1 and the structural unit d derived from pentaerythritol triacrylate and having the number of functional groups n, number average molecular weight/number of functional groups (Mn/n), M S /Mn, and M H /Mn shown in Table 1, and a solvent (methyl ethyl ketone) was used as the curable resin composition.
• main agent X10 containing a urethane ( meth )acrylate containing the structural units a to c of Example 1-1 and the structural unit d derived from pentaerythritol triacrylate and having the number of functional groups n, number average molecular weight/number of functional groups (Mn/n), M S /Mn, and M H /Mn shown in Table 1, and a solvent (
• Test sample 1 and test sample 2 were prepared in the same manner as in Example 1-1, except that main agents X11 to X18 containing urethane ( meth )acrylates with different contents of the structural units a to d of Example 1-1 and the number of functional groups n, number average molecular weight/number of functional groups (Mn/n), M S /Mn, and M H /Mn shown in Table 2, and a solvent (methyl ethyl ketone) were used as curable resin compositions.
• main agents X11 to X18 containing urethane ( meth )acrylates with different contents of the structural units a to d of Example 1-1 and the number of functional groups n, number average molecular weight/number of functional groups (Mn/n), M S /Mn, and M H /Mn shown in Table 2, and a solvent (methyl ethyl ketone) were used as curable resin compositions.
• Example 1-12 A laminate was produced in the same manner as in Example 1-1, except that a base agent 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 contains 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.
• Mn number average molecular weight
• n number of functional groups
• Mn/n number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• M S /Mn number average molecular weight/number of functional groups
• 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) ⁇
• Test Sample 1 and Test Sample 2 were prepared in the same manner as in Example 1, except that a curable resin composition containing a 90/10 ratio of a urethane acrylate having a difunctional polycarbonate skeleton and a hexafunctional acrylate, and a solvent (methyl ethyl ketone) was used as the main component X23.
• Table 3 shows the average molecular weight (Mn), number of functional groups (n), number average molecular weight/number of functional groups (Mn/n), M S /Mn, and M H /Mn of each acrylate.
• 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, with a chuck distance of 5 cm and a tensile speed of 100 mm/min.
• 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, and the difference ⁇ H in haze value before and after the test was measured.
• the surface condition of the hard coat layer was visually inspected every 100 hours to check for the occurrence of cracks. Furthermore, at the 1000-hour point of the weather resistance test, the urethane bond retention rate was calculated using the following method.
• IR spectrum The infrared absorption spectrum (IR spectrum) of the hard coat layer was measured by an attenuated total reflection (ATR) method using an infrared spectrophotometer (JASCO FT/IR-6100, manufactured by JASCO Corporation).
• ATR attenuated total reflection
• JASCO FT/IR-6100 an infrared spectrophotometer
• the horizontal axis represents wave number (cm ⁇ 1 ) and the vertical axis represents absorption intensity
• the absorption intensity of each peak was calculated by the tangent method as follows.
• a baseline is set by connecting the valleys on both sides of the peak observed between 1480 and 1580 cm with a line (for example, the minimum value of the valley near 1480 cm and the minimum value of the valley near 1580 cm ), and the top height of the peak observed near 1520 cm from the baseline is taken as the absorption intensity A1520.
• the absorption intensity A1520 is the absorption intensity of the absorption spectrum derived from urethane groups.
• a baseline is set by connecting the valleys on both sides of the peak observed between 1600 and 1800 cm with a straight line (for example, the minimum value of the valley near 1600 cm and the minimum value of the valley near 1800 cm ), and the top height of the peak observed near 1720 cm from the baseline is taken as the absorption intensity A1720.
• a primer layer was formed by applying the following primer layer material at a coating weight of 3 g/ m2 onto test sample 1 obtained in each of the examples and comparative examples and drying it at 90° C. for 90 seconds. The surface of the laminate on the primer layer side was visually observed to evaluate the presence or absence of cissing of the primer layer material.
• Primer layer material SG131 manufactured by DIC Graphics Corporation
• a hardener manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.
• Examples 1-1 to 1-10 produced cured product layers with excellent elongation, scratch resistance, and weather resistance.
• Comparative Examples 1-9 to 1-12 which used ester-based urethane (meth)acrylate, had a cracking time of 1,000 hours or less.
• 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.
• 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) of less than 900, exhibited reduced elongation.
• 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) of 900 or more, were confirmed to produce cured product layers with excellent elongation.
• Examples 1-1 to 1-10 in which (M S /Mn) was 30% or more and 50% or less and (M H /Mn) was 4% or more and 15% or less, had excellent scratch resistance. It was confirmed that when at least one of (M S /Mn) and (M H /Mn) did not satisfy the above range (Comparative Examples 1-1 to 1-8), the scratch resistance decreased.
• Examples 2-1 to 2-6 A curable resin composition was obtained by mixing the main component X3 used in Example 1-3 with the ultraviolet absorber and light stabilizer of the types and amounts shown in Table 4.
• 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.
• Comparative Example 2-1 A curable resin composition was obtained by mixing the main agent X19 used in Comparative Example 1-9 with the ultraviolet absorber and light stabilizer of the types and amounts shown in Table 4. 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.
• UV absorbers and light stabilizers used in Examples 2-1 to 2-6 and Comparative Example 2-1 are as follows.
• Ultraviolet absorber 4 TINUVIN 400 (manufactured by BASF)
• Light stabilizer 1 LS3410 (reactive light stabilizer, Nippon Nyukazai Co., Ltd.)
• Test Sample 1 of Examples 2-1 to 2-6 and Comparative Example 2-1 was subjected to the above-mentioned elongation and coatability tests. Additionally, Test Sample 2 of Examples 2-1 to 2-6 and Comparative Example 2-1 was subjected to tests for scratch resistance, weather resistance, and chemical resistance. The results are shown in Table 4.
• Example 2-1 the combined use of an ultraviolet absorber and a light stabilizer confirmed further improved weather resistance compared to Example 1-3.
• Comparative Example 2-1 weather resistance was poor even when an ultraviolet absorber and a light stabilizer were used in combination.
• Examples 2-3 and 2-4 the weather stabilizer with an ethylenically unsaturated bond-containing group
• 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, the ultraviolet absorber 3, and the light stabilizer 1 of the types and amounts shown in Table 5.
• 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.
• 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.)
• Test Sample 1 of Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-5 was subjected to the above-mentioned elongation, coatability, and blocking tests described below.
• 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. Chemical resistance tests were conducted using IPA (isopropyl alcohol) and sulfuric acid, respectively.
• IPA isopropyl alcohol
• the content of the other polymerizable compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.
• Release layer material 1 EX-114D Medium (acrylic/melamine 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.)
• LA2 Tego 2100 (silicone-based, manufactured by Shin-Etsu Chemical Co., Ltd.)
• LA3 F-568 (fluorine-based, manufactured by DIC Corporation)
• 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 base agent X3 and the leveling agent shown in Table 6 was used.
• Test Samples 3 of Examples 4-1 to 4-10 were stored in a 60°C constant-temperature oven 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.
• a transfer film having a release substrate and a transfer layer The 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 [1] to [12].

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