Decorative molding laminated film, method for manufacturing the film, and decorative molded body

Abstract

The present invention relates to a laminated film for decoration molding, a method for producing the film, and a decoration molded body. The present invention aims to provide a laminated film for decoration molding which is an excellent decoration molding laminated film in moldability, and which can form a decoration molded body excellent in chipping resistance, scratch resistance, and chemical resistance. A laminated film for decoration molding having a surface protective layer and a base material layer, characterized in that the Martens hardness measured from the surface protective layer side of the laminated film for decoration molding is 100 N / mm 2 ~ 300 N / mm 2 , the surface protective layer has an island structure having domains (D) and a matrix (M), the maximum diameter of the domains (D) in the orientation direction is 0.05 μm to 0.5 μm, and the ratio D:M of the domains (D) to the matrix (M) is 5 to 44:95 to 56.

Description

[0001] This application claims priority based on Japanese Patent Application No. 2020-218119, filed on December 28, 2020, and Japanese Patent Application No. 2021-166124, filed on October 8, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The present invention relates to a decorative molded laminated film having a surface protective layer exhibiting a specific hardness and island structure, a method for manufacturing the film, and a decorative molded body. Background Technology

[0003] Resin molded products are widely used in portable information terminal devices such as smartphones, laptop computers, home appliances, and automotive interior and exterior parts. On the outermost surface of these resin molded products, a surface protective layer, such as a hard coating, is applied by spraying or dipping, or by integrating a decorative film with a pre-applied hard coating during molding.

[0004] Patent Document 1 describes that a multilayer having at least one layer containing an acrylic resin (A) and a layer containing an aliphatic polycarbonate resin (B) is obtained by extruding the two resins together.

[0005] Patent Document 2 discloses a curable resin composition for decorative films for thermoforming, the curable resin composition comprising: a vinyl polymer having carboxyl and hydroxyl groups, a solid component acid value of 15 mgKOH / g to 150 mgKOH / g, a solid component hydroxyl value of 2 mgKOH / g to 80 mgKOH / g, and a glass transition temperature of 70°C to 140°C; and a polyisocyanate compound, wherein the content of the polyisocyanate compound is the amount reacted with the solid component hydroxyl value of the vinyl polymer of 2 mgKOH / g to 80 mgKOH / g.

[0006] Patent document 3 discloses a laminated hard coating film for molding, which is formed by depositing a resin-containing surface protective layer on a substrate film. The laminated hard coating film for molding has an elongation of 10% or more in an atmosphere of 23°C and 50% relative humidity (RH). The use of an active energy line curing resin as the resin contained in the hard coating is disclosed.

[0007] Patent document 4 discloses a decorative sheet having a surface protective layer on a substrate, the surface protective layer being formed by cross-linking and curing a resin composition containing an ionizing radiation-curing resin and a thermoplastic resin in a specific ratio.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2011-161871

[0011] Patent Document 2: Japanese Patent Application Publication No. 2012-097248

[0012] Patent Document 3: Japanese Patent Application Publication No. 2012-210755

[0013] Patent Document 4: Japanese Patent Application Publication No. 2007-290392 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] Decorative molding laminates are used, for example, in automotive interiors and exteriors, thus requiring excellent design capabilities as well as excellent formability for three-dimensional molding. Furthermore, high abrasion resistance and chemical resistance (such as sunscreen resistance) are required after molding. Moreover, assuming outdoor use, damage from sand or stones is not easily caused, and even if damage occurs, it should be minimal (chipping resistance). However, chipping resistance requires resistance to instantaneous impacts, a problem that cannot be solved simply by achieving a balance between hardening and softening the coating. None of the technologies in Patent Documents 1 to 4 fully satisfy these characteristics.

[0016] The present invention is made in view of the background described above, and its object is to provide a decorative molding laminate film, which is a decorative molding laminate film with excellent formability and can form a decorative molded body with excellent crack resistance, abrasion resistance and chemical resistance.

[0017] Technical means to solve the problem

[0018] The present invention solves the aforementioned problem by making the surface protective layer side of the decorative molding laminated film exhibit a specific Martens hardness, and by having islands with a specific maximum diameter in a specific direction in a specific ratio in the surface protective layer.

[0019] That is, the present invention relates to the following [1] to [7].

[0020] [1] A decorative molding laminated film, comprising a surface protective layer and a substrate layer, characterized in that,

[0021] The Martens hardness measured from the surface protective layer side of the decorative molding laminate is 100 N / mm. 2 ~300 N / mm 2 ,

[0022] The surface protective layer has an island structure with a structural domain (D) and a matrix (M).

[0023] The maximum diameter of the structural domain (D) in a given direction is 0.05 μm to 0.5 μm.

[0024] The ratio of domain (D) to matrix (M) is 5–44:95–56.

[0025] [2] According to the decorative molding laminated film described in [1], wherein the substrate (M) is a cured product of a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups and an isocyanate-based curing agent (b) not having photocurable functional groups.

[0026] The structural domain (D) is a hardened product containing a multifunctional active energy line hardening component (c) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate (c2) with a weight average molecular weight of 400 to 5000.

[0027] [3] According to [1] or [2], the decorative molding laminate film, wherein in the tensile test of the decorative molding laminate film at 140°C, the elongation of the surface protective layer is 50% to 200%.

[0028] [4] A decorative molding laminate according to any one of [1] to [3], wherein the haze of the surface protective layer is 5% or less as specified in Japanese Industrial Standards (JIS) K 7136.

[0029] [5] A method is a method for manufacturing a decorative molding laminated film according to any one of [2] to [4], wherein,

[0030] A protective agent comprising a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups, an isocyanate-based curing agent (b) not having photocurable functional groups, an active energy line-curing component (c) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400 to 5000 (c2), and an organic solvent is applied to a substrate layer and dried, thereby allowing at least a portion of the (meth)acrylate resin (a) to react with the isocyanate-based curing agent (b).

[0031] Irradiation with active energy lines causes the hardening components of the active energy lines to harden, forming a surface protective layer.

[0032] [6] A method for manufacturing a decorative molding laminated film according to any one of [2] to [4], wherein,

[0033] A release film is made by applying a protective agent containing a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups, an isocyanate-based curing agent (b) not having photocurable functional groups, an active energy line curing component (c) containing urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400 to 5000 (c2), and an organic solvent, and then drying it to allow at least a portion of the (meth)acrylate resin (a) to react with the isocyanate-based curing agent (b).

[0034] Irradiation with active energy lines causes the hardening components of the active energy lines to harden, forming a surface protective layer.

[0035] Next, the surface protective layer is bonded to the substrate layer via an adhesive layer.

[0036] [7] A decorative molded body, comprising: a body to be decorated, and a decorative molding laminate according to any one of [1] to [4] covering at least a portion of the body to be decorated.

[0037] The effects of the invention

[0038] According to the present invention, a decorative molding laminate film with excellent formability capable of handling various shapes can be provided. Furthermore, decorative molded articles using the aforementioned decorative molding laminate film can provide highly designable articles that are not prone to discoloration or whitening even when their surface comes into contact with pharmaceuticals, and are not easily damaged even in harsh environments. Attached Figure Description

[0039] Figure 1 It is an image of the elastic coefficient measured by scanning probe microscope (SPM) of the cross-section of the surface protective layer.

[0040] Figure 2 It is an image analysis based on the structural domain (D) of image processing software. Detailed Implementation

[0041] Hereinafter, an example of an embodiment of the present invention will be described. Furthermore, in this specification, the specific numerical values ​​"A to B" indicate values ​​A and above and B and below. Additionally, "(meth)acrylic acid" refers to acrylic acid and methacrylic acid, and "(meth)acrylate" refers to acrylate and methacrylate.

[0042] The weight-average molecular weights in this specification are values ​​determined using a gel permeation chromatograph (GPC) manufactured by Tosoh. Details are described in the Examples section.

[0043] <Laminated film for decorative molding>

[0044] The decorative molding laminate of this embodiment includes at least a surface protective layer and a substrate layer, and the Martens hardness measured from the surface protective layer side is 100 N / mm. 2 ~300 N / mm 2 More preferably 150 N / mm 2 ~250 N / mm 2 By making the martensitic hardness 100 N / mm 2 In summary, even friction with steel wool is unlikely to cause damage, thanks to the martensitic hardness of 300 N / mm. 2 Below, the resistance to chipping and elongation become good.

[0045] The Martens hardness is measured using a Fischerscope H-100C microhardness tester manufactured by Fischer Instruments. It is measured by applying a force of 3 mN to a Vickers indenter (a pyramidal shape) and holding it for 5 seconds relative to the surface protective layer of the decorative molding laminate film of this embodiment. Furthermore, the indentation depth of the terminal must not exceed the thickness of the surface protective layer. Preferably, the indentation depth is set as a distance equivalent to 5% to 50% of the thickness of the surface protective layer.

[0046] Marvin hardness increases by decreasing the molecular weight of the active energy line hardening component (c), as described later, or by increasing the number of functional groups (acrylate groups) per molecule. Conversely, Marvin hardness decreases by increasing the molecular weight of the active energy line hardening component (c), as well as by decreasing the number of functional groups per molecule.

[0047] <Surface Protective Layer>

[0048] The surface protective layer exhibits an island structure (nanophase-separated structure) with structural domains (D) and a matrix (M). In this embodiment, the island structure is determined by observing the cross-section of the surface protective layer using a scanning probe microscope (hereinafter sometimes referred to as SPM) and based on the differences in the detected elastic coefficients.

[0049] SPM (Surface Mount Microscope) refers to a microscope that observes the surface condition by gently tapping the sample surface with a tiny probe (cantilever) while scanning. In addition to general surface shapes such as unevenness, the peak voltage generated during tapping corresponds to the elastic modulus of the surface being measured, and thus the magnitude of the surface's elastic modulus can be represented as an image through the voltage peak.

[0050] Specifically, the cross-section of the surface protective layer was observed using an Oxford Instruments MFP-3D with a cantilever (AC-160TS) in dynamic measurement mode. The measurement range was set to 2 μm × 2 μm, and the elastic coefficient image was observed. Methods for obtaining the cross-section observed using SPM include cutting the sample frozen with liquid nitrogen (freezing cutting method), cutting the sample with a sharp tool such as a razor (tweezer method), and processing the cross-section of the sample cut with cutting tools using abrasive paper and then irradiating the sample with an ion beam using a cross-section polishing device (ion milling method). Among these, ion milling is the most preferred.

[0051] However, the state in which inorganic or organic fillers are dispersed in resin is sometimes broadly referred to as an island structure. Furthermore, the surface protective layer in this embodiment may contain inorganic or organic fillers. However, inorganic or organic fillers are not included in either the matrix (M) or the structural domain (D) concept of this embodiment. In this respect, the island structure in this embodiment differs slightly from an island structure in the general sense.

[0052] That is, when a cross-section of a surface protective layer containing inorganic or organic fillers is observed, unevenness caused by the fillers is observed. Although it also depends on the size of the filler, the observed unevenness is at least 5 nm or more. Islands with unevenness observed to be 5 nm or more are not included in the concept of structural domain (D) in this embodiment. In this embodiment, structural domain (D) refers to islands that are detected based on differences in elastic modulus, even if no unevenness is detected.

[0053] No island-like structures were observed in the uneven surface. However, a surface protective layer exhibiting island-like structures based on differences in elastic modulus can be formed, for example, by using a protective agent comprising: a (meth)acrylate resin having hydroxyl groups but lacking photocurable functional groups (a); an isocyanate-based curing agent lacking photocurable functional groups (b); an active energy line curing component (c) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400–5000 (c2); and an organic solvent. The reason or mechanism for this formation is unclear, but the inventors speculate as follows.

[0054] That is, as described later, when a uniform protective agent is applied to a substrate or release film and dried, the (meth)acrylate resin (a) reacts with the isocyanate-based curing agent (b). During the formation of the matrix (sea), a portion of the active energy line curing component (c) slowly separates from the uniform protective agent, forming a predetermined structural domain (island) precursor that will become a structural domain (island). After the (meth)acrylate resin (a) and the isocyanate-based curing agent (b) react to a certain extent, the active energy line curing component (c) contained in the structural domain (island) precursor and the matrix (sea) is cured by irradiation with active energy lines, thereby forming a surface protective layer in which the island structure is not visible in uneven surfaces, but the island structure is visible due to the difference in elastic coefficients.

[0055] That is, the active energy line curing component (c), which contains urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400 to 5000 (c2), has a moderate affinity for the (meth)acrylate resin (a), thus forming a uniform and transparent protective agent. Moreover, since the active energy line curing component (c) has a "urethane" bond or a certain molecular weight, the compatibility decreases during the curing reaction of the (meth)acrylate resin (a) and the isocyanate-based curing agent (b), resulting in a separation under microscopic observation, forming structural domains (islands) with almost no height difference from the matrix (sea).

[0056] By giving the surface protective layer this unique island structure, compared to cases where the compatibility of the active energy line curing component (c) does not decrease during the curing reaction of the (meth)acrylate resin (a) and the isocyanate-based curing agent (b), or cases where only organic fillers are incorporated, high formability, crack resistance, and chemical resistance can be imparted. In the case of only organic fillers, diffuse light reflection easily occurs at the interface between the organic filler and the matrix (sea), but in the case of the island structure of this embodiment, diffuse light reflection at the boundary between the structural domain (island) and the matrix (sea) is also less, exhibiting high transparency.

[0057] <Maximum diameter in a given direction, and the ratio of structural domain (D) to matrix (M)>

[0058] In this embodiment, the maximum diameter of the structural domains (D) of the surface protective layer in a given direction is 0.05 μm to 0.5 μm, and the ratio of structural domains (D) to the substrate (M) is 5 to 44: 95 to 56. Furthermore, regarding the ratio of the two, focusing on the ratio of structural domains (D), the ratio of structural domains (D) is sometimes 5% to 44%.

[0059] By setting the maximum diameter of the structural domain (D) in a given direction and the ratio of the structural domain (D) to the range described above, it is possible to achieve high levels of chemical resistance, formability, and crack resistance simultaneously.

[0060] The maximum diameter in a given direction is the average distance between two points connected by the longest straight line traversing each structural domain (D), preferably 0.05 μm to 0.3 μm, more preferably 0.08 μm to 0.15 μm. Specifically, for all structural domains (D) identified within a 2 μm × 2 μm range at any three locations, the aforementioned "distance between two points connected by the longest straight line" is calculated, and its average value is determined.

[0061] Increasing the weight-average molecular weight (Mw) of the urethane (meth)acrylate (c1) described later tends to increase the maximum directional diameter. Alternatively, its size can be controlled by changing the composition of the solvent(s) used in the protective agent. Specifically, using ketone solvents decreases the maximum directional diameter, while using alcohol solvents allows for significant adjustment of the maximum directional diameter.

[0062] Since the boundary between the structural domain (D) and the matrix (M) can be visually identified in the SPM observation image, the maximum diameter in a given direction can be determined by image analysis using Mac-View Ver.4 (MOUNTECH) analysis software.

[0063] The ratio of the structural domain (D) is obtained by the following formula (1) using the area of ​​the structural domain (D) and the area of ​​the matrix (M) measured by the analysis software Mac-View Ver.4 (MOUNTECH).

[0064] The area of ​​a structural domain (D) refers to the sum of the areas of all structural domains (D) within the observed image. The area of ​​the matrix (M) refers to the area after deducting the sum of the areas of all structural domains (D) within the observed image, the sum of the areas of inorganic fillers, and the sum of the areas of organic fillers from the area of ​​the observed region.

[0065] When the surface protective layer contains inorganic or organic fillers, as described above, the presence of these fillers is detected as unevenness. The detection of the unevenness image is performed simultaneously with the elastic coefficient image based on SPM. Therefore, the area occupied by the structural domains of the inorganic or organic fillers detected as unevenness images is subtracted from the area of ​​the observation area, and this is taken as the area of ​​the observation area obtained by observing the elastic coefficient image, that is, the sum of the areas of each structural domain (D) and the area of ​​the matrix (M).

[0066] The percentage of structural domains (D) = the sum of the areas of all structural domains (D) × 100 / (the sum of the areas of all structural domains (D) + the area of ​​the matrix (M)) Equation (1)

[0067] The ratio of structural domains (D) can be adjusted according to the size and number of each structural domain (D). The ratio of structural domains (D) is 5% to 44%, preferably 5% to 30%, and more preferably 10% to 20%.

[0068] The size of each domain (D) can be increased by increasing the Mw of the (meth)acrylate resin (a) described later, or by increasing the hydroxyl value.

[0069] Furthermore, from the viewpoint of improving the designability of laminated films for decorative molding, the transparency (haze value) of the surface protective layer is preferably 5% or less, more preferably 3.5% or less, even more preferably 1.5% or less, and most preferably less than 0.5%. By making the maximum diameter and ratio of the directional structural domain (D) within the aforementioned range, light scattering can be suppressed and transparency improved.

[0070] In addition, the haze value is obtained by using the following formula (2), and can be measured by using a haze meter in accordance with JIS K 7136.

[0071] Haze (%) = (Diffusion transmittance) × 100 / (Total light transmittance) Equation (2)

[0072] The surface protective layer is formed using a protective agent. The protective agent preferably comprises a plurality of components with moderate affinity, a curing agent capable of reacting with at least one of the components, and a solvent (s). The components can be appropriately selected according to the purpose, and preferably include a protective agent comprising a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups, an isocyanate-based curing agent (b), and an active energy line curing component (c) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400 to 5,000 (c2). In this case, the cured product of the (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups and the isocyanate-based curing agent (b) forms a matrix (M), and the cured product of the active energy line curing component (c) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400 to 5,000 (c2) forms a curing domain (D). The components will be described in detail below.

[0073] <(meth)acrylate resins with hydroxyl groups but without photocurable functional groups (a)>

[0074] The (meth)acrylate resin (a) is obtained by copolymerizing a hydroxyl-containing (meth)acrylate monomer with a non-hydroxyl-containing (meth)acrylate monomer. That is, the (meth)acrylate resin (a) is a copolymer comprising units derived from hydroxyl-containing (meth)acrylate monomers and units derived from other (meth)acrylate monomers.

[0075] The preferred monomers of the (meth)acrylate system containing hydroxyl groups are those with primary hydroxyl groups.

[0076] The reaction with the isocyanate-based curing agent (b), described later, proceeds smoothly due to the primary hydroxyl group, stabilizing the quality of the laminated film for decorative molding. Furthermore, the reaction between the (meth)acrylate resin (a) and the isocyanate-based curing agent (b) readily becomes dense, and phase separation from the urethane (meth)acrylate (c) proceeds smoothly.

[0077] Examples of (meth)acrylate monomers having hydroxyl groups include hydroxyalkyl (meth)acrylates or compounds formed by adding ε-caprolactone to the hydroxyalkyl (meth)acrylate, with hydroxyalkyl (meth)acrylates being preferred.

[0078] Specific examples of hydroxyalkyl methacrylates include: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, and other hydroxyalkyl methacrylates with 1 to 4 carbon atoms in the alkyl group.

[0079] Specific examples of compounds formed by adding ε-caprolactone to hydroxyalkyl methacrylates include ε-caprolactone adducts of 1 mole of 2-hydroxyethyl methacrylate, 2-mole adducts of 2-hydroxyethyl methacrylate, and 3-mole adducts of 2-hydroxyethyl methacrylate, which are ε-caprolactone adducts of hydroxyalkyl methacrylates with 1 to 4 carbon atoms. However, this embodiment is not limited to the examples described above.

[0080] These monomers containing hydroxyl groups can be used individually or in combination. From the viewpoint that crosslinking with isocyanate curing agents results in closer intermolecular distances, improved abrasion resistance, or enhanced chemical resistance, 2-hydroxyethyl (meth)acrylate is particularly preferred.

[0081] Various monomers that are (meth)acrylate monomers without hydroxyl groups can be listed below.

[0082] Examples of alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecanyl methacrylate, lauryl methacrylate, stearyl methacrylate, tert-butylhexyl methacrylate, 2-acetyl acetoxyethyl methacrylate, phenoxyethyl methacrylate, etc.

[0083] Examples of monomers with alicyclic hydrocarbon groups include: cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, cyclododecyl methacrylate, borneol methacrylate, isoborneol methacrylate, dicyclopentenyl methacrylate, and dicyclopentyl methacrylate.

[0084] Examples of monomers with epoxy groups include: glycidyl (meth)acrylate, α-methyl glycidyl acrylate, α-methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, and 3,4-epoxycyclohexyl methyl methacrylate.

[0085] The (meth)acrylate resin (a) is preferably polymerized from methacrylate monomers among the various monomers. In particular, from the viewpoints of abrasion resistance, formability, and chemical resistance, methyl methacrylate, ethyl methacrylate, and tert-butyl methacrylate are preferred. Furthermore, from the viewpoint of phase separation from the active energy line curing component (c), ethyl methacrylate and tert-butyl methacrylate are preferred, and ethyl methacrylate, which has good crack resistance due to its appropriate flexibility, is most preferred.

[0086] The hydroxyl value of the (meth)acrylate resin (a) is preferably 5 mgKOH / g to 190 mgKOH / g, more preferably 55 mgKOH / g to 150 mgKOH / g, and even more preferably 70 mgKOH / g to 120 mgKOH / g. Being within this preferred range, it is easier to separate from the active energy line hardening component (c) and readily form an island structure.

[0087] In addition, the hydroxyl value represents the hydroxyl value of the solid component, which is a value determined according to JIS K1557-1.

[0088] The (meth)acrylate resin (a) may have an acid value. Having an acid value promotes the reaction of hydroxyl groups with isocyanates and reduces unreacted matter.

[0089] When assigning an acid value, the acid value of (meth)acrylate resin (a) is preferably below 20 mgKOH / g. This is because having an acid value improves the compatibility of (meth)acrylate resin (a) with the active energy line curing component (c), making it less likely to stably form an island structure.

[0090] As a method for imparting an acid value to the (meth)acrylate resin (a), it can be obtained by copolymerizing a monomer having an acid value with other monomers. Examples of monomers having an acid value include (meth)acrylic acid, maleic anhydride, 2-(meth)acryloyloxyethyl-succinic acid, 2-(meth)acryloyloxyethyl-hexahydrophthalic acid, 2-(meth)acryloyloxyethyl-phthalic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0091] In addition, the acid value indicates the acid value of the solid components, which is a value determined according to JIS K1557-5.

[0092] The glass transition temperature of the (meth)acrylate resin (a) is preferably between 20°C and 120°C. By setting the glass transition temperature to 20°C or higher, good scratch resistance and abrasion resistance can be obtained; by setting the glass transition temperature to 120°C or lower, moldability is improved. The glass transition temperature of the (meth)acrylate resin (a) is determined by the type of (meth)acrylate monomer with hydroxyl groups and other (meth)acrylate monomers copolymerized with it, as well as the copolymerization ratio.

[0093] Furthermore, the glass transition temperature shown here refers to the glass transition temperature obtained by measuring 100% of the solid components of the (meth)acrylate resin (a) using differential scanning calorimetry (DSC).

[0094] The weight average molecular weight (Mw) of the (meth)acrylate resin (a) is preferably 50,000 to 500,000, more preferably 100,000 to 300,000. By making the weight average molecular weight 50,000 or more, the moldability and abrasion resistance are improved; by making it 500,000 or less, the formation of gels can be prevented, and a surface protective layer with good surface smoothness can be obtained.

[0095] The polydispersity (Mw / Mn) of the (meth)acrylate resin (a) is preferably 2.3 to 10. Compared to polymers with the same weight average molecular weight, polymers with low polydispersity contain relatively fewer low molecular weight components, while polymers with high polydispersity contain relatively more low molecular weight components. The polymer may also contain molecules that do not directly participate in the curing reaction. The low molecular weight components in these non-curing molecules act as plasticizers, thus significantly altering the properties of the cured film due to the polydispersity. That is, by having a polydispersity of 2.3 or higher, the crosslinking density of the cured coating film is moderately reduced, thereby improving moldability. On the other hand, by having a polydispersity of 10 or lower, the plasticity of the cured coating film can be moderately suppressed, maintaining abrasion resistance. A polydispersity of 2.3 to 9 is more preferred, and 2.3 to 8 is even more preferred.

[0096] Methods for polymerizing (meth)acrylate monomers include, for example, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. In terms of the ability to directly use the obtained reaction mixture, solution polymerization is preferred.

[0097] Examples of solvents used for solution polymerization of (meth)acrylate monomers include: aromatic solvents such as toluene and xylene; alcohol solvents such as n-butanol, propylene glycol monomethyl ether, diacetone alcohol, and ethyl cellosolve; ester solvents such as ethyl acetate, butyl acetate, and cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and dimethylformamide, etc. However, this embodiment is not limited to the examples described above. The amount of solvent is preferably determined appropriately based on the concentration of the monomer mixture and the molecular weight of the target (meth)acrylate resin.

[0098] The size of the structural domains can be adjusted by using both ketone-based and alcohol-based solvents when forming the surface protective layer. Therefore, it is preferable to use ketone-based or alcohol-based solvents during synthesis.

[0099] Examples of polymerization initiators used in the polymerization of the (meth)acrylate monomers include azo compounds or organic peroxides. Examples of azo compounds include: 2,2'-azobisisobutyronitrile or 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carboxylonitrile) or 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentanonitrile) or dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid) or 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc. In addition, examples of organic peroxides include: benzoyl peroxide or tert-butyl perbenzoate, cumene hydroperoxide or diisopropyl percarbonate, di-n-propyl percarbonate or di(2-ethoxyethyl) percarbonate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxyneodecanate or tert-butyl peroxynepentanoate, (3,5,5-trimethylhexanoyl) peroxide or dipropionyl peroxide, diacetyl peroxide, etc. This embodiment is not limited to the examples described above.

[0100] <Isocyanate-based hardeners (b)>

[0101] An isocyanate-based curing agent (b) is used to react with the hydroxyl groups in the (meth)acrylate resin (a), which has hydroxyl groups but no photocurable functional groups, as crosslinking functional groups, to form a matrix (M). Regarding the mixing ratio of the (meth)acrylate resin (a) to the isocyanate-based curing agent (b), the molar ratio of isocyanate groups in the isocyanate-based curing agent (b) to hydroxyl groups in the (meth)acrylate resin (a) is preferably NCO / OH = 0.5 / 1 to 3 / 1, more preferably NCO / OH = 1.01 / 1 to 1.5 / 1. In particular, by having more than 1 mol of isocyanate groups relative to 1 mol of hydroxyl groups, the crosslinking reaction between the hydroxyl groups in the (meth)acrylate resin (a) and the isocyanate-based curing agent (b) proceeds smoothly, phase separation occurs, and a surface protective layer with good chemical resistance and crack resistance can be obtained. By having less than 3 mol of isocyanate groups relative to 1 mol of hydroxyl groups, excessive crosslinking reaction is suppressed, resulting in good formability. With an isocyanate group content of 0.5 mol or more relative to 1 mol of hydroxyl groups, the effects of promoting improved drug resistance caused by crosslinking and phase separation of structural domains (D) can be clearly observed.

[0102] The isocyanate-based curing agent (b) is preferably composed of two or more isocyanate groups in one molecule, and examples of its backbone include aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates. From the viewpoint of preventing yellowing of the molded decorative film, an aliphatic isocyanate-based curing agent is preferred. The isocyanate-based curing agent (b) may be one type or a combination of two or more curing agents. Furthermore, curing agents that react with other hydroxyl groups may be used, provided that the physical properties of the decorative film of this embodiment are not affected.

[0103] Examples of aromatic isocyanates include: 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, anisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4',4''-triphenylmethane triisocyanate.

[0104] Examples of aliphatic isocyanates include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylidene diisocyanate, 2,3-butylidene diisocyanate, 1,3-butylidene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0105] Examples of alicyclic isocyanates include: 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), and 1,4-bis(isocyanate methyl)cyclohexane.

[0106] These isocyanate-based curing agents are preferably used as adducts of the isocyanate with polyols such as trimethylolpropane, biuret form of the isocyanate, or isocyanurate form, or adducts of the isocyanate with well-known polyether polyols or polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc.

[0107] Of these isocyanate-based curing agents (b), from a design point of view, aliphatic or alicyclic isocyanates with low yellowing characteristics are preferred, and from the point of view of the strength of the cured film, adducts are preferred. More specifically, adducts of hexamethylene diisocyanate (HDI) and adducts of 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) are preferred. Mixtures of these are also suitable.

[0108] Furthermore, in this embodiment, from the viewpoint of the preservation stability of the protective agent, a block-type isocyanate curing agent can also be used. As a block-type isocyanate curing agent, one can be formed by blocking the non-block-type isocyanate curing agent using various block-forming agents. Preferably, the block-forming agent decomposes at a relatively low temperature of around 80°C to 120°C. Alternatively, when using a non-block-type isocyanate curing agent, it is suitable to use a method that separately encapsulates a hydroxyl-containing (meth)acrylate resin (a) and an isocyanate-based curing agent (b), and then mixes them before use.

[0109] <Active Energy Line Hardening Component (c)>

[0110] In this embodiment, the active energy line hardening component (c) forms a structural domain (D) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate (c2) with a weight average molecular weight of 400 to 5,000.

[0111] <Carbamate (meth)acrylate (c1)>

[0112] Carbamate (meth)acrylates are products of the reaction between a compound having an isocyanate group and a (meth)acrylate having a hydroxyl group, and have a (meth)acryloyl group at the end of the molecule. Carbamate (meth)acrylate (c1) is preferably a carbamate (meth)acrylate having multiple (meth)acryloyl groups. Such carbamate (meth)acrylates having multiple (meth)acryloyl groups can be manufactured, for example, by: using a polyfunctional compound as an isocyanate group to react a (meth)acrylate having one hydroxyl group; or using a monofunctional compound with an isocyanate group to react a (meth)acrylate having multiple hydroxyl groups, etc. Additionally, diols or diamines can be used to adjust the chain length or molecular weight. Carbamate (meth)acrylates having multiple (meth)acryloyl groups are rapidly cured using active energy such as ultraviolet light or electron beams through unsaturated carbon bonds derived from (meth)acrylates. The resulting cured product has high crosslinking density and excellent chemical resistance. When crosslinking components that are prone to free radical polymerization are crosslinked using methods such as ultraviolet light, photopolymerization initiators can be used, and polymerization accelerators can also be used in conjunction. When crosslinking is performed using electron beams, these components do not need to be formulated.

[0113] The weight average molecular weight (Mw) of the urethane (meth)acrylate (c1) is preferably 300 to 4,000. When the Mw is below 4,000, the compatibility with the (meth)acrylate resin (a) decreases, making it easier to form an island structure. When the Mw is above 300, the flexibility of the structural domains (D) increases, and chemical resistance can be maintained at a high level even after molding a laminated film for decorative molding. This is because the structural domains (D) easily deform together with the shape deformation of the matrix (M).

[0114] Mw-sized urethane (meth)acrylates (c1) can be obtained by reacting isocyanate-containing prepolymers, which are obtained by reacting various diols or diamines with compounds having low molecular weight isocyanate groups, with hydroxyl-containing (meth)acrylates.

[0115] Examples of diols include those with a straight-chain aliphatic structure or those with a branched-chain aliphatic structure. Examples of diamines include those with alicyclic structures, as well as those with a similar straight-chain aliphatic structure or those with a branched-chain aliphatic structure.

[0116] Examples of hydroxyl (meth)acrylates with one hydroxyl group used in the formation of urethane (meth)acrylates (c1) include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol di(meth)acrylate, etc.

[0117] Examples of hydroxyl (meth) acrylates with multiple hydroxyl groups used in the formation of urethane (meth) acrylates (c1) include: pentaerythritol mono(meth) acrylate, pentaerythritol di(meth) acrylate, dipentaerythritol mono(meth) acrylate, dipentaerythritol di(meth) acrylate, dipentaerythritol tri(meth) acrylate, dipentaerythritol tetra(meth) acrylate, glycerol (meth) acrylate, etc.

[0118] As a compound with an isocyanate group used in the formation of urethane (meth)acrylate (c1), a compound exemplified as an isocyanate-based curing agent (b) without photocurable functional groups can also be cited.

[0119] Furthermore, examples of compounds with isocyanate groups used in the formation of urethane (meth)acrylate (c1) include 2-isocyanoethyl (meth)acrylate, 2-((meth)acryloyloxy)ethyl isocyanate, and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, which are compounds with both isocyanate and (meth)acryloyl groups.

[0120] <(meth)acrylates (c2) with a weight average molecular weight of 400–5000>

[0121] (Meth)acrylates (hereinafter sometimes referred to as oligomers) with a weight average molecular weight of 400 to 5000 can also be used to form structural domains (D).

[0122] For example, a polyester having carboxyl groups is formed, and the carboxyl groups in the polyester are reacted with glycidyl (meth)acrylate to obtain a polyester having (meth)acryloyl groups. If a polyester with carboxyl groups introduced only at the end is used, then (meth)acryloyl groups can be introduced only at the end. If a polyester with carboxyl groups introduced at both the end and the side chains is used, then (meth)acryloyl groups can be introduced at both the end and the side chains.

[0123] Alternatively, a copolymer can be obtained by copolymerizing a carboxyl-containing (meth)acrylate with other (meth)acrylates, and the carboxyl groups in the copolymer can be reacted with glycidyl (meth)acrylate to obtain an oligomer having (meth)acryloyl groups; or a copolymer can be obtained by copolymerizing glycidyl (meth)acrylate with other (meth)acrylates, and the glycidyl groups in the copolymer can be reacted with (meth)acrylic acid to obtain an oligomer having (meth)acryloyl groups.

[0124] Alternatively, a copolymer can be obtained by copolymerizing (meth)acrylates having hydroxyl groups but not photocurable functional groups with other (meth)acrylates, etc., and then reacting the hydroxyl groups in the copolymer with compounds having isocyanate groups and (meth)acryloyl groups to obtain oligomers having (meth)acryloyl groups.

[0125] For the active energy line curing component (c) in this embodiment, it may include other (meth)acrylate monomers other than the urethane (meth)acrylate (c1) or the (meth)acrylate (c2) with a weight average molecular weight of 400 to 5000, within the range that does not impair the phase separation of the matrix (M) formed by the reaction of a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups with an isocyanate curing agent (b) without photocurable functional groups.

[0126] To promote the photopolymerization of the active energy line hardening component (c), the protective agent preferably contains a photopolymerization initiator. Examples of photopolymerization initiators include the following substances.

[0127] Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl methyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane, oligomeric {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one, and other acetophenone derivatives;

[0128] Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin derivatives;

[0129] Phosphine derivatives such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide;

[0130] Other methyl phenylglyoxalate, etc., but not limited to these.

[0131] More specifically, examples include: Irgacure-651, Irgacure-184, Darocure-1173, Irgacure-500, Irgacure-1000, Irgacure-2959, Irgacure-907, Irgacure-369, Irgacure-379, Irgacure-1700, and others. Irgacure-149, Irgacure-1800, Irgacure-1850, Irgacure-819, Irgacure-784, Irgacure-261, Irgacure-OXE-01 (CGI124), CGI242 (BASF), Adecaoptomer N1414, Adecaoptomer Optimizer N1717 (ADEKA), EsACure 1001M (LAmBerti), diazo-onium compounds, various onium compounds represented by organoazines, o-quinone diazines, and iodonium compounds, metal aromatic complexes, transition metal complexes containing transition metals such as ruthenium, alumina complexes, 2,4,5-triarylimidazolium dimers, carbon tetrabromide or organohalogen compounds, sulfonium complexes or oxosulfonium complexes, aminoketone oxime esters, etc.

[0132] In addition, hydrogen-abstracting free radical initiators can be used as photopolymerization initiators. Specifically, examples include aromatic ketones such as acetophenone, benzophenone, benzyl, mifepristone, thioxanthone, or anthraquinone, but these are not limited to. These compounds are generally used in conjunction with tertiary amines in this field. Specifically, examples include trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, and p-dimethylaminophenylalkyl ester, but these are not limited to.

[0133] Among these, acetophenones and phosphine oxides are preferred as photopolymerization initiators.

[0134] Photopolymerization initiators can be used alone or in combination, and can be mixed arbitrarily depending on the required properties of the reactant or the compound to be cured via an active energy line. When using these photopolymerization initiators, the amount used is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the total solid components containing active energy line curable components such as urethane (meth)acrylate (C1).

[0135] Protective agents may also contain sensitizers. Examples of sensitizers include: unsaturated ketones such as chalcone derivatives or diphenylmethylene acetone; 1,2-dione derivatives such as benzyl or camphorquinone; benzoin derivatives; fluorene derivatives; naphthoquinone derivatives; anthraquinone derivatives; xanthones derivatives; thioxanthones derivatives; xanthonesone derivatives; thioxanthonesone derivatives; coumarin derivatives; coumarin ketone derivatives; anthocyanin derivatives; oxazine derivatives; and polymethyl ester pigments such as acridine derivatives, azazine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulonium derivatives, squaric acid lactone derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazine. The invention includes derivatives of porphyrazine, phthalocyanine, tetrazine porphyrazine, tetraquinoxolinoporphyrazine, naphthyl phthalocyanine, phthalocyanine derivatives, pyranonium derivatives, thiopyranonium derivatives, tetraphyrin derivatives, annulopene derivatives, spiropyran derivatives, spiroxazine derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organorruthenium complexes, mifepristone derivatives, bimidazole derivatives, etc., but is not limited thereto.

[0136] In a total of 100% by mass of the solid components of (meth)acrylate resin (a), isocyanate-based curing agent (b), and active energy line curing component (c), the amount of active energy line curing component (c) is 25% to 49% by mass, more preferably 30% to 40% by mass. By consuming 25% or more by mass, chemical resistance or cracking resistance is improved. On the other hand, by consuming 50% or less by mass, the island structure is well-balanced, and formability is improved.

[0137] <solvent(s)>

[0138] The solvent(s) used in the protective agent can be preferably selected from known solvents, such as esters like ethyl acetate, butyl acetate, and cellolytic acetate; ketones like acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone, acetylacetone, and cyclohexanone; ethers like tetrahydrofuran and dioxane; aromatic hydrocarbons like toluene and xylene; halogenated hydrocarbons like methylene chloride and ethyl chloride; dimethyl sulfoxide and dimethylaminosulfonamide; and alcohols like water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether-1-methoxy-2-propanol. These can be used alone or in combination of two or more. In particular, the size of the structural domain (D) in this embodiment can be controlled by the solvent composition, preferably using a combination of ketones and secondary or tertiary alcohols, and more preferably, the mass ratio of secondary or tertiary alcohols to ketones is 1 to 10. By using a preferred mass ratio, phase separation between the matrix (M) and the structural domain (D) can be promoted, thereby obtaining the desired island structure. Secondary or tertiary alcohols have low reactivity with isocyanate curing agents, and can be used as solvents without affecting the curing reaction.

[0139] The protective agent may be further supplemented with various additives as needed, such as inorganic fillers, organic fillers, fillers, thixotropic agents, anti-aging agents, antioxidants, antistatic agents, flame retardants, thermal conductivity modifiers, plasticizers, anti-collapse agents, antifouling agents, preservatives, bactericides, defoamers, leveling agents, thickeners, pigment dispersants, and silane coupling agents. Specifically, for purposes such as creating an uneven surface on the protective layer to provide an anti-blocking effect, or to increase the strength of the protective layer to improve its abrasion resistance, it is preferable to include inorganic fillers and / or organic fillers. Furthermore, as already explained, the concepts of matrix (M) and structural domain (D) in this embodiment do not include inorganic fillers and organic fillers.

[0140] Specific examples of inorganic fillers include inorganic microparticles containing oxides, hydroxides, sulfates, carbonates, and silicates of metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, and antimony. Further specific examples include inorganic particles containing silicon dioxide, silica gel, alumina, aluminum hydroxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, aluminosilicate, talc, mica, glass fiber, and glass powder. One type of inorganic filler may be used, or two or more may be used in combination.

[0141] Specific examples of organic fillers include: polytetrafluoroethylene resin or polyethylene resin, polypropylene resin, polymethyl methacrylate resin, polystyrene resin, polyamide resin, melamine resin, guanidine resin, phenolic resin, urea resin, silicone resin, methacrylate resin, acrylate resin, and other polymer microparticles; or cellulose powder, nitrocellulose powder, wood flour, waste paper powder, shell powder, starch, etc. One type of organic filler may be used, or two or more may be used in combination.

[0142] Relative to 100 parts by weight of (meth)acrylate resin (a), the inorganic filler and organic filler may each contain 0.1 parts by weight to 20 parts by weight, preferably 0.5 parts by weight to 5 parts by weight. The aforementioned effect is expected when the content is 0.1 parts by weight or more, and excellent moldability without hindering transparency when the content is 20 parts by weight or less.

[0143] Inorganic and organic fillers can achieve sufficient target effects by simply mixing them with dispersants as needed. However, better results can be obtained by further mechanical mixing using kneaders, rollers, mills, ultramills, dry pulverizers, etc.

[0144] <Laminated Films for Decorative Molding and Their Manufacturing Methods>

[0145] The decorative molding laminate of this embodiment has a surface protective layer and a substrate layer with a specific martensitic hardness. As described above, the surface protective layer exhibits an island structure with specific structural domains (D) and a matrix (M).

[0146] <Substrate Layer>

[0147] The substrate layer refers to a membrane that functions as a support, or a substrate layer on which a design layer, metal layer (including vapor-deposited film), adhesive layer, polarizing layer, etc., are formed by applying a coating to impart design features.

[0148] Regarding the membrane itself, which functions as a support, examples include: polyethylene membrane, polypropylene membrane, polyethylene terephthalate membrane, polybutylene terephthalate membrane, polycarbonate membrane, polymethyl methacrylate membrane, polyamide membrane, polyimide membrane, polyvinyl chloride membrane, polyvinylidene chloride membrane, polyvinyl alcohol membrane, polystyrene membrane, polyacrylonitrile membrane, etc. One type or multiple layers can be used to form the membrane. Particularly from the viewpoint of transparency and formability, polyethylene terephthalate membrane, polycarbonate membrane, and polymethyl methacrylate membrane are preferred. These membranes can be used individually or in combination; for example, a PMMA / PC membrane co-extruded from polycarbonate (PC) and polymethyl methacrylate (PMMA), or a membrane laminated with a polyester membrane using an adhesive, can also be used. Depending on the application, the membrane or a combination thereof can be appropriately selected.

[0149] The decorative molding laminate of this embodiment can be manufactured by applying a protective agent to a substrate layer and drying it. After at least a portion of the (meth)acrylate resin (a) reacts with the isocyanate-based curing agent (b), it is irradiated with an active energy line to harden the curing component of the active energy line, forming a surface protective layer. After irradiation with the active energy line, curing can further promote the reaction between the (meth)acrylate resin (a) and the isocyanate-based curing agent (b).

[0150] When a membrane with a softening temperature of 60°C to 150°C, which acts as a support, is used as the substrate layer, the elastic modulus of the membrane decreases during the heating processes such as drying and curing of the protective agent, sometimes causing deformation, dimensional changes, or adhesion. Therefore, when using a membrane with a low softening temperature, a transfer method can be used to transfer the surface protective layer onto the substrate layer using an adhesive.

[0151] Specifically, firstly, a protective agent is applied to the release agent-treated surface of the release film, and then it is placed in a drying oven to allow the solvent to evaporate, mature, and harden, thus obtaining a surface protective layer. Next, an adhesive is applied to the surface protective layer or the substrate layer to form an adhesive layer, and the surface protective layer and the substrate layer are bonded together via the adhesive layer. The release film can be peeled off after lamination.

[0152] As a method for applying a protective agent to a substrate layer or release film, known methods can be used, specifically including: corner wheel coating, gravure coating, reverse coating, roller coating, die lip coating, spray coating, etc.

[0153] Examples of films used as release films include: polyester films formed from polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films formed from polyolefins such as polyethylene, polypropylene, and polymethylpentene; polycarbonate films; plastic films such as polyvinyl acetate films; paper films such as pulp films; or laminates formed from two or more of these materials. Materials treated with release agents on the films can also be used.

[0154] To obtain the decorative molding laminated film of this embodiment, it is preferable to dry the protective agent at 50°C to 200°C, and more preferably at 70°C to 120°C. After drying, in order to complete the curing reaction of the resin of the protective agent, it is preferable to cure it at room temperature to about 50°C for about 10 minutes to about 10 days.

[0155] To prevent damage, a release liner can be laminated on the other side of the substrate layer on which the surface protective layer is laminated. Especially when the substrate layer is made of polycarbonate, it is preferable to protect the substrate surface with a release liner just before use, as the substrate is easily damaged.

[0156] The thickness of the substrate layer is preferably 10 μm to 1000 μm, more preferably 20 μm to 500 μm, and even more preferably 50 μm to 300 μm. By setting it within the above range, the formability and abrasion resistance of the laminated film for decorative molding are improved.

[0157] The thickness of the surface protective layer formed on the substrate layer is preferably 1 μm to 20 μm, more preferably 3 μm to 10 μm. By setting it to 1 μm or more, good chemical resistance and abrasion resistance are achieved, and by setting it to 20 μm or less, good formability and crack resistance are achieved.

[0158] The thickness of the laminated film used for decorative molding only needs to be sufficient for successful embedding, in-mold molding, or compression molding. Preferably, it is in the range of 15 μm to 1000 μm, and more preferably in the range of 50 μm to 500 μm. By being within the preferred range, the film exhibits good conformability to unevenness during molding, and is less prone to film creases or wrinkles during molding.

[0159] In a tensile test conducted at 140°C according to JIS K 7161, the elongation of the decorative molding laminated film until the surface protective layer cracks, peels off from the substrate layer, or breaks is preferably 50% to 200%, more preferably 80% to 200%. By setting it to 200% or less, heat-induced distortion during molding is reduced, and mold marks from the mold during molding are less likely to remain on the surface protective layer. A value of 50% or more provides moderate rigidity and good formability. Furthermore, the elongation of the decorative molding laminated film is a value determined based on the initial state of 0% before the test.

[0160] <Decorative Molded Components>

[0161] Next, the decorative molded body of this embodiment will be described. The decorative molded body of this embodiment refers to a molded body whose surface is covered by a decorative molding laminate. The raw material of the covered molded body (hereinafter also referred to as the decorated body) is not particularly limited, and known raw materials can be used.

[0162] The decorative molded article using the decorative molding laminate film of this embodiment exhibits excellent chemical resistance. It is believed that a portion of the component in the surface protective layer used to form the structural domains (D) is microscopically compatible with the matrix component (M) at the interface. This is because, from the viewpoint of the observed ratio of structural domains (D), it is believed that the active energy line-curing component (c) containing urethane (meth)acrylate (c1) and / or (meth)acrylate (c2) with a weight average molecular weight of 400 to 5000 is not entirely supplied to the formation of the structural domains (D).

[0163] During molding, the matrix (M) in the surface protective layer is stretched, and as it is stretched, the shape of the structural domains (D) also changes slightly, with an increased orientation along the surface of the object being decorated. As a result, it is believed that high chemical resistance can be maintained even after molding.

[0164] Examples of raw materials that can be used as decorative materials include wood, paper, metal, plastic, fiber-reinforced plastic, rubber, glass, minerals, clay, etc., and one or more of these materials can be used in combination.

[0165] Examples of plastics include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, epoxy resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, poly(meth)acrylate, polycarbonate, polyamide, polyimide, polyphenylene ether, polyphenylene sulfide, polyester, polytetrafluoroethylene, etc., and one or more of these can be used in combination.

[0166] As fiber-reinforced plastics, examples include carbon fiber reinforced plastics, glass fiber reinforced plastics, polyaramid fiber reinforced plastics, and polyethylene fiber reinforced plastics, and one or more types can be used in combination.

[0167] Examples of metals that can be used include hot-rolled steel, cold-rolled steel, galvanized steel, electro-galvanized steel, molten galvanized steel, alloyed molten galvanized steel, galvanized alloy steel, copper-plated steel, zinc-nickel steel, zinc-aluminum steel, iron-zinc steel, aluminum-plated steel, aluminum-zinc steel, tin-plated steel, aluminum, stainless steel, copper, aluminum alloys, and electromagnetic steel. One type or two or more can be used in combination. Additionally, a protective coating can be applied to the surface of the metal.

[0168] In this embodiment, the decorative molding laminate and the decorated object can be integrated using known integration methods, such as embedding molding, in-mold molding, vacuum molding, air molding, three-dimensional overlay method (TOM) molding, compression molding, etc.

[0169] Alternatively, for example, after preparing the decorative molding laminate of this embodiment into the desired shape, the plastic or fiber-reinforced plastic can be injection molded such that the decorative molding laminate side becomes the outermost layer, thereby obtaining a decorative molded body.

[0170] Alternatively, a molded body can be obtained in advance from plastic, fiber-reinforced plastic, or metal, and the decorative molding laminate of this embodiment or a pre-molded body prepared to be molded into the desired shape of the decorative molding laminate can be attached to the surface of the molded body in such a way that the surface protective layer side is the outermost layer.

[0171] In this embodiment, the surface protective layer side of the decorative molding laminate film is located on the outermost layer. In the decorative molding laminate film, protective films can be provided on the surface of the surface protective layer and the surface of the substrate layer to prevent damage that may occur during various processes such as coating, drying, curing, and molding. When using the decorative molding body, the protective film is peeled off.

[0172] Decorative molded bodies manufactured using the decorative molding laminated film of this embodiment as decorative film can be used as interior parts of automobiles such as dashboard decorative panels in metallic or piano black tones, shift gate panels, door trims, air conditioning control panels, and car navigation systems, or as exterior parts such as emblems at the front and rear of automobiles, center decorations for tire hubs, and nameplates.

[0173] In addition to automotive interior and exterior parts, and not limited to exterior materials for home appliances, smart keys, smartphones or mobile phones, and laptop computers, it can also be used appropriately for exterior materials for helmets or suitcases, protective films for LCD screens of navigation systems or LCD TVs, exterior materials for battery storage devices, sports equipment such as tennis rackets or golf club handles, and building materials such as doors or partitions and wall materials for residences.

[0174] <Example>

[0175] The embodiments of the present invention will be described in more detail below, but these embodiments do not limit the scope of the present invention in any way. Furthermore, in the embodiments, "parts" means "parts by mass", and "%" means "% by mass".

[0176] In addition, in the following examples, the molecular weights of (meth)acrylate resin (a) and the active energy line curing component (c) were determined by gel permeation chromatography (GPC) using polystyrene-converted weight-average molecular weights. The measuring apparatus used was a GPC-8020 (manufactured by Tosoh Corporation), the eluent was tetrahydrofuran, and the column used was three TSK gelsuper HM-M (manufactured by Tosoh Corporation). The determination was performed at a column temperature of 40°C, a flow rate of 0.6 ml / min, a sample concentration of 0.3%, and an injection volume of 10 μL.

[0177] Furthermore, in this specification, the non-volatile component refers to the value calculated by dividing the mass of the sample after heating (1 g sample heated at 170°C for 10 minutes) by the mass of the sample before heating. However, in the case of commercially available products, the value calculated based on the method specified by the manufacturer may also be used.

[0178] The acid value was determined according to JIS K1557-5 using potentiometric titration, and calculated as follows: Acid value of solid component [mgKOH / g] = Acid value [mgKOH / g] ÷ Non-volatile component [%).

[0179] The hydroxyl value was determined according to JIS K1557-1 using potentiometric titration based on method A (acetylation method), and calculated as: hydroxyl value of solid component [mgKOH / g] = hydroxyl value [mgKOH / g] ÷ non-volatile component [%).

[0180] [Manufacturing Example 1]

[0181] In a four-necked flask including a cooling tube, a stirrer, a thermometer, and a nitrogen inlet tube, 100 parts of methyl ethyl ketone (MEK) were added, and the mixture was heated while stirring under nitrogen. Once the temperature in the flask reached 75°C, this temperature was maintained as the synthesis temperature, and a monomer solution consisting of 76.8 parts of ethyl methacrylate, 23.2 parts of 2-hydroxyethyl methacrylate, and 0.10 parts of 2,2'-azobis(2,4-dimethylpentanonitrile) (V65) was added dropwise over 2 hours. One hour after the monomer addition was complete, 0.05 parts of V65 were diluted in 20 parts of MEK, and the resulting mixture was divided into 5 portions. One portion was added every hour to continue the reaction. The unreacted monomer content in the solution was confirmed to be less than 5% based on the determination of non-volatile components. The solution was diluted with 40 parts of propylene glycol monomethyl ether, cooled, and the reaction was terminated to obtain a (meth)acrylate resin (a-1) solution with approximately 40% solids. The glass transition temperature of the hydroxyl-containing (meth)acrylate resin (a-1) is 63℃, the acid value is 0 mgKOH / g, the hydroxyl value is 100 mgKOH / g, and the Mw is 200,000.

[0182] [Manufacturing Examples 2 to 13]

[0183] Except for changing the raw materials and input amounts as recorded in Table 1, the same synthesis was carried out as in Manufacturing Example 1 to obtain solutions of (meth)acrylate resins with hydroxyl groups (a-2 to a-12) and (meth)acrylate resins without hydroxyl groups (a-13).

[0184] In addition, two-thirds of the polymerization initiator was dissolved in the monomer solution and added dropwise to the flask. After the monomer solution was added, one-third of the monomer solution was dissolved in the solvent and added dropwise. The total amount is recorded in the table.

[0185] The symbols in Table 1 are shown below.

[0186] EMA: Ethyl methacrylate

[0187] tert-BMA: tert-butyl methacrylate

[0188] MAA: Methyl methacrylate

[0189] HEMA: 2-hydroxyethyl methacrylate

[0190] HPMA: Hydroxypropyl methacrylate

[0191] MAA: Methacrylic acid

[0192] V65: 2,2'-azobis(2,4-dimethylvaleronitrile)

[0193] MEK: Methyl ethyl ketone

[0194] PGM: Propylene glycol monomethyl ether

[0195] [Table 1]

[0196]

[0197] The following details the materials used in creating the surface protective layer.

[0198] <Isocyanate-based hardeners (b)>

[0199] • b-1 Asahi Kasei Corporation's Duranate TSE-100 NCO content: 12.0%

[0200] <Active Energy Line Hardening Component (c)>

[0201] <Carbamate (meth)acrylate (c1)>

[0202] • c-1Mw: 400 Trisense

[0203] c-2Mw: 1000 Trisense

[0204] • c-3Mw: 3000 Four Senses

[0205] • c-4Mw: 200 dual-sensory

[0206] c-5Mw: 14000 dual-sensory

[0207] • c-6 Mitsubishi Chemical Corporation manufactured UV-7605B Mw: 1100 hexafunctional

[0208] • c-7 Miramer PU610 Mw: 1800 hexa-sensory engine manufactured by MIWON

[0209] • c-8 Mitsubishi Chemical Corporation's UV-7630B (Mw: 2200, hexafunctional)

[0210] • C-9 Miramer MU9500 Mw: 3200 (manufactured by MIWON Corporation) Ten-Sensory Function

[0211] • c-10 Mitsubishi Chemical Corporation manufactured UV-7610B Mw: 11000 Nine-functional

[0212] • c-11 Miramer SC2152 Mw: 20787 (Made by MIWON Corporation) with 15 functions

[0213] <(meth)acrylates (c2) with a weight average molecular weight of 400–5000>

[0214] • c-12 Miramer PE210 (Bisphenol A Epoxy Diacrylate) Mw: 520 manufactured by MIWON Corporation, a difunctional

[0215] • c-13 Miramer EA2280 (modified epoxy diacrylate) Mw: 1580 manufactured by MIWON Corporation, a difunctional

[0216] • c-14 Miramer PS420 (polyester acrylate) Mw: 3000 tetrafunctional manufactured by MIWON

[0217] • c-15 Miramer PE230 (aliphatic epoxy diacrylate) Mw: 420 manufactured by MIWON Corporation, a difunctional

[0218] <Photoinitiator>

[0219] • Oligomeric {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone}

[0220] <Substrate Layer>

[0221] F-1 S000 (polymethyl methacrylate film, 125 μm thick) manufactured by Sumitomo Chemical Acrylic Sales Co., Ltd.

[0222] • F-2 IUPILON FE-2000 membrane (polycarbonate membrane, 200 μm thick) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0223] • F-3 Purethermo AG-301X (polypropylene film, 300 μm thick) manufactured by UNITEC Corporation

[0224] <Manufacturing of Packing Dispersions>

[0225] [Preparation of Dispersion (1)]

[0226] 25 parts by weight of synthetic spherical silica SO-C5 (average particle size of 1.3 μm to 1.7 μm according to the manufacturer's data), 35 parts by weight of methyl ethyl ketone, and 30 parts by weight of 3-methoxy-1-butanol were mixed, dispersed, and then dispersed using a sand mill to prepare a dispersion with approximately 25% non-volatile components (1). The D50 particle size of the oxides in the obtained dispersion was 1.6 μm. The D50 particle size was determined using a Nanotrack UPA manufactured by Nikkiso Corporation.

[0227] [Preparation of Dispersion (2)]

[0228] 25 parts by weight of alumina (average particle size 150 nm) manufactured by Sumitomo Chemical Co., Ltd., 35 parts by weight of methyl ethyl ketone, and 30 parts by weight of 3-methoxy-1-butanol were mixed, dispersed and stirred, and then dispersed using a sand mill to prepare a dispersion with approximately 25% non-volatile components (2). The D50 particle size of the metal oxide in the obtained metal oxide dispersion was 150 nm. The D50 particle size was determined using a Nanotrack UPA manufactured by Nikkiso Co., Ltd.

[0229] [Preparation of Dispersion (3)]

[0230] The synthetic spherical silica SO-C5 manufactured by Admatechs was replaced with "Epostar FS" (melamine resin, average primary particle size: 200 nm) manufactured by Nippon Shokubai Co., Ltd. Otherwise, the same process was used as for dispersion (1) to obtain dispersion (3). The D50 particle size in the obtained filler dispersion was 200 nm.

[0231] [Preparation of Dispersion (4)]

[0232] The synthetic spherical silica SO-C5 manufactured by Admatechs was replaced with "MX-80H3wT" (acrylate crosslinker, average primary particle size: 800 nm) manufactured by Soken Chemical Co., Ltd. Otherwise, the same process as dispersion (1) was used to obtain dispersion (4). The D50 particle size of the metal oxide in the obtained metal oxide dispersion was 800 nm.

[0233] <<Preparation and Evaluation of Protective Agents and Laminated Films for Decorative Molding>>

[0234] [Example 1]

[0235] <Preparation of Protective Agent>

[0236] A solution of (meth)acrylate resin (a-1) with approximately 40% solids content (a-1) was mixed in a disperser. 100 parts of the solution, 27.5 parts of isocyanate curing agent (b-1), 22.5 parts of urethane (meth)acrylate (c-2), 1.1 parts of photopolymerization initiator (equivalent to 5 parts of the 100 parts of c-2) of oligomer {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone}, 8 parts of the filler dispersion (1), and 213.7 parts of methyl ethyl ketone (MEK) were mixed to obtain a protective agent (X-1) with 25% non-volatile components.

[0237] <Fabrication of Y-1 laminated film for decorative molding>

[0238] A protective agent (X-1) was applied to the substrate layer (F-1) using a bar coater. After drying in an oven at 100°C for 2 minutes, a coated film with a thickness of 5 μm was obtained. A conveyor-type ultraviolet irradiation device (high-pressure mercury lamp 120 W / cm²) was used. 2 Two lamps were used to irradiate the coating film with ultraviolet light at a transmission speed of 5 m / min (cumulative light intensity 1000 mJ / cm). 2 The resin (a-1) is stored (cured) in an oven at 40°C for 7 days to allow the unreacted components of the (meth)acrylate resin (b-1) to react with the unreacted components of the hardener (b-1) to form a protective surface layer. This is then used as a decorative molding laminate (Y-1).

[0239] For the obtained decorative molding laminate before molding, the Martens hardness, the confirmation of the island structure caused by the difference in elastic modulus, elongation, chipping resistance, scratch resistance, and chemical resistance are evaluated according to the method described later. Next, a decorative molded body is made using the aforementioned decorative molding laminate, and the moldability and chemical resistance of the made decorative molded body are evaluated.

[0240] <Evaluation of transparency (haze)>

[0241] Instead of the substrate layer (F-1), a protective agent (X-1) is applied to the release treatment surface of the release film (polyethylene terephthalate (PET) film TN-100 manufactured by Toyobo Co., Ltd.), thus forming a surface protective layer.

[0242] The surface protective layer was separated from the self-peeling film, and the haze value was measured using an NDH-2000 haze meter (manufactured by Tokyo Denshoku Co., Ltd.).

[0243] [Examples 2-5]

[0244] As described in Table 2, the amount of the active energy line hardening component (c) was changed, and otherwise, the protective agent, decorative molding laminate, and transparency evaluation sample were prepared and evaluated in the same manner as in Example 1.

[0245] [Examples 6-9, Examples 27-36]

[0246] As described in Tables 2 and 4, the type of active energy line hardening component (c) was changed. Otherwise, the protective agent, decorative molding laminate, and transparency evaluation sample were prepared and evaluated in the same manner as in Example 1.

[0247] [Examples 10-12]

[0248] As described in Table 2, the amounts of isocyanate-based curing agent (b) and active energy line curing components were changed. Otherwise, protective agents, decorative molding laminates, and transparency evaluation samples were prepared and evaluated in the same manner as in Example 1.

[0249] [Examples 13-14]

[0250] Using a protective agent (X-1), the thickness of the surface protective layer was varied as described in Table 2. Otherwise, the protective agent, decorative molding laminate, and transparency evaluation sample were prepared and evaluated in the same manner as in Example 1.

[0251] [Examples 15 to 24]

[0252] As described in Table 3, (meth)acrylate resin (a-2) solution to (meth)acrylate resin (a-10) solution were used instead of (meth)acrylate resin (a-1) solution, and the amounts of isocyanate-based curing agent (b) and active energy line curing component were changed. Otherwise, protective agent, decorative molding laminate and transparency evaluation sample were prepared and evaluated in the same manner as in Example 1.

[0253] [Examples 25-26]

[0254] As described in Table 3, a protective agent (X-3) was used, and substrate layer F-2 and substrate layer F-3 were used instead of substrate layer F-1. Otherwise, the protective agent, decorative molding laminate and transparency evaluation sample were prepared and evaluated in the same manner as in Example 1.

[0255] [Comparative Examples 1 to 4]

[0256] As described in Table 5, the active energy line hardening component was not formulated, and the filler dispersion (1) to the filler dispersion (4) were formulated instead of the filler dispersion (1). Otherwise, the protective agent, decorative molding laminate and transparency evaluation sample were prepared and evaluated in the same manner as in Example 1.

[0257] Furthermore, following the method described later, we attempted to confirm the island structure caused by the difference in elasticity coefficients, but were unable to do so.

[0258] [Comparative Example 5]

[0259] As described in Table 5, relative to the (meth)acrylate resin (a-1) solution, a large amount of isocyanate-based curing agent b-1 was prepared, and the amount of the active energy line curing component was changed. Otherwise, in the same manner as in Example 1, protective agents, decorative molding laminates, and transparency evaluation samples were prepared and evaluated.

[0260] [Comparative Example 6]

[0261] As described in Table 5, in addition to the (meth)acrylate resin (a-1) solution, a large amount of isocyanate-based curing agent b-1 and active energy line curing components were prepared, and protective agents, decorative molding laminates and transparency evaluation samples were prepared and evaluated in the same manner as in Example 1.

[0262] [Comparative Examples 7 to 9]

[0263] As described in Table 5, solutions of (meth)acrylate resin (a-11) to (meth)acrylate resin (a-13) were used instead of solution (meth)acrylate resin (a-1), and the amounts of isocyanate-based curing agent (b) and active energy line curing component were changed. Otherwise, protective agents, decorative molding laminates, and transparency evaluation samples were prepared and evaluated in the same manner as in Example 1. (Meth)acrylate resin (a-13) does not have hydroxyl groups, therefore the NCO / OH column in Table 5 is set to "-".

[0264] Furthermore, following the method described later, we attempted to confirm the island structure caused by the difference in elasticity coefficients, but were unable to do so.

[0265] [Comparative Example 10]

[0266] As described in Table 5, the (meth)acrylate resin (a-1) solution and the isocyanate-based curing agent b-1 were not used. Otherwise, the protective agent, decorative molding laminate, and transparency evaluation samples were prepared and evaluated in the same manner as in Example 1.

[0267] Furthermore, following the method described later, we attempted to confirm the island structure caused by the difference in elasticity coefficients, but were unable to do so.

[0268] [Comparative Example 11]

[0269] As described in Table 5, without the addition of isocyanate-based curing agent b-1 and active energy line curing components, protective agents, decorative molding laminates, and transparency evaluation samples were prepared and evaluated in the same manner as in Example 1.

[0270] Furthermore, following the method described later, we attempted to confirm the island structure caused by the difference in elasticity coefficients, but were unable to do so.

[0271] <Evaluation of Martens Hardness>

[0272] Using a Fischerscope H-100C microhardness tester manufactured by Fischer Instruments, a Vickers indenter (a four-sided pyramid) was pressed into the surface protective layer side of the decorative molding laminate film with a force of 3 mN, held for 5 seconds, and the value was read. Six points were measured using this method, and the average value was used for evaluation. Furthermore, the indentation depth of the terminal was 0.8 μm.

[0273] <Confirmation of Island Structure>

[0274] <Measurement of the maximum diameter in a fixed direction>

[0275] Cut the decorative molding laminate into 1.5 cm squares and sandwich them between two glass slides with thermosetting epoxy resin (G2 manufactured by Gatan) dripped on them. Cure the resin on a hot plate at 120°C for 5 minutes.

[0276] The hardened sample was cut into 5 mm squares using a razor and placed on the sample stage of the cross-section polishing device (SM-09010 manufactured by Nippon Electronics Co., Ltd.). The accelerating voltage of the argon ion beam was set to 5 kV to create a cross-section for observation.

[0277] For the aforementioned profile, the surface protective layer profile was measured at any three locations within a 2 μm × 2 μm range using an SPM device (Oxford Instruments MFP-3D, cantilever: AC-160TS, dynamic measurement mode, setpoint: 1.4 V, target amplitude: 2 V) to obtain elastic coefficient images and convexity / concave images (height difference images).

[0278] The obtained elastic coefficient image ( Figure 1 The image data was input into the image analysis software "Mac-View Ver.4" manufactured by MOUNTECH. All visible structural domains (D) in the image were manually selected and analyzed. The maximum diameter in a given direction of all selected structural domains (D) was calculated, and their average value was taken. Figure 2 )

[0279] <Ratio of structural domains (D)>

[0280] If an island with a height difference greater than 5 nm is identified in the convex-concave image (height difference image) obtained using the SPM device, the area of ​​the island detected by the height difference is subtracted from the area of ​​the 2 μm × 2 μm area, and the value is used as the reference area.

[0281] Based on the elastic coefficient image obtained for the same observation area, similar to the determination of the maximum diameter in a given direction, all identifiable structural domains (D) are selected in manual mode, and automatic analysis is performed to calculate the total area of ​​the structural domains (D). Using the area of ​​the reference as the denominator, the ratio of structural domains (D) at any given location is calculated. By changing the observation area, the ratio of structural domains (D) is calculated within a total of 3 arbitrary locations within a 2 μm × 2 μm range, and its average value is calculated.

[0282] <Determination of Elongation>

[0283] The decorative molding laminated film was cut into pieces 10 mm wide and 20 mm long, and a tensile test was performed under the following conditions.

[0284] Tensile testing machine: "AGS-X Benchtop Precision Universal Testing Machine" (manufactured by Shimadzu Corporation)

[0285] Heating furnace: "Thermostatic bath TCE-N300" (manufactured by Shimadzu Corporation)

[0286] Sample width: 10 mm

[0287] Temperature: 140℃

[0288] Stretching speed: 30 mm / min

[0289] Chuck spacing: 10 mm

[0290] The elongation rate is calculated from the chuck distance when an appearance abnormality occurs, such as cracking of the surface protective layer, peeling of the surface protective layer from the substrate layer, or breakage of the surface protective layer. Furthermore, when the chuck distance is 20 mm when an appearance abnormality occurs, the 10 mm decorative molding laminate film further elongates by 10 mm, so the elongation rate is calculated to be 100%.

[0291] <Evaluation of Chipping Resistance>

[0292] The decorative molding laminate was cut into 3 cm long x 5 cm wide pieces. The substrate layer was placed side-by-side against a 4 cm long x 10 cm wide stainless steel plate. The ends were secured with 5 mm wide double-sided tape. Using a gravel testing machine (manufactured by Suga Testing Machine Co., Ltd.), 100 g of JIS-standard silica sand (sold by the Japan Powder Industry Association) was applied at a distance of 30 cm at a rate of 3.0 kg / cm². 2 The surface protective layer was impacted at 23°C at a 90-degree angle with air pressure. After impact, the decorative molding laminate was washed with water and dried. The surface of the protective layer was then visually evaluated under sunlight for whitening, while the substrate layer was observed under a microscope at 50x magnification for exposure. S rating indicates best, A rating indicates good, B rating indicates general use, C rating indicates usable depending on the environment, and D rating indicates not usable.

[0293] S: Although there is damage, the whitening caused by the damage is absent or minimal.

[0294] A: Partially whitened.

[0295] B: Overall, there is obvious whitening.

[0296] C: There is obvious whitening overall, and part of the substrate layer can be seen exposed.

[0297] D: The entire substrate layer is visible.

[0298] <Evaluation of abrasion resistance>

[0299] Decorative molding laminates were cut into 10 cm long x 5 cm wide pieces. The surface of the protective layer was rubbed twice with steel wool (#0000) under a 100 g load. Evaluation was based on the number of damaged strips and the change in haze (ΔHAZE) before and after wiping. S represents best, A represents excellent, B represents good, C represents usable, and D represents unusable. The evaluation criteria are as follows.

[0300] S: Less than 5 damages

[0301] A: There are 5 or more but less than 10 damages.

[0302] B: More than 10 damages and ΔHAZE less than 0.5%.

[0303] C: More than 10 injuries with a ΔHAZE of 0.5% or more but less than 3.0%.

[0304] D: More than 10 damages and ΔHAZE greater than 3.0%.

[0305] <Evaluation of Drug Resistance>

[0306] 0.5 g of sunscreen (Neutrogena Ultra Thin Dry-Tooth Sunscreen SPF55, manufactured by Johnson & Johnson) was applied to the surface of the protective layer of the decorative molding laminate and left at 80°C for 4 hours. After leaving the film, the sunscreen was rinsed off with water and the moisture was removed. The appearance of a 3 cm diameter circle centered on the area where the sunscreen was applied was then visually observed.

[0307] Furthermore, as a protective agent imparting chemical resistance, S / A is preferred; B / C is suitable depending on the usage environment of the molded article; and D is not suitable for practical use. The evaluation criteria are as follows.

[0308] S: No visible defects.

[0309] A: Traces of coating are visible, but no whitening / surface roughness is found.

[0310] B: Whitening / roughness is visible in part of the coated area.

[0311] C: Slight whitening / roughness is visible throughout the coated area.

[0312] D: Significant whitening / surface roughness is visible throughout the coated area.

[0313] <Evaluation of formability>

[0314] [Creating Decorative Molded Objects]

[0315] In a TOM molding machine (manufactured by Fuse Vacuum Corporation, NGF0406-T), a decorative molded body is produced by placing the substrate layer of a decorative molding laminate in contact with the body to be decorated under the following conditions.

[0316] As shown below, three aluminum cuboids with the same area but different heights are used as the decorative molded body. With the decorative molding laminate in close contact with the 5 cm x 5 cm face of the cuboid, the decorative molding laminate is stretched primarily along the height direction, covering all five faces of the cuboid. The resulting surface protective layer of the decorative molded body is located on the outermost surface of the convex side.

[0317] Cuboid (1): Length 5 cm × Width 5 cm × Height 1 cm

[0318] Cuboid (2): Length 5 cm × Width 5 cm × Height 0.75 cm

[0319] Cuboid (3): Length 5 cm × Width 5 cm × Height 0.5 cm

[0320] Molding temperature: 120℃

[0321] Compressed air pressure: 300 kPa

[0322] Compressed air time: 10 seconds

[0323] The following criteria are used to evaluate whether there are cracks in the surface protective layer and whether the substrate layer is damaged on the side (height portion) of the decorative molded body.

[0324] S: In any of the cuboids (1) to (3), there are no cracks in the surface protective layer and no damage to the substrate layer.

[0325] A: In the case of cuboid (1), cracks are generated on the surface protective layer, but the substrate layer is not damaged. In the cases of cuboid (2) and cuboid (3), there are no cracks in the surface protective layer and no damage to the substrate layer.

[0326] B: In the case of cuboid (1) and cuboid (2), cracks are generated on the surface protective layer, but the substrate layer is not damaged. In the case of cuboid (3), there are no cracks in the surface protective layer and no damage to the substrate layer.

[0327] C: In the case of all cuboids (1) to cuboids (3), cracks are generated on a portion of the four sides of the surface protective layer, but the substrate layer is not damaged.

[0328] D: In the case of all cuboids (1) to cuboids (3), cracks occur on the entire surface of the four sides of the surface protective layer, or the substrate layer is broken.

[0329] In addition, S, A, and B are easy to mold; C can also be used depending on the shape of the object being molded; and D is not suitable for practical use.

[0330] <Evaluation of Chemical Resistance of Decorative Molded Components>

[0331] Using a cuboid (1) prepared in the formability evaluation, sunscreen was applied to the 5 cm long × 5 cm wide surface of the decorative molded body, and the evaluation was conducted in the same manner as the evaluation of the chemical resistance of the laminated film for decorative molding.

[0332] [Table 2]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340] As shown in the examples in Tables 2, 3, and 4, the martensitic hardness is within a specific range, and the components forming the surface protective layer are partially incompatible to form structural domains (D), thereby maintaining high transparency. At the same time, it exhibits excellent scratch resistance, chemical resistance, elongation, and chipping resistance, demonstrating performance within the practical range in all evaluation items.

[0341] Martens hardness, maximum diameter of structural domain (D) in a specific direction, and its ratio within a specific range indicate that the abrasion resistance, formability, chipping resistance, and chemical resistance of the molded body are within the practical range, thus maintaining or improving the chemical resistance of the molded body.

[0342] Examples 2 to 7, 10, 15 to 18, 27 to 30, and 33 to 36, which are within the particularly preferred range, exhibited high performance in terms of chemical resistance and cracking resistance.

[0343] Comparative Examples 1-4 and 7-11, which are island structures based on elastic coefficient images, were not found to be outside the scope of practical application, especially in terms of chemical resistance and crack resistance. Even in Comparative Examples 5 and 6, which are island structures based on elastic coefficient images, the ratio of structural domains (D) is outside the scope of practical application, and various properties are also outside the scope of practical application.

Claims

1. A laminated film for decorative molding, comprising a surface protective layer and a substrate layer, characterized in that, The Martens hardness measured from the surface protective layer side of the decorative molding laminate is 100 N / mm. 2 ~300 N / mm 2 , The surface protective layer has an island structure with structural domains (D) and a matrix (M). The matrix (M) is a cured product of a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups and an isocyanate-based curing agent (b) not having photocurable functional groups. The structural domain (D) is a hardened product containing a multifunctional active energy line hardening component (c) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate (c2) with a weight average molecular weight of 400-5000. The maximum diameter of the structural domain (D) in a given direction is 0.05 μm to 0.5 μm. The ratio of domain (D) to matrix (M) is 5–44:95–56.

2. The laminated film for decorative molding according to claim 1, wherein, In the tensile test of the decorative molding laminate at 140°C, the elongation of the surface protective layer is 50% to 200%.

3. The laminated film for decorative molding according to claim 1 or 2, wherein, The surface protective layer has a haze of 5% or less as specified in Japanese Industrial Standard K 7136.

4. A method for manufacturing a decorative molding laminated film, comprising the method for manufacturing a decorative molding laminated film as described in any one of claims 1 to 3, wherein, A protective agent comprising a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups, an isocyanate-based curing agent (b) not having photocurable functional groups, an active energy line-curing component (c) comprising urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400 to 5000 (c2), and an organic solvent is applied to a substrate layer and dried, thereby allowing at least a portion of the (meth)acrylate resin (a) to react with the isocyanate-based curing agent (b). Irradiation with active energy lines causes the hardening components of the active energy lines to harden, forming a surface protective layer.

5. A method for manufacturing a decorative molding laminated film, comprising the method for manufacturing a decorative molding laminated film as described in any one of claims 1 to 3, wherein, A release film is made by applying a protective agent containing a (meth)acrylate resin (a) having hydroxyl groups but not photocurable functional groups, an isocyanate-based curing agent (b) not having photocurable functional groups, an active energy line curing component (c) containing urethane (meth)acrylate (c1) and / or (meth)acrylate with a weight average molecular weight of 400 to 5000 (c2), and an organic solvent, and then drying it to allow at least a portion of the (meth)acrylate resin (a) to react with the isocyanate-based curing agent (b). Irradiation with active energy lines causes the hardening components of the active energy lines to harden, forming a surface protective layer. Next, the surface protective layer is bonded to the substrate layer via an adhesive layer.

6. A decorative molded body, comprising: The object to be decorated, and the decorative molding laminated film as described in any one of claims 1 to 3 covering at least a portion of the object to be decorated.

Images