Laminates and surface coating compositions containing a surface layer having scratch resistance and matte finish.

Abstract

Provided are a laminate including a surface layer that has excellent matte properties and gives good results in both needle scratch tests and nail scratch tests, and a surface coating composition that can prepare such a surface layer.

Description

Technical Field

[0001] The present disclosure relates to a laminate and a surface coating composition including a surface layer having scratch resistance and matting properties.

Background Art

[0002] In recent years, films presenting a low gloss appearance and having scratch resistance have been developed.

[0003] Patent Document 1 (Japanese Patent Application Laid-Open No. 2019-123782) describes a scratch-resistant film having a surface layer including a binder containing a urethane resin, urethane resin beads having an average particle diameter of 3 micrometers or more and 30 micrometers or less, hard particles having an average particle diameter of 5 micrometers or more and 45 micrometers or less, and nanosilica particles, wherein the surface layer contains 30 parts by mass or more and 500 parts by mass or less of the hard particles based on 100 parts by mass of the binder, and the glossiness of the surface layer is 5.5 GU or less at 60 degrees.

[0004] Patent Document 2 (Japanese Patent Application Laid-Open No. 2019-072935) describes a stretchable film having a surface layer including a binder containing a urethane resin, urethane resin beads having an average particle diameter of 4 micrometers or more and 20 micrometers or less, and nanosilica particles, wherein the surface glossiness is 5 GU or less at 60 degrees.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Known tests for evaluating scratch resistance include, for example, the pencil hardness test described in Patent Document 1, the steel wool abrasion test described in Patent Document 2, the needle scratch test using a steel needle, and the fingernail scratch test.

[0007] Because the failure modes differ in these tests, for example, a good result might be obtained in the pencil hardness test or needle scratch test, but not in the nail scratch test, or vice versa.

[0008] This disclosure provides a laminate including a surface layer that exhibits excellent mattifying properties and yields good results in both needle scratch tests and fingernail scratch tests, as well as a surface coating composition capable of preparing such a surface layer. [Means for solving the problem]

[0009] According to one embodiment of the present disclosure, a laminate is provided comprising a substrate and a surface layer having scratch resistance and matte finish, the surface layer containing resin beads having an average particle size of about 1 micrometer or more and about 20 micrometers or less, and a glass transition temperature greater than about -30°C and less than about 34°C, wherein the surface layer contains less than about 75% by mass of resin beads based on the total weight of the surface layer, and exhibits an elastic modulus of about 65 MPa or less in the region of the surface layer other than the resin beads when the elastic modulus of the surface layer is measured with an atomic force microscope.

[0010] According to another embodiment of the present disclosure, a surface coating composition is provided which contains resin beads having an average particle size of about 1 micrometer or more and about 20 micrometers or less, and a glass transition temperature greater than about -30°C and less than about 34°C, and a binder precursor, wherein the surface coating composition contains less than about 75 parts by mass of resin beads based on 100 parts by mass of solid content of the surface coating composition, and the surface layer formed by the surface coating composition exhibits an elastic modulus of about 65 MPa or less in the region of the surface layer other than the resin beads when the elastic modulus of the surface layer is measured with an atomic force microscope. [Effects of the Invention]

[0011] According to this disclosure, it is possible to provide a laminate including a surface layer that has excellent matte finish and yields good results in both needle scratch tests and fingernail scratch tests, as well as a surface coating composition that can prepare such a surface layer.

[0012] The foregoing description shall not be deemed to disclose all embodiments of the present invention and all advantages relating to the present invention. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view of a laminate in one embodiment of the present disclosure. [Figure 2] (a) is a photograph of the laminate of Comparative Example 3 after the needle scratch test, and (b) is a photograph of the laminate of Example 1 after the needle scratch test. [Figure 3] (a) is a photograph of the laminate of Reference Comparative Example 1 after the heel mark test, and (b) is a photograph of the laminate of Example 11 after the heel mark test. [Figure 4] (a) is an atomic force microscope topography image of the laminate surface of Example 1, and (b) is an atomic force microscope amplitude image of the laminate surface of Example 1. [Modes for carrying out the invention]

[0014] Hereinafter, for the purpose of exemplifying typical embodiments of the present invention, a more detailed description will be given with reference to the drawings as necessary, but the present invention is not limited to these embodiments.

[0015] In the present disclosure, "matte property" is intended to exhibit a lower surface glossiness compared to a surface layer that does not contain resin beads.

[0016] In the present disclosure, "scratch resistance" is intended to exhibit good results in both the needle scratch test and the fingernail scratch test described later.

[0017] In the present disclosure, "(meth)acryl" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0018] In the present disclosure, "curing" can generally include the concept called "crosslinking".

[0019] In the present disclosure, "film" includes an article called "sheet".

[0020] In the present disclosure, for example, in "the surface layer is disposed on the substrate", "on" means that the surface layer is directly disposed on the upper side of the substrate, or the surface layer is indirectly disposed on the upper side of the substrate through another layer.

[0021] In the present disclosure, for example, in "the adhesive layer is disposed under the substrate", "under" means that the adhesive layer is directly disposed on the lower side of the substrate, or the adhesive layer is indirectly disposed on the lower side of the substrate through another layer.

[0022] In the present disclosure, "substantially" means including variations caused by manufacturing errors or the like, and is intended to allow a variation of about ±20%.

[0023] In this disclosure, "transparent" means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm), measured in accordance with JIS K 7375, is approximately 80% or higher, preferably approximately 85% or higher, or approximately 90% or higher. There are no particular restrictions on the upper limit of the average transmittance, but for example, it may be less than approximately 100%, approximately 99% or lower, or approximately 98% or lower.

[0024] In this disclosure, "translucent" means that the average transmittance in the visible light region (wavelength 400nm to 700nm), measured in accordance with JIS K 7375, is less than approximately 80%, preferably less than approximately 75%, and is intended not to completely conceal the substrate.

[0025] In one embodiment, the laminate of the present disclosure includes a substrate and a surface layer having scratch resistance and matte finish, which contains resin beads having an average particle size of about 1 micrometer or more and about 20 micrometers or less, and a glass transition temperature greater than about -30°C and less than about 34°C, and a binder, wherein the surface layer contains less than about 75% by mass of resin beads based on the total weight of the surface layer, and when the elastic modulus of the surface layer is measured with an atomic force microscope, the region of the surface layer other than the resin beads exhibits an elastic modulus of about 65 MPa or less. The surface layer may be a single layer or a laminated structure.

[0026] The fracture mode of the surface layer in needle scratch tests is thought to be influenced by factors such as the sliding or fracture of resin beads caused by the needle. The resin beads of this disclosure have a glass transition temperature within a predetermined range, which contributes to the flexibility of the beads, thus preventing or reducing the sliding or fracture of resin beads caused by the needle.

[0027] When considering how to further prevent the destruction of the surface layer by the needle in a needle scratch test, it is generally thought that the hardness of the surface layer can be increased by incorporating, for example, a hard binder or hard inorganic particles into the surface layer. However, the inventors have found that in such cases, although needle scratch resistance is improved, nail scratch resistance decreases because the hardened surface layer makes the nail more susceptible to wear.

[0028] The laminate of this disclosure has a surface layer containing a predetermined amount of resin beads having an average particle size and glass transition temperature within the above range, and exhibiting a predetermined elastic modulus. Therefore, in addition to excellent mattifying properties, it is possible to provide a laminate that is excellent in scratch resistance, both in needle scratch resistance and fingernail scratch resistance.

[0029] Figure 1 shows a schematic cross-sectional view of a laminate according to one embodiment of the present disclosure. The laminate 100 in Figure 1 includes a surface layer 10 and a substrate 20. The surface layer 10 includes a binder 11 and resin beads 12 having an average particle size of about 1 micrometer or more and about 20 micrometers or less, and a glass transition temperature greater than about -30°C and less than about 34°C.

[0030] The binder is not particularly limited as long as the surface layer containing the binder exhibits the above-mentioned elastic modulus. Examples include resins having urethane bonds, (meth)acrylic resins, epoxy resins, phenolic resins, polyvinyl alcohol, vinyl acetate resins, vinyl chloride resins, and silicone resins. Among these, resins having urethane bonds are preferred from the viewpoint of scratch resistance, and urethane resins are more preferred. In this disclosure, "resins having urethane bonds" can include not only urethane resins but also resins prepared using at least one selected from, for example, urethane (meth)acrylate and urethane (meth)acrylate oligomers, and urethane resins can also include (meth)acrylic urethane resins. The binder can be used alone or in combination of two or more types.

[0031] The binder content can be, for example, more than approximately 25% by mass, approximately 26% or more by mass, approximately 28% or more by mass, or approximately 30% or more by mass, based on the total weight of the surface layer. There is no particular upper limit on the binder content, but from the viewpoint of matte finish, scratch resistance, etc., it can be approximately 90% or less by mass, approximately 80% or less by mass, approximately 70% or less by mass, approximately 60% or less by mass, approximately 50% or less by mass, or less by mass. The amount of binder blended can be appropriately selected from this range based on the required performance (e.g., matte finish, scratch resistance) according to the intended use.

[0032] In one embodiment, the binder may be an aqueous or non-aqueous resin prepared using an aqueous or non-aqueous (solvent-based) composition. However, it is advantageous to use a resin prepared using an aqueous composition (sometimes referred to as "aqueous resin") because it is easier to prepare a flexible surface layer. Examples of aqueous resins include aqueous resins having urethane bonds (sometimes referred to as "aqueous urethane resin"), aqueous (meth)acrylic resins, aqueous vinyl chloride resins, aqueous vinyl acetate resins, and aqueous silicone resins. Among these, aqueous urethane resins are preferred from the viewpoint of scratch resistance.

[0033] The water-based urethane resin used as a binder can be prepared, for example, by using a water-based urethane resin composition dispersed in an aqueous dispersion medium in the form of an emulsion containing oil droplets (urethane resin particles). By applying such a water-based urethane resin composition to a substrate, drying it, and optionally crosslinking it, a layer containing the water-based urethane resin can be formed on the substrate.

[0034] Water-based urethane resins can be obtained, for example, by reacting polyols and polyisocyanates with polyamines, if necessary. Here, the polyamine is not particularly limited as long as it is a compound having an amino group and / or an imino group, and can function, for example, as a chain extender.

[0035] The polyols that can form water-based urethane resins are not particularly limited as long as they are compounds having multiple hydroxyl groups. Suitable examples of polyols include polyether polyols; polyester polyols; polymer polyols having carbon-carbon bonds in their main chain skeleton, such as (meth)acrylic polyols, polybutadiene diols, and hydrogenated polybutadiene polyols; polycarbonate polyols; and polycaprolactone polyols. Polyols can be used alone or in combination of two or more.

[0036] Polyisocyanates capable of forming aqueous urethane resins are not particularly limited as long as they are compounds having multiple isocyanate groups. Examples of suitable polyisocyanates include aromatic polyisocyanates (e.g., 2,6-toluenediisocyanate, 2,5-toluenediisocyanate, 2,4-toluenediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, methylenebis(o-chlorophenyldiisocyanate), methylenediphenylene-4,4'-diisocyanate, polycarbodiimide-modified methylenediphenyl Diisocyanates, (4,4'-diisocyanato-3,3',5,5'-tetraethyl)diphenylmethane, 4,4'-diisocyanato-3,3'-dimethoxybiphenyl (o-dianisidine diisocyanate), 5-chloro-2,4-toluene diisocyanate, 1-chloromethyl-2,4-diisocyanatobenzene); aromatic-aliphatic polyisocyanates (e.g., m-xylylene diisocyanate, tetramethyl-m- Examples include xylylene diisocyanates; aliphatic polyisocyanates (e.g., 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,12-diisocyanatododecane, 2-methyl-1,5-diisocyanatopentane); alicyclic polyisocyanates (e.g., dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 2,2,4-trimethylhexyl diisocyanate, cyclohexylene-1,4-diisocyanate); and polymer compounds or oligomer compounds (e.g., polyoxyalkylenes, polyesters, polybutadienyl, etc.) terminated with two isocyanate functional groups (e.g., diurethane of polypropylene oxide glycol terminated with toluene-2,4-diisocyanate). Furthermore, modified forms such as dimers, trimers, or biuret compounds of these polyisocyanates can also be mentioned. In some embodiments, aliphatic diisocyanates are preferred as polyisocyanates from the viewpoint of scratch resistance and other factors. Polyisocyanates can be used alone or in combination of two or more types.

[0037] In some embodiments, the aqueous resin may optionally have one or more functional groups that can enhance dispersibility and / or solubility in aqueous solvents. Such functional groups are not particularly limited as long as they are hydrophilic groups, for example, hydroxyl groups, carboxyl groups, -COO groups, etc. - , sulfo group, -SO3 - Examples include quaternary ammonium and polyethylene glycol chains. In particular, from the viewpoint of durability and long-term stability, carboxyl groups or -COO - A carboxyl group is preferred, and a carboxyl group is more preferred. As a component (compound) for introducing carboxyl groups into an aqueous resin, for example, polyols having carboxyl groups such as dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and dihydroxysuccinic acid can be used. By examining the presence of such functional groups in the binder in the surface layer, it is possible to determine whether or not the binder is an aqueous resin.

[0038] In some embodiments, the binder may include a crosslinked product obtained by crosslinking a crosslinkable composition. For example, an aqueous urethane resin is dispersed in an aqueous dispersion medium in the form of an emulsion containing oil droplets (urethane resin particles). By preparing a crosslinkable composition by incorporating a crosslinking agent into such a composition and then applying it to a substrate to crosslink it, a crosslinked structure (network structure) can be formed between the urethane resin particles. As a result, the durability and long-term stability of the surface layer can be further improved.

[0039] There are no particular restrictions on the crosslinking agent, and examples include polyaziridine, polycarbodiimide, epoxy, oxazoline group-containing polymers, or combinations thereof.

[0040] The surface layer of this disclosure contains resin beads having an average particle size of about 1 micrometer or more and about 20 micrometers or less, and a glass transition temperature greater than about -30°C and less than about 34°C. As illustrated in Figure 1, the resin beads can form fine irregularities on the surface of the laminate's surface layer, thereby forming a suitable low-gloss (matte) structure.

[0041] In some embodiments, from the viewpoint of matte finish and scratch resistance, the average particle diameter of the resin beads is preferably about 2 micrometers or more, about 3 micrometers or more, about 4 micrometers or more, or about 5 micrometers or more, and preferably about 18 micrometers or less, about 17 micrometers or less, about 16 micrometers or less, about 15 micrometers or less, about 14 micrometers or less, about 13 micrometers or less, about 12 micrometers or less, about 11 micrometers or less, or about 10 micrometers or less. The average particle diameter of the resin beads is the 50% cumulative volume particle diameter measured using a laser diffraction particle size distribution analyzer.

[0042] In some embodiments, from the viewpoint of scratch resistance, the glass transition temperature (sometimes abbreviated as "Tg") of the resin beads is preferably about -28°C or higher, about -25°C or higher, about -23°C or higher, about -20°C or higher, about -18°C or higher, or about -15°C or higher, and preferably about 32°C or lower, about 30°C or lower, about 25°C or lower, about 20°C or lower, about 15°C or lower, about 10°C or lower, about 5°C or lower, or about 0°C or lower. The glass transition temperature of the resin beads is the temperature at the midpoint of the temperature range in which glass transition occurs, as measured by differential scanning calorimeter (DSC).

[0043] There are no particular restrictions on the resin beads, and examples include resin beads prepared from resins having urethane bonds, styrene resins, nylon resins, polyester resins, melamine resins, silicone resins, (meth)acrylic resins, etc. Such resin beads may be solid or have voids, and can be used alone or in combination of two or more types. Among these, resin beads containing resins having urethane bonds (sometimes referred to as "urethane resin beads") are preferred from the viewpoint of matte finish, scratch resistance, and conformability when the surface layer is stretched. The surface of the resin beads may be modified with a known surface modifier.

[0044] As the urethane resin beads, cross-linked urethane resin beads obtained by suspension polymerization, seed polymerization, emulsion polymerization, etc., can be used. Such resin beads have excellent flexibility, toughness, and scratch resistance, and these properties can be imparted to the surface layer.

[0045] When the resin beads and binder are made of the same type of resin component, for example, when the resin beads and binder contain a urethane component, or when the resin beads and binder contain a (meth)acrylic component, such resin beads have excellent affinity with the binder, thus improving adhesion to the binder. As a result, even if the laminate is stretched or deformed, the detachment of the resin beads from the binder can be reduced or suppressed. Here, "same type of resin component" does not mean that the constituent components of the resin are completely identical, but also includes cases where there is one or more common resin component among the components that make up the resin. For example, resin beads prepared from urethane acrylate contain two types of components, urethane and acrylic. Therefore, such resin beads can be said to be made of the same type of resin component as a urethane resin binder, as well as the same type of resin component as an acrylic resin binder.

[0046] In addition to the light scattering effect based on the surface irregularities of the surface layer, if the light scattering or refraction effect by the resin beads within the surface layer is also expected, it is preferable that the refractive index of the resin beads differs from that of the binder.

[0047] From the viewpoint of matte finish and scratch resistance, the surface layer of the laminate of this disclosure contains resin beads in an amount of less than approximately 75% by mass based on the total weight of the surface layer. In some embodiments, the resin bead content in the surface layer may be approximately 74% by mass or less, approximately 72% by mass or less, or approximately 70% by mass or less, based on the total weight of the surface layer. There is no particular lower limit to the resin bead content in the surface layer, but from the viewpoint of matte finish, etc., it can be approximately 10% by mass or more, approximately 20% by mass or more, approximately 30% by mass or more, approximately 40% by mass or more, approximately 50% by mass or more, or more than approximately 50% by mass. The amount of resin beads can be appropriately selected from this range based on the required performance (e.g., matte finish, scratch resistance) according to the intended use.

[0048] The surface layer of the laminate of this disclosure contains the resin beads and binder described above, and when the elastic modulus of such surface layer is measured using an atomic force microscope (sometimes referred to as "AFM"), the region of the surface layer other than the resin beads exhibits an elastic modulus of approximately 65 MPa or less. AFM measurement can be performed in minute regions on the order of nanometers. Therefore, for example, when measuring the surface area of ​​the surface layer near symbol 12 on the right side of Figure 1, even if resin beads are present below the surface layer, the elastic modulus of the region of the surface layer other than the resin beads can be measured without being affected by the resin beads. AFM measurement is performed by applying a minute needle to the surface. Sloping areas caused by the resin beads may induce sliding motion of the needle. Therefore, it is preferable to perform AFM measurement in the region of the surface layer other than the resin beads in a substantially flat region located between the resin beads (for example, the white rectangular area in Figure 4(b)). There are no particular restrictions on the size of the measurement area. From the viewpoint of obtaining good measurement results, the size of the measurement area is, for example, approximately 0.5 × approximately 0.5 square micrometers (μm). 2 ) ~ approximately 3 x 3 square micrometers (μm) 2 It is preferable that the range be approximately 1 × approximately 1 square micrometer (μm). 2 ) ~ approximately 2 x approximately 2 square micrometers (μm) 2) is more preferable. The modulus of elasticity is the average value of 6 points in a substantially flat area, for example, any 5 or more points on the surface layer, measured using AFM based on the conditions described later.

[0049] In some embodiments, from the viewpoint of scratch resistance, the elastic modulus in the area of ​​the surface layer other than the resin beads can be approximately 65 MPa or less, approximately 60 MPa or less, approximately 55 MPa or less, approximately 50 MPa or less, approximately 45 MPa or less, approximately 40 MPa or less, approximately 35 MPa or less, or approximately 30 MPa or less. There are no particular restrictions on the lower limit of the elastic modulus, and it can be set appropriately based on the required performance (e.g., scratch resistance) according to the application. For example, the lower limit of the elastic modulus can be approximately 1 MPa or more, approximately 5 MPa or more, approximately 10 MPa or more, approximately 15 MPa or more, approximately 18 MPa or more, or approximately 20 MPa or more. If the lower limit of the elastic modulus is approximately 1 MPa or more, the effect of reducing or preventing the adhesion of dirt, foreign matter, etc. to the surface layer can also be achieved.

[0050] In some embodiments, the surface layer may contain additives such as antifouling agents, fillers other than resin beads, UV absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow enhancers, leveling agents, pigments, dyes, and fragrances as other optional components. These additives can be used individually or in combination of two or more. The individual and total amounts of these additives can be determined within a range that does not impair the properties required for the surface layer.

[0051] For example, in applications requiring antifouling properties, it is advantageous to incorporate an antifouling agent into the surface layer. There are no particular restrictions on the antifouling agent; for example, silicone-based or fluorine-based antifouling agents can be used. Among these, antifouling agents having at least one functional group that can be incorporated into the binder are preferred. Examples of such functional groups include hydroxyl groups, carboxyl groups, amino groups, epoxy groups, and thiol groups. In particular, antifouling agents having hydroxyl groups, when combined with, for example, aqueous isocyanates, become less likely to bleed out from the surface layer, thus providing antifouling properties over a long period of time. Here, "incorporated into the binder" means a state in which, compared to antifouling agents without functional groups, they become less likely to bleed out from the surface layer by being compatible with, bonding to, or entangled with the binder components.

[0052] In some embodiments, an antifouling agent containing a resin having a crosslinked structure, such as an antifouling agent containing a silicone resin having urethane bonds, is preferred. The silicone resin having urethane bonds can be prepared, for example, by crosslinking a polyether-modified silicone having hydroxyl groups (antifouling component) with an aqueous isocyanate (crosslinking component). Such a resin having a crosslinked structure is easily incorporated into the binder and less likely to bleed out from the surface layer, thus providing antifouling performance over a long period of time. In particular, when the binder is a crosslinked aqueous urethane resin as described above, the binder component also forms a crosslinked structure between the urethane resin particles, making it easier to intertwine with the resin having a crosslinked structure, which is the antifouling agent. As a result, an antifouling agent containing such a resin having a crosslinked structure is less likely to bleed out from the surface layer, thus providing antifouling performance over a longer period of time.

[0053] The use of fillers other than resin beads (e.g., metal particles, inorganic particles) may reduce the results of the nail scratch test. Therefore, the content of such fillers is preferably about 10% by mass or less, about 5% by mass or less, about 3% by mass or less, about 1% by mass or less, or about 0.5% by mass or less, based on the total weight of the surface layer, or it is more preferable that such fillers are not incorporated into the surface layer.

[0054] The surface coating composition of this embodiment for preparing the surface layer may contain various materials that can be used in the surface layer described above, and contains at least resin beads having an average particle size of about 1 micrometer or more and about 20 micrometers or less, and a glass transition temperature greater than about -30°C and less than about 34°C, and a binder precursor. Here, "binder precursor" means a component that will ultimately become a binder in the surface layer, and examples include curable or crosslinkable monomers and / or curable or crosslinkable oligomers, resins that have been pre-cured or crosslinked therefrom, and non-curable or non-crosslinkable resins such as thermoplastic resins. Therefore, the surface coating composition may contain additives such as crosslinking agents and curing agents as optional components. A surface coating composition containing a crosslinking agent may be called a crosslinkable composition, and a surface coating composition containing a curing agent may be called a curable composition.

[0055] Furthermore, when the elastic modulus of the surface layer formed by the surface coating composition of this embodiment is measured using an atomic force microscope, the region of the surface layer other than the resin beads exhibits an elastic modulus of approximately 65 MPa or less. In addition, the surface layer formed by the surface coating composition can similarly exhibit an elastic modulus within the range described above.

[0056] As mentioned above, since it is easy to prepare a flexible surface layer with an elastic modulus of approximately 65 MPa or less, it is advantageous for the surface coating composition to be an aqueous composition.

[0057] The resin bead content in the surface coating composition can be less than approximately 75 parts by mass, approximately 74 parts by mass or less, approximately 72 parts by mass or less, or approximately 70 parts by mass or less, based on 100 parts by mass of solid content of the surface coating composition. There is no particular lower limit to the resin bead content, but from the viewpoint of mattifying properties, it can be approximately 10 parts by mass or more, approximately 20 parts by mass or more, approximately 30 parts by mass or more, approximately 40 parts by mass or more, approximately 50 parts by mass or more, or more than approximately 50 parts by mass.

[0058] The binder precursor content in the surface coating composition can be more than approximately 25 parts by mass, approximately 26 parts by mass or more, approximately 28 parts by mass or more, or approximately 30 parts by mass or more, based on 100 parts by mass of solid content of the surface coating composition. There is no particular upper limit on the binder precursor content, but from the viewpoint of matte finish, scratch resistance, etc., it can be approximately 90 parts by mass or less, approximately 80 parts by mass or less, approximately 70 parts by mass or less, approximately 60 parts by mass or less, approximately 50 parts by mass or less, or less than approximately 50 parts by mass.

[0059] The various additive components described above can be appropriately blended as long as they do not impair the necessary properties of the surface layer obtained by the surface coating composition. Here, when introducing an antifouling agent into the surface layer using an aqueous surface coating composition containing a polyether-modified silicone having hydroxyl groups, which is an antifouling agent, it is advantageous to blend an aqueous isocyanate (crosslinking component) into the composition. The hydroxyl groups bound to the polyether-modified silicone are prone to adsorbing dirt, which may reduce the antifouling performance. By blending an aqueous isocyanate together with the polyether-modified silicone having hydroxyl groups into the composition, the hydroxyl groups are consumed during crosslinking, thus suppressing the reduction in antifouling performance. At the same time, the crosslinking reaction of these components creates a crosslinked structure that is easily incorporated into the binder of the surface layer, thus suppressing the bleed-out of the antifouling agent from the surface layer and allowing the antifouling performance to be maintained over a long period of time.

[0060] From the viewpoint of suppressing the deterioration of antifouling performance, achieving long-term antifouling performance, scratch resistance, matte finish, etc., the mass ratio of aqueous isocyanate to binder precursor can be approximately 30% or more, approximately 50% or more, approximately 70% or more, or approximately 100% or more in terms of solid content, and can be less than approximately 400%, approximately 350% or less, approximately 300% or less, approximately 250% or less, or approximately 200% or less. Furthermore, the amount of polyether-modified silicone having hydroxyl groups can be approximately 0.5 parts by mass or more, approximately 0.6 parts by mass or more, approximately 0.7 parts by mass or more, approximately 0.8 parts by mass or more, approximately 0.9 parts by mass or more, or approximately 1.0 part by mass or more, based on 100 parts by mass of solid content of the surface coating composition, and can be approximately 5.0 parts by mass or less, approximately 4.0 parts by mass or less, approximately 3.0 parts by mass or less, or approximately 2.0 parts by mass or less.

[0061] As the aqueous isocyanate, for example, a water-dispersible isocyanate crosslinking agent can be used. Examples of water-dispersible isocyanate crosslinking agents include a compound in which a polyisocyanate compound having two or more isocyanate groups in one molecule is modified with hydrophilic groups such as polyethylene oxide, carboxyl groups, or sulfonic acid groups to make it self-emulsifying (hereinafter also referred to as "self-emulsifying isocyanate crosslinking agent"), or a compound in which it is emulsified with a surfactant or the like to make it water-dispersible (hereinafter also referred to as "forced emulsifying isocyanate crosslinking agent").

[0062] Among self-emulsifying isocyanate crosslinking agents and forced-emulsifying isocyanate crosslinking agents, blocked isocyanate crosslinking agents are preferred, in which the isocyanate groups are protected with a blocking agent to prevent them from reacting with an aqueous medium.

[0063] Examples of polyisocyanate compounds in water-dispersible isocyanate crosslinking agents include aromatic polyisocyanate compounds such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tolylene diisocyanate; linear or cyclic aliphatic polyisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated versions of the aforementioned aromatic polyisocyanate compounds; burettes, dimers, trimers, or pentamers of these polyisocyanate compounds; and adducts of these polyisocyanate compounds with polyol compounds such as trimethylolpropane. Water-dispersible isocyanate crosslinking agents can be used alone or in combination of two or more types.

[0064] More specifically, examples of polyisocyanate compounds in water-dispersible isocyanate crosslinking agents include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and adducts of these polyisocyanate compounds with polyol compounds such as trimethylolpropane, as well as burettes and isocyanurates of these polyisocyanate compounds.

[0065] Examples of known blocking agents include phenols, alkylphenols, active methylene compounds, oximes, lactams, bisulfites, and imidazoles. Blocking agents can be used alone or in combination of two or more.

[0066] Commercially available water-dispersible isocyanate crosslinking agents may be used. Among water-dispersible isocyanate crosslinking agents, commercially available blocked isocyanate crosslinking agents include, for example, Covestro's "Desmodule® BL1100", "Desmodule® BL1265 MPA / X", "Desmodule® VPLS2253", "Desmodule® BL3475 BA / SN", "Desmodule® BL3272 MPA", "Desmodule® BL3370 MPA", and "Desmodule® BL4265". Examples include "SN", "Desmosarm (trademark) 2170", "Sumijoul (trademark) BL3175", "Takenate (trademark) B-830N", "Takenate (trademark) B-815N", "Takenate (trademark) B-820NSU", "Takenate (trademark) B-846N", "Takenate (trademark) B-870N", "Takenate (trademark) B-874N", "Takenate (trademark) B-882N", "Takenate (trademark) B-883NS", "Takenate (trademark) WB-3936", and "Takenate (trademark) WB-3021", as well as "Aqua BI200" and "Aqua BI220" from Baxenden.

[0067] Examples of commercially available water-dispersible isocyanate crosslinking agents other than blocked isocyanate crosslinking agents include, for example, "Duranate® WB40-100", "Duranate® WT20-100", "Duranate® WT30-100", "Duranate® WL70-100", "Duranate® WR80-70P", and "Duranate® WE50-100" from Asahi Kasei Chemicals Corporation, and from Mitsui Chemicals, Inc. "Takenate (trademark) WD-720", "Takenate (trademark) WD-723", "Takenate (trademark) WD-725", "Takenate (trademark) WD-726", "Takenate (trademark) WD-730", "Barnock (trademark) DNW-5000", "Barnock (trademark) DNW-6000" manufactured by DIC Corporation, "Baihijule (trademark) 3100", "Baihijule (trademark) VPLS2306", "Baihijule ( "(Trademark) VPLS2319", "Baihijule (Trademark) VPLS2336", "Baihijule (Trademark) VPLS2150 / 1", "Baihijule (Trademark) VPLS2150RA", "Baihijule (Trademark) BL5140", "Baihijule (Trademark) BL5235", "Baihijule (Trademark) VPLS2240", "Baihijule (Trademark) VPLS2310", "Elastron (Trademark) BN-04" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Examples include "Lastron (trademark) BN-11", "Elastron (trademark) BN-27", "Elastron (trademark) BN-69", "Elastron (trademark) BN-77", and "Aquanate (trademark) 100", "Aquanate (trademark) 105", "Aquanate (trademark) 110", "Aquanate (trademark) 120", "Aquanate (trademark) 130", "Aquanate (trademark) 200", and "Aquanate (trademark) 210" manufactured by Tosoh Corporation.

[0068] The surface coating composition may optionally contain organic solvents, aqueous dispersions, etc., to improve workability, coating properties, etc. Among these, the use of an aqueous dispersion is advantageous from the viewpoint of safety for the human body and obtaining an aqueous composition that is easy to prepare a flexible surface layer. As the aqueous dispersion, for example, water such as distilled water, purified water, ion-exchanged water, or tap water can be used. Insofar as it does not affect the effects of the present invention, water-soluble alcohols such as ethanol may be used in combination with such water. The aqueous composition may contain organic solvents such as toluene as long as it is in the range of about 1000 ppm or less, but from the viewpoint of safety for the human body, it is preferable that such organic solvents are not included.

[0069] There are no particular limitations on the method for forming a surface layer using a surface coating composition, and known methods can be employed. For example, a surface coating composition can be applied to a substrate by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, etc., and the surface layer can be formed by drying as needed and optionally by thermal curing or ionizing radiation curing.

[0070] The thickness of the surface layer can be, for example, about 1 micrometer or more, about 3 micrometers or more, about 4 micrometers or more, about 5 micrometers or more, about 6 micrometers or more, about 8 micrometers or more, or about 10 micrometers or more, and can be about 50 micrometers or less, about 30 micrometers or less, about 20 micrometers or less, or about 15 micrometers or less. The thickness of the surface layer can be appropriately selected from this range based on the required performance (e.g., scratch resistance) according to the intended use. Here, the thickness of the surface layer in this disclosure means the thickness of the thickest part, i.e., the maximum thickness. The maximum thickness is the average value of values ​​measured at 5 or more locations, preferably 10 locations, using a micrometer (model number: ID-C112XB) manufactured by Mitutoyo Corporation in accordance with JIS K6783.

[0071] There are no particular limitations on the substrate constituting the laminate of this disclosure. For example, an organic substrate containing at least one selected from the group consisting of polyvinyl chloride resin, polyurethane resin, polyolefin resin, polyester resin, vinyl chloride-vinyl acetate resin, polycarbonate resin, (meth)acrylic resin, cellulose resin, and fluororesin can be used. Inorganic substrates such as glass and metallic substrates such as aluminum can also be used as substrates.

[0072] There are no particular restrictions on the shape or configuration of the substrate; for example, it may be in the shape of a film, a plate, a curved surface, an irregular shape, or a three-dimensional shape, and it may be a single-layer configuration, a laminated configuration, or a composite configuration in which multiple substrates of different shapes are combined.

[0073] The substrate may be colored or colorless. The substrate may be opaque, translucent, or transparent. The substrate may have a substantially smooth surface or a structured surface that can be formed by surface treatment such as embossing.

[0074] In one embodiment, the substrate may include a transparent resin layer and a colored resin layer, for example, a transparent polyvinyl chloride resin layer and a colored polyvinyl chloride resin layer. In the laminate of this embodiment, the colored resin layer is supported or protected by the transparent resin layer, thereby providing durability to the decorative properties of the laminate. The laminate of this embodiment can be suitably used, for example, for application as an interior or exterior material for buildings or vehicles.

[0075] The thickness of the substrate can be, for example, approximately 25 micrometers or more, approximately 50 micrometers or more, or approximately 80 micrometers or more, and approximately 5 mm or less, approximately 1 mm or less, or approximately 0.5 mm or less.

[0076] In some embodiments, an extensible substrate can be used as the base material. The tensile elongation rate of the extensible substrate can be approximately 10% or more, approximately 20% or more, or approximately 30% or more, and approximately 400% or less, approximately 350% or less, or approximately 300% or less. The tensile elongation rate of the extensible substrate is calculated as [Chuck spacing at break (mm) - Chuck spacing before elongation (mm) (=100mm)] / Chuck spacing before elongation (mm) (=100mm) × 100 (%) when a sample with a width of 25 mm and a length of 150 mm is prepared and stretched using a tensile testing machine at a temperature of 20°C, a tensile speed of 300 mm / min, and a chuck spacing of 100 mm until the sample breaks.

[0077] In some embodiments, the laminate of this embodiment may optionally have additional layers applied, such as a coloring layer, decorative layer, glossy layer, bonding layer (primer layer), or adhesive layer, between the surface layer and the substrate, or on the substrate surface opposite the surface layer. The additional layers can be used alone or in combination of two or more types, and can be applied to the entire surface or to a portion of the laminate.

[0078] As the adhesive layer, commonly used solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or radiation-curing (e.g., UV-curing) adhesives such as acrylic, polyolefin, polyurethane, polyester, and rubber-based adhesives can be used. The thickness of the adhesive layer can generally be about 5 micrometers or more, about 10 micrometers or more, or about 20 micrometers or more, and can be about 100 micrometers or less, about 80 micrometers or less, or about 50 micrometers or less.

[0079] A release liner may be applied to the surface of the adhesive layer. Examples of release liners include paper; plastic materials such as polyethylene, polypropylene, polyester, and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface that has been treated with silicone or the like to release the adhesive. The thickness of the release liner can generally be about 5 micrometers or more, about 15 micrometers or more, or about 25 micrometers or more, and can be about 500 micrometers or less, about 300 micrometers or less, or about 250 micrometers or less.

[0080] The laminate in this embodiment may be, for example, a single sheet, a roll wound into a roll, or a three-dimensional article.

[0081] The surface layer of the laminate of this disclosure has a matte finish. The matte finish can be evaluated, for example, by the surface gloss when the measurement angle is 60 degrees, i.e., the 60-degree surface gloss. In some embodiments, the surface layer of the laminate of this disclosure can exhibit a 60-degree surface gloss of about 5.0 GU or less, about 4.0 GU or less, about 3.0 GU or less, about 2.0 GU or less, or about 1.0 GU or less. There is no particular limit to the lower limit of the 60-degree surface gloss, but for example, it can be about 0.1 GU or more, about 0.2 GU or more, about 0.3 GU or more, or about 0.4 GU or more. Here, the surface gloss is a value measured using a portable gloss meter GMX-203 (Murakami Color Technology Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan).

[0082] The surface layer of the laminate of this disclosure has scratch resistance and can obtain good results in both needle scratch tests and fingernail scratch tests.

[0083] The needle scratch test is performed using a Clemens-type scratch hardness tester in accordance with JIS K5600-5-4 under the following conditions. The laminates of this disclosure can exhibit a maximum load capacity of 50g or more, 60g or more, or 70g or more, at which no damage is detected on the surface outside the initial area (1mm) when the surface layer of the laminate is scratched and observed from the front to determine whether there is cohesive failure damage outside the initial area. (Test conditions) The test specimen is prepared by attaching the sample to a 0.7 mm thick aluminum plate and fixing it horizontally to the test stand. Working load: 10g to 200g (in 10g increments) Needle: steel needle Needle tip radius: 5 / 100mm Needle tip angle: 90° Scratch angle: 90° relative to the test specimen Movement speed: 10mm / 4 seconds Travel distance: 10mm

[0084] The fingernail scratch test is performed by placing the test sample on an aluminum plate with the surface layer facing upwards, setting the fingernail of the index finger on the test sample at an angle of approximately 90°, and moving the fingernail at a speed of approximately 300 mm / second to scratch the surface layer. No scratches are observed on the surface layer of the laminate of this disclosure in such a test.

[0085] In some embodiments, the laminates of the present disclosure may have antifouling properties. Antifouling properties can be evaluated by a heel mark resistance test in accordance with JIS K3920. Such a test can be performed by attaching test samples with the surface layer side facing up to each face of a hexagonal test drum, placing black rubber inside the drum, and then rotating the drum under conditions equivalent to 10,000 people. In one embodiment of the laminate of the present disclosure, after the test, water is applied to the surface layer of the laminate and wiped with a Kimwipe, and no stains are observed on the surface layer.

[0086] The applications of the laminates of this disclosure are not particularly limited. For example, the laminates of this disclosure can be used for decorative applications, optical applications, etc. For example, the laminates of this disclosure can be used as interior materials such as walls, stairs, ceilings, columns, and partitions of buildings such as office buildings, apartments, and houses, or as exterior materials such as exterior walls, and can be used as interior or exterior materials for various vehicles such as railway cars, ships, airplanes, and automobiles including two-wheeled and four-wheeled vehicles. They can also be used as covering materials for all kinds of articles such as road signs, billboards, furniture, and electrical appliances. Furthermore, the laminates of this disclosure can also be used as light diffusing members used in display devices such as liquid crystal displays and organic EL displays, for example, light diffusing films or light diffusing plates to ensure uniformity of backlight brightness, or anti-glare (AG) films to reduce or prevent reflections of light from fluorescent lamps, etc. [Examples]

[0087] The following examples illustrate specific embodiments of the present disclosure, but the present invention is not limited thereto. All parts and percentages are by mass unless otherwise specified. Numerical values ​​include errors inherent to the measurement principle and measuring device. Numerical values ​​are shown with significant figures after normal rounding.

[0088] Table 1 shows the materials, reagents, etc., used in this example and comparative example.

[0089] [Table 1]

[0090] <Example 1> A transparent polyvinyl chloride (PVC) film substrate was obtained by heat laminating a polyvinyl chloride (PVC) film with a polyethylene terephthalate (PET) film. The composition of the PVC film was PVC / ester-based plasticizer / organic stabilizer (acrylic resin, zinc stearate, etc.) = 72 / 16 / 12 (mass ratio). The PET film was 50 micrometers thick Teijin™ Tetron™ Film G2 (Teijin Film Solutions Limited, Chiyoda-ku, Tokyo, Japan).

[0091] Each material shown in Table 2 was placed in a self-rotating centrifugal stirrer, Thinky AR-250 (Thinky Co., Ltd., Chiyoda-ku, Tokyo, Japan), and mixed for 2.0 minutes to obtain a surface coating composition. The surface coating composition was coated onto a transparent polyvinyl chloride film substrate using a knife coater. Drying and heat curing were performed in an oven at 65°C for 2 minutes and then in an oven at 150°C for 5 minutes to form a surface layer with a dry thickness of approximately 12 micrometers. After peeling the PET film from the transparent polyvinyl chloride film substrate, the transparent polyvinyl chloride film substrate with the surface layer and a black polyvinyl chloride film with a satin surface embossing were heat-laminated to obtain a laminated decorative film. Here, the composition of the black polyvinyl chloride film was polyvinyl chloride / ester-based plasticizer / organic stabilizer, pigment, etc. (acrylic resin, zinc stearate, carbon black, etc.) = 72 / 16 / 12 (mass ratio).

[0092] <Example 2> The decorative film was prepared in the same manner as in Example 1, except that the binder was changed to ETERNACOLL (trademark) ST-053D.

[0093] <Examples 3-7> A decorative film was prepared in the same manner as in Example 1, except that the resin bead content was changed to 30% by mass, 40% by mass, 50% by mass, 60% by mass, and 65% by mass, based on the total weight (solid content) of the surface layer.

[0094] <Examples 8-10> A decorative film was prepared in the same manner as in Example 1, except that the average particle size of the resin beads was changed to 3 micrometers, 10 micrometers, and 15 micrometers.

[0095] <Example 11> A decorative film was prepared in the same manner as in Example 1, except that the glass transition temperature of the resin beads was changed to -25°C.

[0096] <Comparative Examples 1 and 2> The decorative film was prepared in the same manner as in Example 1, except that the binder was changed to ETERNACOLL® UW-3039E and ETERNACOLL® UW-5002E.

[0097] <Comparative Examples 3 and 4> A decorative film was prepared in the same manner as in Example 1, except that the resin bead content was changed to 75% by mass and 80% by mass, based on the total weight (solid content) of the surface layer.

[0098] <Comparative Examples 5-7> A decorative film was prepared in the same manner as in Example 1, except that the glass transition temperatures of the resin beads were changed to 34°C, -34°C, and -30°C.

[0099] <Comparative Examples 8 and 9> A decorative film was prepared in the same manner as in Example 1, except that the average particle size of the resin beads was changed to 22 micrometers and 32 micrometers.

[0100] <Comparative Example 10> The decorative film was prepared in the same manner as in Example 1, except that the materials were changed as shown in Table 4.

[0101] The following evaluations were performed on each sample from Examples 1-11 and Comparative Examples 1-10, and the results are shown in Tables 2-4.

[0102] (Elastic modulus of the surface layer) Using an atomic force microscope (Cypher AFM, Oxford Instruments Ltd.), at room temperature, the image was taken at a size of 10 × 10 square micrometers (μm). 2 Within the specified region, the surface morphology of the surface layer of each test sample was observed. Then, within that region, force curve measurements were performed in a roughly flat area of ​​2 × 2 square micrometers or 1 × 1 square micrometer located between the resin beads, and the elastic modulus of the surface layer was measured. The elastic moduli shown in each table are the average values ​​of measurements taken at any six locations. The measurement conditions were as follows: (Measurement conditions) (A) Probe OMCL-AC240TS (Spring constant (k) = 2N / m, Tip radius: 7nm, Frequency: 58~65kHz, Olympus Corporation) Calibration of spring constant: Thermal noise method (B) Image Target amplitude: 2V Set point: 1.6V Integral gain: 78 Drive amplitude: 100~300mV (C) Force Curve Force distance: 1 micrometer Trigger point: 1V Chip speed: 1.98 micrometers / second

[0103] (Needle scratch test) Each test sample was attached to a 0.7 mm thick aluminum plate to prepare a test specimen. This specimen was then placed in a Clemens-type scratch hardness tester conforming to JIS K5600-5-4, and the test was conducted under the following conditions. After the test, the surface of the test specimen was visually inspected. A specimen was evaluated as "Good" if scratches occurred at a load of 50 g or more, and as "Poor" if scratches occurred at a load of less than 50 g. In each table, the "Good" result also includes the maximum load at which no scratches occurred. Furthermore, scratches were observed at loads of 40 g or less for all evaluated samples that received a "Poor" result. (Test conditions) Working load: 10g to 200g (in 10g increments) Needle: steel needle Needle tip radius: 5 / 100mm Needle tip angle: 90° Scratch angle: 90° relative to the test specimen Movement speed: 10mm / 4 seconds Travel distance: 10mm

[0104] (Nail scratch test) Each test sample was placed on an aluminum plate with the surface layer facing upwards. The fingernail of the index finger was positioned on the test sample at an angle of approximately 90°, and the test was performed by moving the fingernail at a speed of approximately 300 mm / second to scratch the surface layer. After the test, the surface of the test sample was visually inspected, and it was evaluated as "good" if no changes in appearance such as scratches had occurred, and as "poor" if changes in appearance had occurred.

[0105] (60-degree surface gloss) The surface gloss of each test sample was measured at a 60° angle using a portable gloss meter GMX-203 (Murakami Color Technology Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan).

[0106] [Table 2]

[0107] [Table 3]

[0108] [Table 4]

[0109] <Example 12> A decorative film was prepared in the same manner as in Example 1, except that the composition of the surface coating composition in Example 1 was changed to the composition shown in Table 5. In this case, the surface coating composition in Example 11 further contains Takenate® WB-3936 (water-based blocked isocyanate), BYK®-SILCLEAN 3720 (polyether-modified polydimethylsiloxane with hydroxyl groups), Tinuvin 292 (light stabilizer), Tinuvin 1130 (ultraviolet absorber), and ACRYSOL® RM-8W (nonionic urethane rheology modifier) ​​compared to the surface coating composition in Example 1.

[0110] <Examples 13-18> A decorative film was prepared in the same manner as in Example 1, except that the composition was modified so that the mass ratio of Takenate® WB-3936 to the binder precursor (ETERNACOLL® UW-1005E) was 30%, 40%, 60%, 90%, 150%, and 200% in terms of solid content, and the amount of BYK®-SILCLEAN 3720 was 1.2 parts by mass, 1.3 parts by mass, 1.5 parts by mass, 1.6 parts by mass, and 1.7 parts by mass, based on 100 parts by mass of solid content of the surface coating composition.

[0111] <Examples 19, 20> A decorative film was prepared in the same manner as in Example 1, except that the composition was modified so that the amount of BYK(trademark)-SILCLEAN 3720 added was 0.5 parts by mass and 1.0 part by mass, based on 100 parts by mass of solid content in the surface coating composition.

[0112] <Reference Comparison Example 1> A decorative film was prepared in the same manner as in Example 1, except that Takenate (trademark) WB-3936 (aqueous blocked isocyanate) was not used and the composition was changed to that shown in Table 6. Here, in this disclosure, "reference comparative example" refers to an example that corresponds to an example in terms of matte finish and scratch resistance, but corresponds to a comparative example in terms of the additional effect of antifouling.

[0113] <Reference Comparison Example 2> A decorative film was prepared in the same manner as in Example 1, except that BYK(trademark)-SILCLEAN 3720 (polyether-modified polydimethylsiloxane with hydroxyl groups) was not used and the composition was changed to that shown in Table 6.

[0114] <Reference Comparison Example 3> The decorative film from Example 1, which does not use Takenate® WB-3936 and BYK®-SILCLEAN 3720, was adopted as the decorative film for Reference Comparative Example 3.

[0115] <Comparative Example 11> A decorative film was prepared in the same manner as in Example 1, except that the composition was modified so that the mass ratio of Takenate® WB-3936 to the binder precursor (ETERNACOLL® UW-1005E) was 400% in terms of solid content, and the amount of BYK®-SILCLEAN 3720 added was 0.9 parts by mass based on 100 parts by mass of solid content of the surface coating composition.

[0116] The above evaluation tests were conducted on each sample from Examples 12-20, Reference Comparative Examples 1-3, and Comparative Example 11. In addition, the following heel mark resistance test for stain resistance was performed, and the results are shown in Tables 5 and 6.

[0117] (Heel mark resistance test) In accordance with JIS K3920, test samples were attached to each side of a hexagonal test drum with the surface layer facing upwards. After placing black rubber inside the drum, the drum was rotated to simulate conditions equivalent to 10,000 people. After the test, water was applied to the surface layer of the test samples and wiped with Kimwipes. The surface was then visually inspected, and evaluated as "good" if the dirt was not noticeable, and "poor" if the dirt was clearly noticeable. In Reference Comparative Example 1, despite containing the antifouling component BYK(trademark)-SILCLEAN 3720 (polyether-modified polydimethylsiloxane with hydroxyl groups), the result in this test was "poor." This is thought to be because the hydroxyl groups contained in this component were not consumed. Regarding antifouling properties, if the level of antifouling properties required under such harsh conditions as in this test is not necessary, the decorative film in Reference Comparative Example 1 may have sufficient antifouling properties.

[0118] [Table 5]

[0119] [Table 6]

[0120] It will be apparent to those skilled in the art that the above embodiments and examples can be modified in various ways without departing from the basic principles of the present invention. Furthermore, it will be apparent to those skilled in the art that various improvements and modifications of the present invention can be implemented without departing from the spirit and scope of the invention. Some embodiments of this disclosure are described in the following sections [1]-

[15] . [Item 1] Substrate, and, A surface layer having scratch resistance and a matte finish, comprising resin beads having an average particle size of 1 micrometer or more and 20 micrometers or less, and a glass transition temperature greater than -30°C and less than 34°C, and a binder, wherein the surface layer contains less than 75% by mass of the resin beads based on the total weight of the surface layer, and when the elastic modulus of the surface layer is measured with an atomic force microscope, the region of the surface layer other than the resin beads exhibits an elastic modulus of 65 MPa or less. A laminate containing the above. [Item 2] The aforementioned surface layer is a laminate according to item 1, having a surface gloss of 60 degrees of 5.0 GU or less. [Item 3] The laminate according to item 1 or 2, wherein the binder comprises a resin having urethane bonds. [Item 4] The laminate according to any one of items 1 to 3, wherein the binder comprises a resin having a carboxyl group. [Item 5] The laminate according to any one of items 1 to 4, wherein the binder comprises a crosslinked product obtained by crosslinking a crosslinkable composition. [Item 6] The laminate according to any one of items 1 to 5, wherein the surface layer further comprises an antifouling agent. [Item 7] The laminate according to item 6, wherein the antifouling agent comprises a silicone resin having urethane bonds. [Item 8] A laminate as described in any one of items 1 to 7, used as interior or exterior material for buildings or vehicles. [Item 9] A surface coating composition comprising resin beads having an average particle size of 1 micrometer or more and 20 micrometers or less, and a glass transition temperature greater than -30°C and less than 34°C, and a binder precursor, A surface coating composition comprising less than 75 parts by mass of the resin beads based on 100 parts by mass of the solid content of the surface coating composition, wherein the surface layer formed by the surface coating composition exhibits an elastic modulus of 65 MPa or less in the region of the surface layer other than the resin beads when the elastic modulus of the surface layer is measured with an atomic force microscope. [Item 10] The surface coating composition according to item 9, wherein the binder precursor comprises a resin having urethane bonds. [Item 11] A surface coating composition according to item 9 or 10, further comprising an antifouling agent. [Item 12] A surface coating composition according to any one of items 9 to 11, which is an aqueous composition. [Item 13] The surface coating composition according to item 12, wherein the binder precursor comprises a resin having a carboxyl group. [Item 14] A surface coating composition according to item 12 or 13, comprising an aqueous isocyanate and a polyether-modified silicone having hydroxyl groups as the antifouling agent. [Item 15] The surface coating composition according to item 14, wherein the mass ratio of the aqueous isocyanate to the binder precursor is 30% or more and less than 400% in terms of solid content, and the surface coating composition contains 0.5 parts by mass or more of the polyether-modified silicone having hydroxyl groups, based on 100 parts by mass of solid content of the surface coating composition.

Claims

1. Substrate, and, A surface layer having scratch resistance and matte finish, comprising resin beads having an average particle size of 1 micrometer or more and 20 micrometers or less, and a glass transition temperature greater than -30°C and less than 34°C, and a binder, wherein the surface layer contains 20% by mass or more and less than 75% by mass of the resin beads based on the total weight of the surface layer, the resin beads contain a resin having urethane bonds, the binder contains a resin having urethane bonds, and when the elastic modulus of the surface layer is measured with an atomic force microscope, the region of the surface layer other than the resin beads exhibits an elastic modulus of 65 MPa or less. A laminate containing the above.

2. The laminate according to claim 1, wherein the surface layer has a surface gloss of 60 degrees of 5.0 GU or less.

3. The laminate according to claim 1 or 2, wherein the binder comprises a resin having a carboxyl group.

4. The laminate according to any one of claims 1 to 3, wherein the binder comprises a crosslinked product obtained by crosslinking a crosslinkable composition.

5. The laminate according to any one of claims 1 to 4, wherein the surface layer further comprises an antifouling agent.

6. The laminate according to claim 5, wherein the antifouling agent comprises a silicone resin having urethane bonds.

7. A laminate according to any one of claims 1 to 6, used as an interior or exterior material for a building or vehicle.

8. A surface coating composition comprising resin beads having an average particle size of 1 micrometer or more and 20 micrometers or less, and a glass transition temperature greater than -30°C and less than 34°C, and a binder precursor, A surface coating composition comprising 20 parts by mass or more and less than 75 parts by mass of the resin beads, based on 100 parts by mass of the solid content of the surface coating composition, wherein the resin beads contain a resin having urethane bonds, the binder precursor contains a resin having urethane bonds, and the surface layer formed by the surface coating composition exhibits an elastic modulus of 65 MPa or less in the region of the surface layer other than the resin beads when the elastic modulus of the surface layer is measured with an atomic force microscope.

9. The surface coating composition according to claim 8, further comprising an antifouling agent.

10. The surface coating composition according to claim 8 or 9, which is an aqueous composition.

11. The surface coating composition according to claim 10, wherein the binder precursor comprises a resin having a carboxyl group.

12. The surface coating composition according to claim 10 or 11, comprising an aqueous isocyanate and a polyether-modified silicone having hydroxyl groups as an antifouling agent.

13. The surface coating composition according to claim 12, wherein the mass ratio of the aqueous isocyanate to the binder precursor is 30% or more and less than 400% in terms of solid content, and the surface coating composition contains 0.5 parts by mass or more of the polyether-modified silicone having hydroxyl groups, based on 100 parts by mass of solid content of the surface coating composition.

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