JP2023074354A - Decorative laminate comprising metallic layer and adhesive layer - Google Patents

Abstract

To provide a decorative laminate comprising a metallic layer and an adhesive layer, which is excellent in metallic luster and can reduce or prevent appearance failures.SOLUTION: A decorative laminate according to one embodiment of the present invention comprises an adhesive layer, and a metallic layer comprising metallic pigment particles in the state order. An outermost surface of the metallic layer, which is opposite the adhesive layer, has clarity of about 0.5 or more.SELECTED DRAWING: Figure 1

Description

FIELD OF THE DISCLOSURE The present disclosure relates to decorative laminates that include a metallic layer and an adhesive layer.

In recent years, for example, decorative sheets exhibiting a metallic design have been developed and used in a wide range of fields such as interior and exterior products.

Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-100051) describes a decorative sheet obtained by laminating at least a concealing layer, a metallic layer and a surface protective layer in this order on a base material, wherein a bright pigment contained in the metallic layer is in the range of 15 to 45 parts by mass with respect to 100 parts by mass of the resin solid content of the metallic layer, and the surface protective layer is formed by cross-linking and curing an ionizing radiation-curable resin composition, and the ionizing A decorative sheet having a radiation-curable resin composition applied in an amount of 3 to 8 g/m ² is described.

Patent Document 2 (Japanese Patent Application Laid-Open No. 05-111991) describes a decorative sheet in which an acrylate emulsion layer containing aluminum particles having a scaly surface and a smooth surface is provided on a base layer. .

JP 2010-100051 A JP-A-05-111991

The decorative sheets described in Patent Documents 1 and 2 form a metallic layer using metallic pigment particles such as aluminum particles. A conventional metallic layer formed on such a decorative sheet typically exhibits a sparkling design like lame, and has a metallic luster that the metal itself can exhibit (for example, a luster like metal plating). ) was not expressed.

With respect to metallic luster, for example, by forming a vapor-deposited metal layer on a base material, metallic luster that the metal itself can exhibit can be expressed. However, compared with a metallic layer formed using a bright pigment, the metal vapor deposition layer tends to crack when stretched or bent, and the metallic gloss tends to decrease, which may cause poor appearance.

For example, in the field of decorative films, there is known a technique of bonding a decorative film to an adherend via an adhesive layer. However, it has been difficult to apply a metallic layer containing metallic pigment particles to such an adhesive layer to develop the metallic luster that the metal itself can exhibit.

The present disclosure provides a decorative laminate including a metallic layer and an adhesive layer that has excellent metallic luster and can reduce or prevent poor appearance.

According to one embodiment of the present disclosure, an adhesive layer and a metallic layer containing metal pigment particles are sequentially included, and the outermost surface located on the opposite side to the adhesive layer side surface of the metallic layer has a sharpness , is about 0.5 or greater.

According to another embodiment of the present disclosure, a metallic coating composition comprising metallic pigment particles is applied to a substrate having a substantially smooth surface to form a metallic layer, and an adhesive layer is applied to the metallic layer. A method of making a decorative laminate is provided, comprising: applying

According to another embodiment of the present disclosure, an article is provided wherein the decorative laminate described above is adhered to a support member.

According to another embodiment of the present disclosure, there is provided a method of making an article having a three-dimensional shape comprising applying the decorative laminate described above to a support member having a three-dimensional shape.

According to another embodiment of the present disclosure, a metallic coating composition comprising metallic pigment particles, a binder precursor and a silane coupling agent, wherein the metallic pigment particle content is about 20.0 on a solids basis. % by mass or more and about 40.0% by mass or less, the content of the binder precursor is about 0.1% by mass or more and about 10.0% by mass or less, and the content of the silane coupling agent is about A metallic coating composition is provided that is greater than or equal to 50.0 weight percent and less than or equal to about 79.9 weight percent.

According to the present disclosure, it is possible to provide a decorative laminate including a metallic layer and an adhesive layer that has excellent metallic luster and can reduce or prevent poor appearance.

The above description should not be considered to disclose all embodiments of the invention or all advantages associated with the invention.

FIG. 1 is a schematic cross-sectional view of a decorative laminate according to one embodiment of the present disclosure. FIG. 2 is a diagram of a method for manufacturing a decorative laminate according to one embodiment of the present disclosure. FIG. 3 is a diagram of a method for manufacturing a decorative laminate according to another embodiment of the present disclosure; FIG. 4 is an exterior photograph of an article comprising a decorative laminate according to one embodiment of the present disclosure.

Hereinafter, for the purpose of illustrating representative embodiments of the present invention, the present invention will be described in more detail with reference to the drawings as necessary, but the present invention is not limited to these embodiments. With respect to drawing reference numbers, like-numbered elements in different drawings indicate similar or corresponding elements.

In the present disclosure, for example, "in order" in "a decorative laminate sequentially including an adhesive layer and a metallic layer containing metal pigment particles" means that when focusing on two components, the adhesive layer and the metallic layer, , the decorative laminate is intended to include these components in that order, with other layers, such as printed layers, interposed between the components.

In the present disclosure, for example, “upper” in “a metallic layer is arranged on an adhesive layer” means that the metallic layer is arranged directly above the adhesive layer, or that the metallic layer is arranged on another adhesive layer. is intended to be placed indirectly on the upper side of the substrate via a layer of

In the present disclosure, for example, “below” in “the bonding layer is disposed under the metallic layer” means that the bonding layer is disposed directly under the metallic layer, or that the bonding layer is disposed under another It is intended to be placed indirectly through the layer below the metallic layer.

In the present disclosure, “metallic pigment particles” mean particles capable of imparting a metallic design to the metallic layer. Here, the “metallic design” is not a glittering design like lame or a flip-flop design in which the hue changes depending on the viewing angle, but a metallic luster that the metal itself can exhibit ( For example, it is intended for designability such as specular gloss like metal plating).

In the present disclosure, the term “metallic layer” means a layer capable of exhibiting a metallic design (for example, specular gloss like metal plating).

In the present disclosure, "substantially" means including variations caused by manufacturing errors, etc., and is intended to allow for variations of about ±20%.

In the present 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 about 80% or more, preferably about 85% or more, or about It may be 90% or more. Although the upper limit of the average transmittance is not particularly limited, it can be, for example, less than about 100%, about 99% or less, or about 98% or less.

In the present disclosure, “translucent” means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured according to JIS K 7375 is less than about 80%, preferably about 75% or less. and is intended not to completely hide the substrate.

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

In the present disclosure, the “film” also includes a member called a “sheet”.

Hereinafter, the decorative laminate of the present disclosure will be described with reference to the drawings as necessary.

Decorative laminate 100 in FIG. 1 includes release liner 101 , adhesive layer 103 and metallic layer 105 . Here, the release liner is an optional component, and the decorative laminates of the present disclosure may or may not include a release liner.

In the following, for the purpose of illustrating representative embodiments of the present disclosure, details of each component will be described with some reference numerals omitted.

The decorative laminate of the present disclosure (sometimes simply referred to as "laminate") includes an adhesive layer and a metallic layer containing metal pigment particles in this order, and the adhesive layer side of the metallic layer The sharpness of the outermost surface located on the opposite side of the is about 0.5 or more. Here, "the outermost surface of the metallic layer opposite to the surface facing the adhesive layer" means, for example, in FIG. The surface of the metallic layer 105 when folded is intended.

When applying the metallic layer to the adhesive layer, for example, the adhesive is applied to the release liner to form the adhesive layer, and then the metallic coating composition is applied to the adhesive layer. is common. However, when the metallic coating composition is applied to the adhesive layer by such a method, streaky defects occur in the metallic layer or the haze of the metallic layer increases, resulting in a metallic layer exhibiting good metallic luster. I didn't. Although the principle is not clear, the reason for this is that the adhesive layer is more flexible than the base material (e.g., PET base material) used in the release liner and the like, so the Mayer used when applying the coating composition It is easily affected by the bar, resulting in streaks, or the solvent in the coating composition causes the adhesive layer to swell or the adhesive component to migrate to the metallic layer, resulting in a metallic coating. It is thought that the haze of the layer has increased.

As will be described later, the present inventors apply a metallic coating composition containing metallic pigment particles to a support having a substantially smooth surface to form a metallic layer, and then apply an adhesive layer to the metallic layer. When applied, it was found that a metallic layer exhibiting good metallic luster (specular luster like metal plating) as shown in the photograph of FIG. 4 can be obtained.

In addition, since the metallic layer of the present disclosure is formed using metal pigment particles, it is possible to reduce or prevent appearance defects due to cracks compared to a metal vapor deposition layer formed by vapor deposition.

The metallic luster of the metallic layer can be evaluated, for example, by the definition test described later. Since this definition is a parameter that reflects the metallic luster of the metallic layer, for example, as shown in FIG. Even when a transparent surface layer is applied on the metallic layer 105, the metallic luster of the metallic layer can be evaluated by measuring the definition of the outermost surface of the decorative laminate. Decorative laminates of the present disclosure can achieve a definition of about 0.5 or greater, about 0.6 or greater, or about 0.7 or greater. The upper limit of the sharpness is not particularly limited, and can be, for example, about 2.0 or less, about 1.8 or less, or about 1.5 or less.

The metallic layer of the present disclosure contains at least metallic pigment particles. The metallic layer may have a single layer structure or a multilayer structure. The metallic layer may be formed over the entire surface of the decorative laminate, or may be formed partially.

The shape of the metal pigment particles is not particularly limited, and examples thereof include scale-like, flat-like, and plate-like shapes. Among them, the scaly shape is preferable from the viewpoint of obtaining good metallic luster.

The size of the metallic pigment particles is not particularly limited as long as the metallic layer can exhibit a metallic design. The particle size of the metal pigment particles can be evaluated by D50, for example. D50 is preferably about 1 micrometer or more, about 2 micrometers or more, about 3 micrometers or more, about 4 micrometers or more, or about 5 micrometers or more from the viewpoint of obtaining good metallic luster, Preferably, it is no greater than about 20 microns, no greater than about 17 microns, no greater than about 15 microns, no greater than about 12 microns, or no greater than about 10 microns. The particle diameter (D50) of the metal pigment particles is measured using a laser diffraction scattering particle size distribution analyzer "Microtrac MT3300EX II Series" manufactured by Microtrac Bell under measurement conditions in accordance with JIS Z 8825:2013. can be measured.

The material of the metal pigment particles is not particularly limited, and examples include metals such as aluminum, chromium, nickel, tin, titanium, indium, copper, gold, silver, and brass, and alloys or compounds containing such metals. can. Above all, from the viewpoint of metallic luster, the metallic pigment particles preferably contain aluminum. The metallic pigment particles blended in the metallic layer and the metallic coating composition can be used singly or in combination of two or more.

The metallic layer may be composed only of metal pigment particles, but may contain optional components such as a binder, which will be described later. When optional components (especially binder and silane coupling agent) are included, the content of the metal pigment particles is, for example, about 20.0% by mass or more, about 22.0% by mass or more, based on the total weight of the metallic layer. , about 25.0% or more, about 27.0% or more, or about 30.0% or more, and about 40.0% or less, about 38.0% or less, or about 35% 0% by mass or less. When the content of the metallic pigment particles is within such a range, a metallic layer having excellent performance such as metallic luster can be obtained.

In some embodiments, metallic layers of the present disclosure include a binder. The binder is not particularly limited, and examples thereof include resins having urethane bonds, phenoxy resins, (meth)acrylic resins, epoxy resins, phenol resins, polyvinyl alcohol, and vinyl acetate resins. A binder can be used individually or in combination of 2 or more types. In the present disclosure, the term "resin having a urethane bond" includes not only urethane resins but also resins prepared using at least one selected from urethane (meth)acrylates and urethane (meth)acrylate oligomers. Urethane resins can also include (meth)acrylic urethane resins. Among them, resins having urethane bonds and phenoxy resins are preferable from the viewpoint of metallic luster, adhesion between metal pigment particles, and the like.

The content of the binder is, for example, about 0.1% by mass or more, about 0.3% by mass or more, about 0.6% by mass or more, about 0.8% by mass or more, about 1.0 wt% or more, about 1.5 wt% or more, about 2.0 wt% or more, about 2.5 wt% or more, or about 3.0 wt% or more, and about 10.0 wt% % or less, about 9.0 wt.% or less, about 8.0 wt.% or less, about 7.0 wt.% or less, about 6.0 wt.% or less, or about 5.5 wt.% or less. While the binder can improve the adhesion between the metal pigment particles, for example, it may increase the haze of the metallic layer in some cases. When the content of the binder is within such a range, a metallic layer having excellent performance such as metallic luster can be obtained.

In some embodiments, metallic layers of the present disclosure include silane coupling agents. The silane coupling agent is not particularly limited as long as it is a compound having an alkoxysilane at the end, and is selected from the group consisting of a vinyl group, an epoxy group, a (meth)acrylic group, an amine group, a mercapto group, and an isocyanate group. more preferably at least one selected from the group consisting of an epoxy group, an amine group, and an isocyanate group, and at least one selected from the group consisting of an epoxy group and an amine group. It is particularly preferred to have A silane coupling agent can be used individually or in combination of 2 or more types.

Silane coupling agents having a vinyl group include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane.

Silane coupling agents having epoxy groups include, for example, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-glycidoxypropyltri Mention may be made of methoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropyltriethoxysilane.

Silane coupling agents having a (meth)acryl group include, for example, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, Mention may be made of ethoxysilane and γ-(meth)acryloxypropyltriethoxysilane. Here, "(meth)acryloxy" means acryloxy or methacryloxy.

Silane coupling agents having an amine group include, for example, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) Mention may be made of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane.

Silane coupling agents having a mercapto group include, for example, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

Silane coupling agents having an isocyanate group include, for example, γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane.

The content of the silane coupling agent is, for example, about 50.0% by mass or more, about 55.0% by mass or more, about 60.0% by mass or more, about 63.0% by mass, based on the total weight of the metallic layer. or more, or about 65.0 wt% or more, about 79.9 wt% or less, about 79.7 wt% or less, about 79.4 wt% or less, about 79.2 wt% or less, about 79 wt% 0 wt% or less, about 78.5 wt% or less, about 78.0 wt% or less, about 77.5 wt% or less, or about 77.0 wt% or less. A silane coupling agent can improve adhesion between metal pigment particles, for example. When the content of the silane coupling agent is within such a range, a metallic layer having excellent performance such as metallic luster can be obtained. When the silane coupling agent is used in combination with the binder described above, the binder and the silane coupling agent can be bonded together, and at the same time, the metal pigment particles and the silane coupling agent can also be bonded, thereby further improving the adhesion between the metal pigment particles. can be made As a result, even if the decorative laminate is applied to a molding method that is subjected to heat and/or pressure, such as vacuum molding or vacuum pressure molding, the loss of metallic luster of the metallic layer can be reduced or prevented. can be done. When the silane coupling agent and the binder are used in combination, the contents described above can be adopted for each content.

The metallic layer of the present disclosure includes optional components such as fillers other than metal pigment particles, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, leveling agents, and other than metal pigment particles. Additives such as pigments, dyes, and fragrances may also be included. An arbitrary component can be used individually or in combination of 2 or more types. The individual and total blending amounts of optional components can be determined within a range that does not impair the properties required for the metallic layer.

The metallic coating composition of the present disclosure for forming a metallic layer can contain various materials that can be used in the metallic layer described above, and contains at least metallic pigment particles. Among them, in addition to metal pigment particles, it contains a binder precursor and a silane coupling agent, and the content of the metal pigment particles is about 20.0% by mass or more and about 40.0% by mass or less in terms of solid content. and the content of the binder precursor is about 0.1% by mass or more and about 10.0% by mass or less, and the content of the silane coupling agent is about 50.0% by mass or more and about 79.9% by mass Preferred are metallic coating compositions that are: Since the metallic layer formed from such a composition has excellent metallic luster and excellent adhesion between metal pigment particles, it can be applied by a molding method in which heat and/or pressure is applied (e.g., a vacuum molding method, a vacuum pressure molding method, etc.). ), the decrease in metallic luster of the metallic layer can be reduced or suppressed.

Here, the "binder precursor" means a component that finally becomes a binder in the metallic layer, such as a curable or crosslinkable monomer and/or a curable or crosslinkable oligomer, or Non-curable or non-crosslinkable resins such as crosslinked resins and thermoplastic resins can be mentioned. Therefore, the metallic coating composition can optionally contain additives such as a cross-linking agent and a curing agent. A metallic coating composition that includes a crosslinker can be referred to as a crosslinkable composition, and a metallic coating composition that includes a curing agent can be referred to as a curable composition.

The content of each of the metallic pigment particles, the binder precursor, and the silane coupling agent in the metallic coating composition can similarly employ the content of each component in the metallic layer described above. Here, "based on the total weight of the metallic layer" and "binder" can be read as "in terms of solid content" and "binder precursor".

The various optional additives described above can be appropriately blended within a range that does not adversely affect the metallic layer obtained from the metallic coating composition. The metallic coating composition may optionally contain an organic solvent such as toluene or an aqueous dispersion medium in order to improve workability and coatability. As the aqueous dispersion medium, water such as distilled water, purified water, ion-exchanged water, and tap water can be used. A water-soluble alcohol such as ethanol may be used in combination with such water as long as the effect of the present invention is not affected.

The metallic layer of the decorative laminate of the present disclosure is not formed by applying a metallic coating composition to an adhesive layer, but is a support having a substantially smooth surface (sometimes simply referred to as a "support"). ) is formed by applying Here, the "substantially smooth surface support" does not include a support having an adhesive layer to which the metallic coating composition can be applied.

The metallic coating composition contains metallic pigment particles (for example, scale-like metallic pigment particles), and such particles are oriented substantially uniformly in a direction substantially parallel to the support, resulting in a good metallic layer. A metallic luster can be obtained. According to the manufacturing method of the decorative laminate of the present disclosure, the metal pigment particles are more likely to be oriented substantially uniformly when the thickness of the metallic layer is thin. Therefore, from the viewpoint of obtaining good metallic luster, the thickness of the metallic layer is, for example, about 0.07 micrometers or more, about 0.10 micrometers or more, about 0.15 micrometers or more, about 0.20 micrometers or more. , about 0.25 micrometers or more, about 0.30 micrometers or more, about 0.35 micrometers or more, about 0.40 micrometers or more, about 0.45 micrometers or more, or about 0.50 micrometers or more preferably no greater than about 1.1 micrometers, no greater than about 1.0 micrometers, no greater than about 0.90 micrometers, no greater than about 0.85 micrometers, or no greater than about 0.80 micrometers . Here, the thickness of the metallic layer in the present disclosure is JIS K 5600-1-7 Section 7: Measurement of film thickness, 5 dry film thickness, 5.2.1 b) Painting method (nondestructive test method) Measured according to Specifically, first measure the thickness of the substrate before applying the metallic layer, then measure the entire thickness of the same measurement range after applying and drying the metallic layer, and the difference is the thickness of the metallic layer. bottom. This thickness is the average value of the values measured at any three points using a micrometer (model number: VL-50S) manufactured by Mitutoyo Corporation.

Decorative laminates of the present disclosure include an adhesive layer. The adhesive layer is typically a layer applied to an adherend, such as a support member of an article described below.

The adhesive layer may be applied directly to the metallic layer, or indirectly via another layer (eg, a bonding layer).

The material for the adhesive layer is not particularly limited, and examples include commonly used (meth)acrylic, polyolefin, polyurethane, polyester, rubber, and other solvents, emulsion types, pressure sensitive types, and heat sensitive types. , heat-curable or UV-curable adhesives can be used.

Among such materials, pressure-sensitive adhesives and heat-sensitive adhesives are preferable from the viewpoint of ease of bonding to adherends. A heat-sensitive adhesive is more preferable from the viewpoint of availability. For the purposes of this disclosure, a "pressure sensitive adhesive" is an adhesive that is permanently tacky at room temperature (e.g., about 20°C), adheres to a variety of surfaces with light pressure, and does not exhibit a phase change (liquid to solid). refers to the drug. A "heat-sensitive adhesive" is an adhesive that can develop adhesiveness (tackiness) by heating. The heat-sensitive adhesive layer in the present disclosure does not exhibit adhesiveness at room temperature (e.g., about 20°C), and exhibits adhesiveness during molding at, for example, about 100°C or higher, about 120°C or higher, or about 140°C or higher. can demonstrate. Pressure sensitive and heat sensitive adhesives may also be thermally crosslinked or radiation (eg, electron beam or ultraviolet) crosslinked by means of a crosslinking agent.

Materials for the pressure-sensitive adhesive are not particularly limited, and examples include (meth)acrylic polymers, natural rubbers, synthetic rubbers, polyester polymers, polyether polymers, polyurethane polymers, silicone polymers, and other polymers. can be used. Among them, (meth)acrylic polymer pressure-sensitive adhesives are preferable because they are excellent in transparency, weather resistance and adhesiveness.

There are no particular restrictions on the material of the heat-sensitive adhesive. For example, the following component: (A) a glass transition temperature (Tg) of about 25° C. or less, in which the ratio of repeating units containing a carboxyl group to the total number of repeating units in the polymer is about 4.0 to about 25%; and (B) about 75 ° C. or higher, wherein the ratio of the number of repeating units containing an amino group to the total number of repeating units of the polymer is about 3.5 to about 15%. containing an amino group-containing (meth)acrylic polymer having a glass transition temperature (Tg) of about 62: about 38 to about 75: about 25 in mass ratio of component (A) and component (B); Materials can be mentioned. Here, the (meth)acrylic polymer may be a copolymer optionally combined with other non-(meth)acrylate monomers other than (meth)acrylic monomers, such as vinyl unsaturated monomers.

Monoethylenically ^unsaturated monomers that make up (meth)acrylic polymers generally have the formula _CH2 = ^CR1COOR2 , where ^R1 is hydrogen or a methyl group, and ^R2 is a linear, branched or cyclic Alkyl groups, phenyl groups, alkoxyalkyl groups, and phenoxyalkyl groups) are used as main components, but other aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, and vinyl acetate vinyl esters such as Such monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, n -hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, decyl ( Alkyl (meth)acrylates such as meth)acrylate and dodecyl (meth)acrylate; Phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; Alkoxy such as methoxypropyl (meth)acrylate and 2-methoxybutyl (meth)acrylate Alkyl (meth)acrylate etc. can be mentioned. For example, in order to obtain the desired glass transition temperature, adhesiveness, hot adhesiveness and hot holding power, one or more of these monomers can be appropriately used depending on the purpose. The monoethylenically unsaturated monomer is preferably a (meth)acrylic acid alkyl ester, wherein the alkyl group preferably has 1 to 12 carbon atoms.

Component (A) is a (meth)acrylic polymer having a glass transition temperature (Tg) of about 25° C. or less and is a soft component. The soft component (A) itself is sticky at room temperature, but the composition mixed with the component (B) in the above amount exhibits almost no stickiness at room temperature. However, the adhesive obtained by mixing the component (A) and the component (B) in the above amounts can exhibit good adhesiveness when heat-pressed to an adherend.

A (meth)acrylic polymer having a glass transition temperature (Tg) of about 25° C. or less can be easily provided by using as a main component a monomer whose homopolymer has a glass transition temperature (Tg) of about 25° C. or less. Such monomers can include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isoamyl acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and dodecyl (meth)acrylate. can. Considering the adhesiveness at room temperature and the cohesive force at high temperature, the Tg of the (meth)acrylic polymer is preferably about 0°C to about -50°C.

Here, the glass transition temperature (°C) of the polymer in the present disclosure is a value obtained by measuring as follows:
<Measurement of Tg (glass transition temperature) (less than 30°C)>
Rheometric Scientific, using ARES, Mode: Shear, Frequency: 1.0 Hz, Temperature: -60 ° C. to 30 ° C. (5.0 ° C./min), loss tangent (tan δ) (loss elastic modulus G''/ The peak temperature of the storage modulus G') was measured.
<Measurement of Tg (glass transition temperature) (30°C or higher)>
Using RSA-III manufactured by Rheometric Scientific, Mode: Tension, Frequency: 10.0 Hz, Temperature: 30° C. to 150° C. (loss tangent (tan δ) at (5.0° C./min) (loss elastic modulus E′ '/storage modulus E') peak temperature was measured.

Component (A) is a (meth)acrylic polymer containing carboxyl groups. Since component (A) contains a carboxyl group and component (B) contains an amino group, the compatibility between component (A) and component (B) is improved, and component (A ) and component (B) can be avoided, and good performance (for example, heat adhesion, hot adhesion, hot holding power) can be exhibited. From the viewpoint of developing good compatibility, the carboxyl group contained in the (meth)acrylic polymer of component (A) is such that the ratio of the number of repeating units containing a carboxyl group to the total number of repeating units of the polymer is about 4.5. It is preferably contained in an amount of 0 to about 25% (also expressed as carboxyl group amount mol%).

A (meth)acrylic polymer can be made to contain a carboxyl group by copolymerizing an unsaturated monomer containing a carboxyl group with the monoethylenically unsaturated monomer. Examples of such monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxypolycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, β-carboxyethyl (meth)acrylate. , 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid and the like. The unsaturated monomer containing a carboxyl group is preferably (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, or β-carboxyethyl (meth)acrylate in consideration of yellowing resistance.

The molecular weight of the carboxyl group-containing (meth)acrylic polymer of component (A) is not particularly limited, but in general, the weight average molecular weight is preferably from about 100,000 to about 1,000,000, more preferably from about 200,000 to about 800,000. . If the weight-average molecular weight is small, the cohesiveness tends to decrease, and if the weight-average molecular weight is large, the compatibility tends to decrease. Here, the "weight average molecular weight" in the present disclosure intends the weight average molecular weight in terms of polystyrene in gel permeation chromatography measurement.

Component (B) is a (meth)acrylic polymer having a glass transition temperature (Tg) of about 75° C. or higher and is the hard component. If the hard component (B) is not included or is small, the adhesive becomes a pressure-sensitive adhesive at room temperature with component (A) alone. By including component (B) having a glass transition temperature (Tg) of about 75° C. or higher, the adhesive develops tackiness during heat bonding. As a result, for example, even if a decorative laminate stretched and attached to a three-dimensional adherend is exposed to high temperatures and stretches due to residual stress, the adhesive layer can withstand the stretching force. Therefore, it is possible to prevent slippage or peeling of the decorative laminate from the edge. Preferably, component (B) has a glass transition temperature (Tg) of about 75°C or higher. The upper limit of the Tg of component (B) is preferably about 250° C. or less from the viewpoints of, for example, the balance between high-temperature adhesive strength and room-temperature adhesive strength, and the application temperature during thermocompression bonding. More preferably, the Tg of component (B) ranges from about 80°C to about 120°C.

A (meth)acrylic polymer having a glass transition temperature (Tg) of about 75° C. or higher can be easily provided by using a monomer whose homopolymer has a Tg of about 75° C. or higher as a main component. Examples of such monomers include methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like.

Component (B) is a (meth)acrylic polymer containing amino groups. When component (A) contains a carboxyl group and component (B) contains an amino group, the compatibility between component (A) and component (B) is improved. As a result of being able to avoid the phase separation of the component (A) and the component (B) in the adhesive composition, it is possible to exhibit good performance (for example, heat adhesiveness, hot adhesiveness, hot holding power). From the viewpoint of developing good compatibility, the amino group contained in the (meth)acrylic polymer of component (B) should be such that the ratio of the number of repeating units containing amino groups to the total number of repeating units of the polymer is about 3. It is preferably contained in an amount of 5 to about 15% (also expressed as amino group amount mol%).

Specific examples of unsaturated monomers containing amino groups, which are copolymerized with the monoethylenically unsaturated monomers to form amino group-containing (meth)acrylic polymers, include N,N-dimethylaminoethyl acrylate (DMAEA ), dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl methacrylate (DM), N,N-dimethylaminopropylacrylamide (DMAPAA), dialkylaminoalkyls such as N,N-dimethylaminopropyl methacrylamide ( Monomers having a tertiary amino group typified by vinyl monomers having a nitrogen-containing heterocycle such as meth)acrylamide and vinylimidazole can be mentioned.

The molecular weight of the amino group-containing (meth)acrylic polymer of component (B) is not particularly limited. to about 200,000, and more preferably about 40,000 to about 150,000.

From the viewpoint of room temperature adhesiveness, heat adhesiveness, hot adhesiveness, hot holding power, etc., the blending ratio of component (A) and component (B) is about It is preferably contained in an amount of 62:about 38 to about 75:about 25, more preferably about 65:about 35 to about 70:about 30.

The (meth)acrylic polymer can be produced by a radical polymerization method, and known methods such as solution polymerization method, suspension polymerization method, emulsion polymerization method and bulk polymerization method can be employed as the production method.

Examples of initiators for polymerization include organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis(4-tertiarybutylcyclohexyl)peroxydicarbonate; 2,2′-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis(2-methylpropionate)dimethyl, azobis 2,4-dimethylvaleronitrile Azo polymerization initiators such as (AVN) can be used. The amount of initiator used can be about 0.05 to about 5 parts by weight per 100 parts by weight of the monomer mixture.

The adhesive of the present disclosure and the adhesive layer obtained from the adhesive may include optional components such as a tackifying resin, a cross-linking agent, a conductive filler, a filler such as a thermally conductive filler (filler), and a silane coupling agent. , a plasticizer, a thickener, a pigment, a dye, a flame retardant, an antioxidant, an ultraviolet absorber, a stabilizer, and the like. Such optional components can be used alone or in combination of two or more.

In one embodiment, the adhesive contains a tackifying resin for the purpose of adjusting tackiness. Examples of the tackifying resin to be blended include rosin-based tackifying resins, terpene-based tackifying resins, petroleum-based tackifying resins, coal-based tackifying resins, and other known tackifying resins. Tackifying resins can be used singly or in combination. The tackifying resin can be used in the range of about 0.5 parts by weight or more, or about 1 part by weight or more, and about 100 parts by weight or less, or about 50 parts by weight or less, based on 100 parts by weight of the rubber and/or polymer. .

In one embodiment the adhesive contains a polyfunctional compound as a cross-linking agent. Polyfunctional compounds generally have at least two, preferably two to four, functional groups in one molecule. Examples of such polyfunctional compounds include isocyanate-based compounds, epoxy-based compounds, amine-based compounds, metal chelate-based compounds, and aziridine-based compounds. When a polymer such as a (meth)acrylic polymer contains a carboxyl group, use of an epoxy compound among these cross-linking agents can particularly improve heat resistance.

The cross-linking agent is used in an amount of about 0.05 parts by mass or more and about 10 parts by mass or less with respect to 100 parts by mass of the polymer. By using the cross-linking agent in such an amount, suitable three-dimensional cross-linking is formed in the polymer (for example, (meth)acrylic polymer), and excellent heat resistance can be exhibited. The above-mentioned cross-linking agents can be used singly or in combination.

In one embodiment the adhesive layer contains a white pigment. A white pigment can be used alone or in combination of two or more. It is advantageous to use titanium dioxide as the white pigment because of its high degree of whiteness. Talc, kaolin, aluminum paste, carbon black or calcium carbonate may be used as additives used in combination with the white pigment. The white pigment may be particles of various shapes such as spherical, needle-like, tabular or flake-like, and spherical particles are preferred because of their good dispersibility. The white pigment may be surface-treated with a coupling agent such as silane or titanate in order to further enhance dispersibility. The white pigment is about 1 part by mass or more, about 3 parts by mass or more, about 5 parts by mass or more, or about 8 parts by mass or more, or about 60 parts by mass with respect to 100 parts by mass of the rubber and/or polymer that constitutes the adhesive. Below, it can be about 50 parts by weight or less, about 40 parts by weight or less, about 30 parts by weight or less, about 20 parts by weight or less, or about 10 parts by weight or less.

The thickness of the adhesive layer of the present disclosure is not particularly limited, and can be, for example, about 5 micrometers or more, about 10 micrometers or more, or about 20 micrometers or more, about 100 micrometers or less, about 80 micrometers or more. It can be micrometers or less, or about 50 micrometers or less.

In some embodiments, decorative laminates of the present disclosure optionally include additional layers. Such additional layers can include, for example, at least one selected from the group consisting of surface layers, decoration layers (eg, color layers, pattern layers, relief layers), bonding layers, and release liners. Additional layers can be applied, for example, on the metallic layer, between the metallic layer and the adhesive layer, or on the side of the adhesive layer opposite to the side on which the metallic layer is located. Additional layers can be applied to all or part of the laminate as long as they do not completely mask the metallic luster of the metallic layer. Additional layers may have three-dimensional features, such as embossed patterns, on their surfaces.

The material of the surface layer is not particularly limited, and examples include (meth)acrylic resins including polymethyl methacrylate (PMMA) and (meth)acrylic copolymers, resins having urethane bonds (e.g., polyurethane), and ethylene-tetrafluoroethylene. Fluororesins such as copolymers (ETFE), polyvinylidene fluoride (PVDF), methyl methacrylate-vinylidene fluoride copolymers (PMMA/PVDF), silicone resins, polyvinyl chloride (PVC), polycarbonate (PC), polyethylene ( PE), polyolefins such as polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides such as nylon, ethylene/acrylic acid copolymers (EAA) and their ionomers, ethylene-acrylic acid Copolymers such as ethyl copolymers, ethylene-vinyl acetate copolymers and ethylene-vinyl alcohol copolymers (EVOH) can be used alone or in combination of two or more. The surface layer may have a multilayer structure. For example, the surface layer may be a laminate of films formed from the above resins, or may be a multi-layer coating of the above resins. The surface layer may have a three-dimensional uneven shape such as an embossed pattern on the entire surface or part of the surface.

The surface layer can be formed by coating the resin composition on the metallic layer directly or via a bonding layer or the like. Coating of the surface layer can be performed before or after applying the decorative laminate to an adherend (eg, a support member as described below). Alternatively, a release liner may be coated with a resin composition to form a surface layer film, and the film may be laminated to the metallic layer via a bonding layer. For example, when the metallic layer has adhesiveness to the surface layer film, the surface layer film can be directly laminated to the metallic layer without using the bonding layer. The surface layer film is formed by applying a resin material such as a curable (meth)acrylic resin composition or a reactive polyurethane composition to a release liner or the like by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, or the like. can be formed by coating on and optionally curing with light or heat.

As the surface layer, a film formed in advance by extrusion, stretching, or the like may be used. Such films can be laminated to the metallic layer via a bonding layer. Alternatively, if the metallic layer has adhesive properties to such a film, the film can be laminated directly to the metallic layer without a bonding layer. By using a film with high flatness as such a film, it is possible to give the article (structure) an appearance with a higher surface flatness. The surface layer can also be formed by multilayer extrusion with other layers. As another layer, for example, a (meth)acrylic film can be used. Examples of (meth)acrylic films include resins containing polymethyl methacrylate (PMMA), polybutyl acrylate, (meth)acrylic copolymers, ethylene/acrylic copolymers, ethylene vinyl acetate/acrylic copolymers, and the like. It can be used in the form of a film. A (meth)acrylic film has excellent transparency and/or scratch resistance, is resistant to heat and/or light, and is resistant to fading and/or gloss change. In addition, it is excellent in moldability even without using a plasticizer, and is also excellent in stain resistance because it is not necessary to use a plasticizer. Among them, those containing PMMA as a main component are preferable. For example, when using a (meth)acrylic resin with excellent scratch resistance as the other layer, and using a fluorine resin such as ETFE, PVDF, PMMA/PVDF, etc. with excellent chemical resistance as the surface layer, it is formed The surface layer can combine the performance of both layers.

The surface layer of the present disclosure includes optional components such as fillers, antioxidants, ultraviolet absorbers, light stabilizers, heat Stabilizers, hard coat materials, brighteners, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, pigments, dyes, and the like can be included. Among them, benzotriazole, ultraviolet absorbers such as Tinuvin (trademark) 400 (manufactured by BASF), hindered amine light stabilizers (HALS) such as Tinuvin (trademark) 292 (manufactured by BASF), etc. It is possible to effectively prevent discoloration, fading, deterioration, etc. of the positioned metallic layer. The hard coat material may be contained in the surface layer, or may be applied as a hard coat layer by coating separately on the surface layer.

The surface layer may be partially translucent or opaque, but is preferably transparent from the viewpoint of visibility of metallic luster. From the viewpoint of protective performance such as transparency and chemical resistance of the surface layer, the surface layer does not contain pigments, fillers, light diffusing particles, or the like having a size that contributes to light scattering. is preferred.

The thickness of the surface layer may vary, but may be, for example, about 1 micrometer or more, about 5 micrometers or more, or about 10 micrometers or more, and about 200 micrometers or less, about 100 micrometers or less. , or about 80 microns or less. When applying a decorative laminate to a support member having a complicated shape, a thinner surface layer is advantageous from the viewpoint of conformability, for example, about 100 micrometers or less, or about 80 micrometers or less. is preferred. On the other hand, when imparting high chemical resistance, weather resistance, scratch resistance, etc. to the article, it is advantageous for the surface layer to be thick. Preferably.

A decoration layer as an additional layer is intended to be a layer capable of imparting decoration other than decoration by a metallic layer. Examples of such decorative layers include, but are not limited to the following, color layers exhibiting paint colors such as light colors such as white and yellow, dark colors such as red, brown, green, blue, gray and black, wood grain, Examples include a pattern layer that imparts a pattern such as a stone grain, a geometric pattern, a leather pattern, a logo, a pattern, etc. to an article, a relief (embossed pattern) layer having an uneven surface, and a combination thereof.

The decorative layer is not limited to the following, but is applied directly or through a bonding layer, etc., to the entire or part of the layers constituting the decorative laminate, such as the surface layer, metallic layer, adhesive layer, etc. be able to.

Materials for the color layer include, but are not limited to, the following: inorganic pigments such as carbon black, yellow lead, yellow iron oxide, red iron oxide, and red iron oxide; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; Pigments such as organic pigments such as pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, and quinacridone pigments such as quinacridone red are used in (meth) acrylic resins, resins with urethane bonds, etc. A material dispersed in a binder resin can be used. Among them, a resin having a urethane bond is preferable from the viewpoint of impact resistance and the like.

The color layer can be formed using such materials by coating methods such as gravure coating, roll coating, die coating, bar coating, and knife coating.

The pattern layer is not limited to the following, but for example, patterns such as patterns, logos, and patterns are printed on the surface using a printing method such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, and screen printing. Layers, metallic layers, adhesive layers, etc. may be employed, or patterns formed by coating such as gravure coating, roll coating, die coating, bar coating, knife coating, punching, etching, etc. Films, sheets, etc. having logos, patterns, etc. can also be used. As a material for the pattern layer, for example, the same material as that used for the color layer can be used.

As the relief layer, a thermoplastic resin film having an uneven surface formed by a conventionally known method such as embossing, scratching, laser processing, dry etching, or hot pressing can be used. A relief layer can also be formed by applying a thermosetting or radiation-curable resin such as a curable (meth)acrylic resin to a release liner having an uneven shape, curing the resin by heating or irradiation, and removing the release liner. can.

The thermoplastic resin, thermosetting resin, and radiation-curable resin used in the relief layer are not particularly limited, but examples include fluorine-based resins, polyester-based resins such as PET and PEN, (meth)acrylic resins, polyethylene, and polypropylene. Polyolefin resins such as thermoplastic elastomers, polycarbonates, polyamides, ABS resins, acrylonitrile-styrene resins, polystyrene, vinyl chloride, resins having urethane bonds, and the like can be used. Among them, a resin having a urethane bond is preferable from the viewpoint of impact resistance and the like. The relief layer may contain at least one of the pigments used in the color layer.

The decorative layer of the present disclosure contains optional components such as fillers, reinforcing agents, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, as long as they do not adversely affect the effects of the present disclosure. Plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, and the like can be included.

The thickness of the decorative layer may be appropriately adjusted according to the required decorativeness, and is not particularly limited. It can be a meter or more, and can be about 50 microns or less, about 40 microns or less, or about 30 microns or less.

Decorative laminates of the present disclosure may employ a bonding layer (sometimes referred to as a "primer layer" or the like) to bond additional layers in the laminate. Solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, heat-curable or UV-curable adhesives such as (meth)acrylic, polyolefin, polyurethane, polyester, and rubber that are generally used as bonding layers can be used. The bonding layer can be applied by a known coating method or the like. In order to distinguish from the above-described adhesive layers, the above-described adhesive layer can also be referred to as the first adhesive layer, the joining layer as the second adhesive layer, and the like.

Decorative laminates of the present disclosure typically may have a release liner applied to the adhesive layer. Release liners can include, for example, paper; plastic materials such as polyethylene, polypropylene, polyester (eg, PET), and cellulose acetate; paper coated with such plastic materials; These liners may have a release treated surface with a release agent such as silicone. The thickness of the release liner can generally be about 5 micrometers or greater, about 15 micrometers or greater, or about 25 micrometers or greater, and about 500 micrometers or less, about 300 micrometers or less, or about 250 micrometers. can be:

The decorative laminate of the present disclosure may be, for example, a sheet product, a rolled body, or a three-dimensional product.

The decorative laminate of the present disclosure comprises applying a metallic coating composition containing metallic pigment particles to a substrate having a substantially smooth surface to form a metallic layer, and then applying an adhesive layer to the metallic layer. formed by The method for manufacturing the decorative laminate of the present disclosure will be exemplified below with reference to FIGS. 2 and 3, but the method for manufacturing the decorative laminate is not limited thereto.

FIG. 2 is a method of making a decorative laminate by laminating and laminating an adhesive layer to a metallic layer. In such a method, a support 207 having a substantially smooth surface is prepared (step (a)), and a metallic coating composition is applied to the substantially smooth surface of the support 207 to form a metallic layer 205 (step (b)). Here, as means for applying the metallic coating composition in step (b), for example, known methods such as knife coater, die coater, roll coater, bar coater, cast coater, notch bar coater, gravure coater, and rod coater. can be used. These methods can be used alone or in combination of two or more. In forming the metallic layer, additional steps such as a drying step, a heat curing step, and an ionizing radiation curing step can be appropriately applied as necessary. One or more of such additional steps can be employed, or two or more of them can be combined.

The viscosity of the metallic coating composition is preferably, for example, about 140 mPa·s or less, about 130 mPa·s or less, or about 120 mPa·s or less at 25°C. When the viscosity is within this range, the metal pigment particles are more likely to be oriented substantially uniformly on the surface of the support, and as a result, good metallic luster can be obtained. The lower limit of the viscosity is not particularly limited, and can be, for example, approximately 4 mPa·s or more, approximately 5 mPa·s or more, or approximately 6 mPa·s or more. The viscosity defined here is a value measured using a B-type viscometer (TVB-15 type) manufactured by Toki Sangyo Co., Ltd. (Minato-ku, Tokyo, Japan), and the measurement is M2 or The measurement is performed at 25° C. using an M3 rotor (rotation speed: 100 rpm), and the value measured 1 minute after the start of measurement is taken as the measured value.

Following step (b), an adhesive film prepared by applying an adhesive layer 203 to a release liner 201 is applied via the adhesive layer 203 to a metallic layer 205 (step (c)) to form a decorative laminate. A body can be obtained (step (d)). Here, the support 207 can constitute the surface layer or release liner of the decorative laminate. If the support constitutes a release liner, the decorative laminate of step (d) can be referred to as a decorative laminate intermediate. In order to distinguish from the release liner of the adhesive film, the release liner that is the support can be called the first release liner, and the release liner of the adhesive film can be called the second release liner. These release liners can similarly use the release liners described above. When the support constitutes the surface layer, the surface layer in the form of a film among the surface layers described above can be used in the same manner.

In FIG. 2, the support constitutes a release liner. In this case, the support 207 of the release liner can be peeled off from the intermediate (step (e)) to obtain the decorative laminate (step (f)).

Subsequent to step (f), additional layers may also be applied to the metallic layer 205, such as, for example, a surface layer, either directly or indirectly via a bonding layer.

FIG. 3 is a method of making a decorative laminate by coating an adhesive to a metallic layer. In such a method, a support 307 having a substantially smooth surface is prepared (step (a)), a metallic coating composition is applied to the substantially smooth surface of the support 307 to form a metallic layer 305, An adhesive is applied to the metallic layer 305 to form an adhesive layer 303 (step (b)). Here, as means for applying the metallic coating composition and the adhesive in step (b), the above-described known methods can be similarly used. In forming the metallic layer and the adhesive layer, additional steps such as a drying step, a thermal curing step, and an ionizing radiation curing step can be appropriately applied as necessary. One or more of such additional steps can be employed, or two or more of them can be combined.

Following step (b), a release liner 301 can be applied to the adhesive layer 303 (step (c)) to obtain a decorative laminate (step (d)). Here, the support 307 can constitute the surface layer or release liner of the decorative laminate. If the support constitutes a release liner, the decorative laminate of step (d) can be referred to as a decorative laminate intermediate. In order to distinguish from the release liner applied to the adhesive layer, the release liner as the support can be called the first release liner, and the release liner applied to the adhesive layer can be called the second release liner. These release liners can similarly use the release liners described above. When the support constitutes the surface layer, the surface layer in the form of a film among the surface layers described above can be used as well.

In FIG. 3, the support constitutes a release liner. In this case, the support 307 of the release liner can be peeled off from the intermediate (step (e)) to obtain the decorative laminate (step (f)).

Subsequent to step (f), additional layers may also be applied to the metallic layer 305, such as, for example, a surface layer, either directly or indirectly via a bonding layer.

The support used in the method of manufacturing the decorative laminate of the present disclosure has a substantially smooth surface on which the metallic coating composition is applied. The smoothness of the substantially smooth surface of the support can be evaluated by the surface roughness test described below. Such roughness (Sa) is about 3.0 micrometers or less, about 0.5 micrometers or less, about 0.3 micrometers or less, about 0.2 micrometers or less, about 0.15 micrometers or less, about It can be 0.1 microns or less, or about 0.08 microns or less. The lower limit of roughness is not particularly limited, and may be, for example, about 0.01 micrometers or more, about 0.03 micrometers or more, about 0.05 micrometers or more, or about 0.07 micrometers or more. can. When a support exhibiting such roughness is used, the metallic pigment particles tend to be oriented substantially uniformly on the surface of the support, and as a result, good metallic luster can be obtained.

As a result of transferring the smooth surface of the support to the surface of the metallic layer prepared by the manufacturing method of the present disclosure, the surface of the metallic layer can also typically exhibit the above roughness (Sa) as well. The surface roughness of the metallic layer can also be measured and calculated in the same manner as described above.

According to one embodiment of the present disclosure, an article is provided having the decorative laminate described above adhered to a support member. Such articles include, for example, a substantially flat article before molding in which a decorative laminate is attached to a support member such as a polycarbonate plate, or a three-dimensional shape obtained by further molding such a substantially flat article. or an article having a three-dimensional shape obtained by bonding a decorative laminate to a supporting member having a shape such as a curved surface. In the present disclosure, a “three-dimensional shape” typically means a three-dimensional shape obtained by adding the Z axis to a two-dimensional shape (a planar shape with only X and Y axes).

An article having a three-dimensional shape is preferably produced by applying the decorative laminate described above to a support member having a three-dimensional shape, from the viewpoint of productivity and the like. Application of the decorative laminate to the support member is preferably carried out by vacuum forming or vacuum pressure forming from the viewpoint of obtaining a highly accurate article. Decorative laminates of the present disclosure can be used for vacuum forming or vacuum pressure forming with stretching. Among them, a decorative laminate having a metallic layer prepared using a metallic coating composition containing metallic pigment particles, a binder precursor, and a silane coupling agent has excellent adhesion between metallic pigment particles, and even after stretching. Since excellent metallic luster can be maintained, it can be used more preferably for vacuum molding or vacuum pressure molding.

In vacuum forming and vacuum pressure forming processes, decorative laminates are typically subjected to heat and vacuum. The heating temperature can generally be about 50° C. or higher, about 80° C. or higher, about 100° C. or higher, about 120° C. or higher, or about 130° C. or higher, and about 180° C. or lower, about 170° C. or lower, or about 160° C. or lower. can be The degree of vacuum of the reduced pressure atmosphere can be about 0.10 atm or less, about 0.05 atm or less, or about 0.01 atm or less, where atmospheric pressure is 1 atm. The lower limit of the degree of vacuum is not particularly limited, and can be, for example, about 0.0001 atm or more, about 0.0005 atm or more, about 0.001 atm or more, or about 0.005 atm or more. In the vacuum pressure molding process, the decorative laminate is subjected to additional pressure. Such a pressure can be, for example, greater than about 3 atm, greater than about 4 atm, or greater than about 5 atm, where atmospheric pressure is 1 atm. Although the upper limit of the pressure is not particularly limited, it can be, for example, about 20 atm or less, about 15 atm or less, or about 10 atm or less.

The maximum area elongation of the decorative laminate after molding is about 0% or more, about 5% or more, about 10% or more, about 30% or more, about 50% or more, about 100% or more, about 200% or more, or It can be greater than or equal to about 300%, less than or equal to about 1,000%, less than or equal to about 700%, less than or equal to about 500%, or less than or equal to about 450%.

The area elongation rate is: area elongation rate (%) = (B - A) x 100 / A (A: the area before molding of the part with the decorative laminate, B: the part corresponding to A of the decorative laminate area after molding). For example, if a portion of the decorative laminate had an area of 100 cm ² before molding and that portion was 250 cm ² on the surface of the support member after molding, then 150%. The maximum area elongation refers to the value of the highest area elongation in the decorative laminate on the entire surface of the article.

For example, when a flat decorative laminate is attached to a support member having a three-dimensional shape by vacuum forming, for example, the portion of the film that first hits the support member is hardly stretched and the area elongation rate is almost 0%, and finally The end portion where the tape is attached to the tape is greatly stretched and has an area elongation rate of 200% or more. Thus, the area elongation rate of the decorative laminate greatly varies depending on the place where it is attached. The success or failure of molding is determined by whether or not defects such as failure to follow the supporting member or tearing of the film occur at the portion where the film is stretched the most. Therefore, not the average areal elongation of the entire article, but the areal elongation of the most stretched portion, ie, the maximum areal elongation, is a substantial indicator of the acceptance or rejection of the finally obtained article.

For the maximum area elongation rate, for example, a 1 mm square grid is printed on the entire surface of the decorative laminate before molding, and the change in the area is measured after molding, or the thickness of the decorative laminate before and after molding is measured. It can be confirmed by measuring.

The material of the support member is not particularly limited, and examples thereof include resins having urethane bonds (e.g., polyurethane resin), polyolefin resins (e.g., polyethylene and polypropylene), glycol-modified polyethylene terephthalate resin (PET-G), (meth)acrylic resin ( Examples include polymethyl methacrylate resins), polycarbonate resins, and acrylonitrile-butadiene-styrene copolymers (ABS). These can be used alone or in combination of two or more.

The support member may be wholly or partially transparent, translucent, or opaque in the visible range to provide the desired appearance.

The thickness of the support member is not particularly limited, and can be, for example, about 0.2 mm or more, about 0.5 mm or more, about 1.0 mm or more, or about 1.5 mm or more, about 3.0 mm or less, It can be about 2.5 mm or less, or about 2.0 mm or less.

Articles to which the decorative laminates of the present disclosure are applied can be used in a variety of applications. Such applications include, for example, signboards (e.g. internally illuminated signboards and externally illuminated signboards); signs (e.g. internally illuminated signs and externally illuminated signs); Interior or exterior parts for vehicles such as aircraft and ships (e.g., roof members, pillar members, door trim members, instrument panel members, front members such as bonnets, bumper members, fender members, side sill members, and interior panel members) building materials (for example, doors); electrical appliances such as personal computers, smart phones, mobile phones, refrigerators, and air conditioners; stationery; furniture; Among others, articles to which the decorative laminate of the present disclosure is applied can be suitably used for interior or exterior parts of vehicles.

The following examples illustrate specific embodiments of the present disclosure, but the invention is not limited thereto. All parts and percentages are by weight unless otherwise specified. Numerical values inherently contain errors resulting from measurement principles and measurement equipment. Numbers are shown to significant digits with normal rounding applied.

The products used in this example are shown in Table 1 below.

<<Test example 1>>
In Test Example 1, the metallic luster of the metallic layer was evaluated depending on whether or not a support having a substantially smooth surface was used.

(Preparation of metallic coating composition 1)
Metallic coating composition 1 was prepared by uniformly mixing 20 parts by mass of Toyal Shine (trademark) TS-408PM, which are metal pigment particles, and 80 parts by mass of MEK.

(Preparation of metallic coating composition 2)
Metallic coating composition 2 was prepared by uniformly mixing 20 parts by mass of Toyal Shine (trademark) TS-710PM, which are metal pigment particles, and 80 parts by mass of MEK.

(Preparation of metallic coating composition 3)
Metallic coating composition 3 was prepared by uniformly mixing 20 parts by mass of Toyal Shine (trademark) EMRS-710 and 80 parts by mass of MEK, which are metal pigment particles.

(Preparation of Adhesive 1)
94 parts by mass of butyl acrylate (BA) and 6 parts by mass of acrylic acid (AA) are dissolved in a mixed solution of 100 parts by mass of toluene and 100 parts by mass of ethyl acetate, and azobis(2,4-dimethylvalero) is used as a polymerization initiator. Nitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-65) 0.2 parts by mass was added, and then reacted at 50 ° C. for 24 hours in a nitrogen atmosphere to give a toluene / ethyl acetate mixed solution of acrylic resin 1 (solid min 33%) was made. The acrylic resin 1 had a weight average molecular weight of 760,000 and a glass transition temperature (Tg) of -20°C.

60 parts by mass of methyl methacrylate (MMA), 34 parts by mass of n-butyl methacrylate (BMA), and 6 parts by mass of dimethylaminoethyl methacrylate (DMAEMA) were dissolved in 150 parts by mass of ethyl acetate to obtain dimethyl-2 as a polymerization initiator. , 2'-Azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) 0.6 parts by mass was added, and then reacted at 65 ° C. for 24 hours in a nitrogen atmosphere to form an acrylic An ethyl acetate solution of Resin 2 (39% solids) was prepared. The acrylic resin 2 had a weight average molecular weight of 68,000 and a glass transition temperature (Tg) of 104°C.

49.16 parts by mass of acrylic resin 1, 17.85 parts by mass of acrylic resin 2, 0.23 parts by mass of SONGNOX (trademark) 1010, 1.08 parts by mass of Ti-Pure (trademark) R-960, E- A white adhesive 1 was prepared by uniformly mixing 0.46 parts by weight of 5XM and 31.22 parts by weight of MIBK.

(Preparation of Adhesive 2)
A white adhesive 2 was prepared by uniformly mixing 16 parts by weight of Desmocoll™ 530 and 84 parts by weight of MEK.

(Preparation of Adhesive 3)
75.05 parts by mass of pressure sensitive adhesive 1, 0.94 parts by mass of cross-linking agent, 0.41 parts by mass of acrylic resin 2, 0.83 parts by mass of Ti-Pure (trademark) R-960, 0 parts by mass of MIBK A white adhesive 3 was prepared by uniformly mixing 0.26 parts by weight and 22.51 parts by weight of MEK.

(Example 1)
On the substantially smooth surface of the release liner 1, No. Metallic Coating Composition 1 was coated in a Meyer bar coater using a Meyer bar of No. 8 and then dried in an oven at about 100° C. for about 1 minute to produce a laminate with a metallic layer about 0.4 micrometers thick. bottom.

After coating the adhesive 1 on another release liner 1, it is dried in an oven at about 80° C. for about 3 minutes and in an oven at about 120° C. for about 5 minutes to prepare an adhesive layer about 40 micrometers thick, and then A release liner 2 was laminated on this adhesive layer by a heat lamination method to prepare an adhesive transfer film.

After removing the separator of the adhesive transfer film, the adhesive transfer film was bonded to the metallic layer of the laminate via the adhesive layer by a heat lamination method. Subsequently, the release liner 1 on the metallic layer side was removed to obtain the decorative laminate of Example 1.

(Example 2)
A laminate having a metallic layer was prepared in the same manner as in Example 1, and the metallic layer was coated with the adhesive 2, followed by heating in an oven at about 80°C for about 3 minutes and in an oven at about 120°C for about 5 minutes. An adhesive layer having a thickness of about 40 micrometers was prepared by drying, and then a release liner 1 was separately laminated to this adhesive layer by a heat lamination method. Subsequently, the release liner 1 on the metallic layer side was removed to obtain a decorative laminate of Example 2.

(Example 3)
No. 4 is applied to the substantially smooth surface of the release liner 2 . After coating the metallic coating composition 1 with a Meyer bar coater using a Meyer bar of No. 5, it is dried in an oven at about 100° C. for about 1 minute to produce a laminate with a metallic layer about 0.2 micrometers thick. bottom.

After coating the adhesive 1 on the metallic layer, it is dried in an oven at about 80° C. for about 3 minutes and in an oven at about 120° C. for about 5 minutes to prepare an adhesive layer with a thickness of about 40 micrometers; A release liner 1 was laminated on this adhesive layer by a heat lamination method at 60°C. Subsequently, the release liner 2 on the metallic layer side was removed to obtain a decorative laminate of Example 3.

(Example 4)
A decorative laminate of Example 4 was obtained in the same manner as in Example 3, except that the metallic coating composition 2 was used to prepare the metallic layer.

(Example 5)
A metallic layer was prepared using metallic coating composition 3, an adhesive layer was prepared using adhesive 3, and the drying conditions during adhesive layer preparation were an oven at about 65 ° C. for about 3 minutes and about A decorative laminate of Example 5 was obtained in the same manner as in Example 3, except that the oven temperature was changed to 95° C. for about 5 minutes.

(Comparative example 1)
After coating the substantially smooth surface of the release liner 1 with the adhesive 1, it was dried in an oven at about 80° C. for about 3 minutes and in an oven at about 120° C. for about 5 minutes to prepare an adhesive layer with a thickness of about 40 μm. . Next, No. Metallic Coating Composition 1 is coated onto the adhesive layer with a Meyer bar coater using a Meyer bar of No. 8 and then dried in an oven at about 100° C. for about 1 minute to provide a metallic layer about 0.4 micrometers thick. , a decorative laminate of Comparative Example 1 was produced.

(Comparative example 2)
An adhesive layer was prepared in the same manner as in Comparative Example 1, and then No. Leaf Powder (trademark) 49CJ-1120 containing propylene glycol monomethyl ether as a solvent was coated on the adhesive layer with a Meyer bar coater using a Meyer bar of No. 5, and then dried in an oven at about 100°C for about 1 minute to give a thickness of about A decorative laminate of Comparative Example 2 was made with a 2.3 micrometer thick metallic layer.

<Physical property evaluation test 1>
The properties of each decorative laminate were evaluated by conducting the following tests. Table 2 shows the results.

(Metallic luster test: clarity)
Three locations were arbitrarily selected from the metallic layer of the laminate, the clarity (Gd value) was measured for each selected portion, and the average value was calculated. A clearness and gloss meter (PGD-IV) manufactured by Japan Color Research Institute was used to measure the clearness.

(Appearance test)
The surface of the metallic layer was visually observed under a white fluorescent lamp of 400 lux for reflection of the subject's own face. Here, the distance between the metallic layer and the face was about 50 cm. "Good" when metallic luster is present and the outline of the face is clear; was evaluated as "bad" when was visually recognized. Here, the "defective appearance portion" means, for example, a streak-like portion, a portion with an increased haze, or a portion where the metallic luster is clearly reduced.

(Surface roughness test: Sa value)
An object to be measured (for example, a support or a laminate for decoration) was fixed on a substantially smooth aluminum plate so that the surface of the object to be measured faces upward. Using a 3D measurement laser microscope (LEXT (trademark) OLS4100, manufactured by Olympus Corporation), the surface roughness (Sa) of the metallic layer was arbitrarily measured at five points with a 20x objective lens, and the average value was calculated. Table 2 describes the surface roughness of the outermost surface of the metallic layer.

<<Test example 2>>
In Test Example 2, the effects of the binder and silane coupling agent on the metallic layer were evaluated.

(Preparation of metallic coating composition (MC1-12))
Each component was mixed in the mixing ratio shown in Table 3 to prepare each metallic coating composition (MC1 to MC12). Here, the numerical value for each component shown in Table 3 means the content (% by mass) based on the solid content of each component.

(Example 6)
No. 4 is applied to the substantially smooth surface of the release liner 2 . After coating the metallic coating composition MC1 with a Meyer bar coater using a Meyer bar of No. 5, it is dried in an oven at about 100° C. for about 1 minute to produce a laminate with a metallic layer about 0.2 micrometers thick. bottom. Subsequently, after coating adhesive 1 on this metallic layer, it was dried in an oven at about 80° C. for about 3 minutes and in an oven at about 120° C. for about 5 minutes to prepare an adhesive layer with a thickness of about 40 micrometers. Then, a release liner 1 was laminated on this adhesive layer by a heat lamination method. Subsequently, the release liner 2 on the metallic layer side was removed to obtain a laminate comprising the metallic layer and the adhesive layer.

A multilayer film (surface layer) prepared by laminating DX14S, S014G, a bonding layer made of a phenoxy resin having a thickness of about 0.5 micrometers, and a transfer sheet in this order, was coated with the metallic layer of the laminate and the transfer sheet of the multilayer film. After arranging them so that they were in contact with each other, they were laminated together by a heat lamination method to obtain a decorative laminate of Example 6.

The release liner 1 is removed from the laminate for decoration, and the laminate is formed into a support member (PC/ABS plate (CK43 black, manufactured by Techno Polymer Co., Ltd.) at a molding temperature of 145°C using a vacuum pressure molding method (TOM molding method). , Minato-ku, Tokyo, Japan)) to form an article.

(Examples 7-17)
Articles of Examples 7 to 17 were produced in the same manner as in Example 6, except that the metallic coating composition shown in Table 4 was used.

<Physical property evaluation test 2>
The properties of each article were evaluated by performing the Clarity and Appearance Tests described above and the Adhesion Test below. Table 4 shows the results. It should be noted that the decorative laminates of the present disclosure may be used without heat and/or pressure as applied in vacuum pressure molding. In such cases, the adhesion requirements as implemented below are not necessarily required. In other words, if good metallic luster is obtained, it corresponds to the examples. Further, if the adhesiveness is also excellent, it can be said that it can be suitably used for molding involving heating and/or pressure.

(Adhesion test)
Adhesion performance of the decorative laminate on the article was evaluated by the cross-cut method according to JIS K 5600 according to the following criteria. Here, a 10×10 grid with a grid interval of 2 mm and Scotch (trademark) filament tape 898 (manufactured by 3M Japan Ltd.) were used. Also, the number of remaining squares of the metallic layer after the tape was peeled off was visually confirmed.

It will be apparent to those skilled in the art that various modifications may be made to the above-described embodiments and examples without departing from the underlying principles of the invention. In addition, it will be apparent to those skilled in the art that various modifications and alterations of this invention can be made without departing from its spirit and scope.

100 decorative laminate 101, 201, 301 release liner 103, 203, 303 adhesive layer 105, 205, 305 metallic layer 207, 307 support

Claims (20)

an adhesive layer, and
sequentially comprising a metallic layer containing metallic pigment particles;
The definition of the outermost surface of the metallic layer located on the side opposite to the adhesive layer side is 0.5 or more.
Decorative laminate. The decorative laminate according to claim 1, wherein the metal pigment particles have a scaly shape. The decorative laminate according to claim 1 or 2, wherein the metallic layer has a thickness of 0.07 µm or more and 1.1 µm or less. The decorative laminate according to any one of claims 1 to 3, wherein the content of the metal pigment particles in the metallic layer is 20.0% by mass or more and 40.0% by mass or less. The decorative laminate according to any one of claims 1 to 4, wherein the metallic layer comprises a binder and a silane coupling agent. The content of the binder in the metallic layer is 0.1% by mass or more and 10.0% by mass or less, and the content of the silane coupling agent in the metallic layer is 50.0% by mass or more. The decorative laminate according to claim 5, which is 79.9% by mass or less. The decorative laminate according to claim 5 or 6, wherein the silane coupling agent contains at least one selected from the group consisting of epoxy groups and amine groups. The decorative laminate according to any one of claims 5 to 7, wherein the binder contains at least one selected from the group consisting of resins having urethane bonds and phenoxy resins. The decorative laminate according to any one of claims 1 to 8, wherein the adhesive layer contains a white pigment. The decorative laminate according to any one of claims 1 to 9, comprising at least one selected from the group consisting of a surface layer, a decorative layer, a bonding layer and a release liner. The decorative laminate according to any one of claims 1 to 10, which is used for vacuum molding or vacuum pressure molding. applying a metallic coating composition comprising metallic pigment particles to a substrate having a substantially smooth surface to form a metallic layer;
applying an adhesive layer to the metallic layer;
A method of making a decorative laminate comprising: 13. The manufacturing method of claim 12, wherein the support constitutes a surface layer or release liner of the decorative laminate. 14. The manufacturing method according to claim 12 or 13, wherein the surface roughness (Sa) of the support is 0.5 micrometers or less. An article, wherein the decorative laminate of any one of claims 1-11 is adhered to a support member. 16. The article of claim 15, having a three-dimensional shape. 17. An article according to claim 15 or 16, which is a vehicle interior or exterior article. A method of manufacturing an article having a three-dimensional shape, comprising applying the decorative laminate according to any one of claims 1 to 11 to a support member having a three-dimensional shape. 19. The manufacturing method of claim 18, wherein applying the film to the support member is done by vacuum forming or vacuum pressure forming. A metallic coating composition comprising metallic pigment particles, a binder precursor and a silane coupling agent,
In terms of solid content, the content of the metal pigment particles is 20.0% by mass or more and 40.0% by mass or less, and the content of the binder precursor is 0.1% by mass or more and 10.0% by mass or less. and the content of the silane coupling agent is 50.0% by mass or more and 79.9% by mass or less,
Metallic coating composition.

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