Silver glossy film, and production method and application of the same

Abstract

To provide a silver glossy film which improves silver glossiness, adhesion, scratch resistance and weather resistance.SOLUTION: A silver glossy film includes a silver layer 2 stacked on a base material 3, and a top coat layer 1 stacked on the silver layer 2, wherein the silver layer 2 is formed of a first interface layer (A) on a base material side formed of composite nanoparticles (a) of metal containing silver and protective colloid, an intermediate layer (B) which is stacked on the first interface layer (A), and has a phase-separation structure which is phase-separated into a first phase containing composite nanoparticles (b1) metal containing silver and protective colloid and a first resin (b2), and a second phase which contains composite nanoparticles (b3) of metal containing silver and protective colloid and a second resin (b4), and has a content ratio of the metal containing the silver less than that of the first phase, and a second interface layer (C) which is stacked on the intermediate layer (B) and is formed of composite nanoparticles (c) of metal containing silver and protective colloid, and the top coat layer 1 is formed of an epoxy cured product including a metaxylylenediamine unit.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a silver gloss film for metallic decoration of various objects to be decorated, a method for producing the same, and uses thereof.

Background Art

[0002] Metallic decoration is required in a wide range of fields such as, for example, interior and exterior parts of automobiles, emblems, electronic devices, containers for cosmetics, and shafts of golf clubs. In order to obtain a high-class feeling, a high-level metallic gloss comparable to that of metal is required. In particular, silver has a high light reflectance and thus has a beautiful metallic gloss (metallicity, brilliance, specularity), and is expected as a metal suitable for a high level of design. As a method for forming a silver gloss film, a method using an ink containing silver nanoparticles is known because of its excellent metallic gloss. Japanese Patent Application Laid-Open No. 2022-008104 (Patent Document 1) discloses a method for forming a silver gloss film excellent in glossiness, adhesion, and abrasion resistance using an ink.

[0003] On the other hand, when such an ink is used as a decorative paint for the interior and exterior of automobiles or containers, characteristics related to the color tone of the paint film are also important, and it is also required that discoloration due to use is small and weather resistance is excellent.

[0004] Japanese Patent Application Laid-Open No. 2018-114747 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2019-031086 (Patent Document 3) disclose a surface decoration structure provided with a silver mirror film layer having good gloss and good corrosion resistance. By adding a combination of a specific ultraviolet absorber and a specific light stabilizer or a specific rust preventive to at least one of the undercoat paint film and the topcoat paint film laminated on both sides of the silver mirror film layer, it is described that corrosion resistance, weather resistance, adhesion, and long-term brilliance can be improved.

[0005] Japanese Patent Application Laid-Open No. 2007-169685 (Patent Document 4) discloses a metal-plated material provided with a silver mirror layer. It is described that by adding a benzotriazole compound to at least one of the undercoat layer and the topcoat layer laminated on both sides of the silver mirror layer, the corrosion resistance of the silver mirror layer can be improved.

[0006] Japanese Patent Application Laid-Open No. 2014-191171 (Patent Document 5) discloses a film mirror excellent in crack resistance and light resistance of a barrier layer, which has a resin substrate, a metal reflection layer formed of silver, and an organic barrier layer formed of a constituent material having an epoxy group or an isocyanate group, and the oxygen permeability of the organic barrier layer is 10 ml / m 2 / day / atm or less.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, in the silver gloss films of Patent Documents 2 to 5, it is impossible to achieve both silver glossiness and adhesion and abrasion resistance. Furthermore, although Patent Documents 2 to 5 describe weather resistance, they do not specifically describe discoloration resistance, and the color tone of the silver gloss film has not been evaluated.

[0009] Note that the index used for the characteristic evaluation regarding color and taste is the index of color difference (ΔE). The color difference (ΔE) is the difference in lightness (ΔL * ), and the difference in chromaticity (Δa * , Δb * ), and is represented by the following formula. It is expressed as follows.

[0010] ΔE = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ) 1 / 2

[0011] In particular, when using ink as a decorative paint, it is important that the discoloration due to light such as sunlight is small. Even when using the color difference (ΔE) evaluated considering both the difference in lightness (ΔL * ) and the difference in chromaticity (Δa * , Δb * ), it is required that this color difference (ΔE) is small.

[0012] As a general method for evaluating discoloration due to light, there is a method of evaluating the color difference (ΔE) before and after a weather resistance test using a xenon weather meter. A xenon weather meter is a tester that irradiates a sample with a xenon lamp as a light source approximated to sunlight, and by increasing the illuminance of the irradiated light to promote deterioration, it is possible to reproduce the discoloration due to use in a short time. Since this weather resistance test is also standardized in JIS K 5600-7-7:2008, it is required by many users.

[0013] For example, although the silver gloss ink described in Patent Document 1 can obtain a silver gloss film excellent in silver gloss, adhesion, and abrasion resistance, the color difference (ΔE) before and after the weather resistance test is large, and discoloration occurs, so there is a problem that it cannot meet the required characteristics of the user's weather resistance test.

[0014] Therefore, an object of the present invention is to provide a silver gloss film capable of improving silver gloss, adhesion, abrasion resistance, and weather resistance (discoloration resistance), and a method for producing the same.

Means for Solving the Problem

[0015] As a result of intensive studies to achieve the above object, the present inventor has found that on a substrate (or an object to be decorated), a first interface layer (A) formed of composite nanoparticles (a) of a metal containing silver and a protective colloid, a first phase containing composite nanoparticles (b1) of a metal containing silver and a protective colloid and a first resin (b2), and a second phase containing composite nanoparticles (b3) of silver and a protective colloid and a second resin (b4) and having a lower silver content ratio than the first phase, an intermediate layer (B) having a phase-separated structure in which the second phase is phase-separated, and a second interface layer (C) formed of composite nanoparticles (c) of a metal containing silver and a protective colloid are sequentially laminated to form a silver layer having a structure, and on this silver layer, a cured product of a curable composition containing an epoxy resin and a curing agent is formed, and the cured product forms a top coat layer containing a metaxylylenediamine unit, and it has been found that silver glossiness, adhesion, scratch resistance, and weather resistance (discoloration resistance) can be improved, and the present invention has been completed.

[0016] That is, the present invention includes the following aspects.

[0017] Aspect [1]: A silver gloss film laminated on a substrate, The silver gloss film includes a silver layer laminated on the substrate and a top coat layer laminated on this silver layer, The silver layer includes a first interface layer (A) on the substrate side formed of composite nanoparticles (a) of a metal containing silver and a protective colloid, Laminated on the first interface layer (A), a first phase containing composite nanoparticles (b1) of a metal containing silver and a protective colloid and a first resin (b2), and a second phase containing composite nanoparticles (b3) of a metal containing silver and a protective colloid and a second resin (b4) and having a phase-separated structure in which the content ratio of the metal containing silver is less than that of the first phase, an intermediate layer (B), Laminated on the intermediate layer (B) and formed of a second interface layer (C) formed of composite nanoparticles (c) of a metal containing silver and a protective colloid, The top coat layer is formed of a cured product of a curable composition containing an epoxy resin and a curing agent, and the cured product is a silver gloss film containing a metaxylylenediamine unit.

[0018] Aspect [2]: The silver gloss film according to Aspect [1], wherein the color difference ΔE before and after a weather resistance test with an irradiance of 120 W / m 2 , a black panel temperature of 63°C, and an irradiation time of 100 hours is less than 5.

[0019] Aspect [3]: The silver gloss film according to Aspect [1] or [2], wherein the average thickness of the top coat layer is 0.5 to 20 μm.

[0020] Aspect [4]: The silver gloss film according to any one of Aspects [1] to [3], wherein the oxygen permeability of the top coat layer is 30 mL / m 2 / day / atm or less.

[0021] Aspect [5]: The silver gloss film according to any one of Aspects [1] to [4], wherein at least one of the epoxy resin and the curing agent in the top coat layer contains a metaxylylenediamine unit.

[0022] Aspect [6]: The silver gloss film according to any one of Aspects [1] to [5], further including an undercoat layer interposed between the base material and the first interface layer (A), wherein the undercoat layer is formed of a cured product of a curable composition containing an epoxy resin and a curing agent, the cured product contains a metaxylylenediamine unit, and the average thickness of the undercoat layer is 20 to 100 μm.

[0023] Aspect [7]: The silver gloss film according to any one of Aspects [1] to [6], wherein the first resin (b2) is at least one selected from the group consisting of (meth)acrylic resins, polyvinyl acetal resins, and cellulose resins, and the second resin (b4) is at least one selected from the group consisting of (meth)acrylic resins, polyvinyl acetal resins, cellulose resins, and silicone resins.

[0024] Aspect [8]: The silver glossy film according to any one of Aspects [1] to [7], wherein the first resin (b2) is a cellulose-based resin and the second resin (b4) is a (meth)acrylic-based resin.

[0025] Aspect [9]: A method for producing a silver glossy film according to any one of Aspects [1] to [8], wherein a silver layer and a top coat layer are laminated on a substrate.

[0026] Aspect

[10] : A coating step of applying, onto a substrate, a liquid composition containing composite nanoparticles of a metal containing silver and a protective colloid, a first resin, a second resin, and a solvent; and a phase separation step of drying the coating film formed from the liquid composition to obtain a silver layer having a phase separation structure. The production method according to Aspect [9].

[0027] Aspect

[11] : A decorative body having the silver glossy film according to any one of Aspects [1] to [8] laminated on a substrate.

[0028] Aspect

[12] : A method for decorating a body to be decorated as a substrate by laminating the silver glossy film according to any one of Aspects [1] to [8] on the body to be decorated.

Advantages of the Invention

[0029] In the present invention, on a substrate (or a body to be decorated), a first interface layer (A) formed of composite nanoparticles (a) of a metal containing silver and a protective colloid, a first phase containing composite nanoparticles (b1) of a metal containing silver and a protective colloid and a first resin (b2), and a second phase containing composite nanoparticles (b3) of silver and a protective colloid and a second resin (b4) and having a lower content ratio of the metal containing silver than the first phase, and having a phase separation structure in which the two phases are phase-separated; an intermediate layer (B); and a second interface layer (C) formed of composite nanoparticles (c) of a metal containing silver and a protective colloid are sequentially laminated. The silver layer has a structure in which a top coat layer formed of a cured product of a curable composition containing an epoxy resin and a curing agent and having an average thickness of 0.5 to 30 μm and containing a metaxylylenediamine unit is sequentially laminated. Therefore, the silver glossiness, adhesion, scratch resistance, and weather resistance (discoloration resistance) can be improved.

Brief Description of the Drawings

[0030]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Modes for Carrying Out the Invention

[0031] [Silver Glossy Film] The silver glossy film of the present invention may include a silver layer laminated on a substrate and a top coat layer laminated on this silver layer. For example, as shown in FIG. 1, it may be formed of a silver layer 2 laminated on a decorated object (substrate) 3 and a top coat layer 1 laminated on this silver layer 2.

[0032] Furthermore, the silver layer has a structure in which a first interface layer (A), an intermediate layer (B), and a second interface layer (C) are sequentially laminated. In the intermediate layer (B), a phase separation structure (such as a sea-island structure or a co-continuous structure) is formed in which a phase containing a relatively large amount of composite nanoparticles and a phase containing only a small amount are phase-separated. In addition, in the second interface layer (C) and the first interface layer (A), the composite nanoparticles are arranged or oriented, resulting in a high shielding effect (non-transparency) and the manifestation of a high-degree silver luster (mirror surface).

[0033] In addition, for a silver luster film, in addition to silver luster properties, adhesion and abrasion resistance are also required. By containing a resin component (binder), adhesion and abrasion resistance can be improved. However, on the other hand, the higher the resin component content, the lower the proportion of silver, resulting in a decrease in the light shielding effect of silver and a reduction in silver luster properties. In the present invention, in the intermediate layer, the composite nanoparticles are unevenly distributed by two types of resin components, forming a phase (a phase containing a relatively large amount of composite nanoparticles) that can shield light. Therefore, even when a large amount of resin component is blended, high-degree silver luster properties are manifested. That is, by blending a large amount of resin component while maintaining high-degree silver luster properties, adhesion and abrasion resistance can be improved.

[0034] On the other hand, when a silver layer having such a structure is exposed to ultraviolet rays during use, it turns yellow. The mechanism of this discoloration can be estimated as follows. That is, FIG. 2 is a schematic diagram comparing the layer structures of the silver layer before and after discoloration. In the silver layer before discoloration, as shown in FIG. 2(a), between a first interface layer 11 and a second interface layer 12 having a structure in which composite nanoparticles of a metal containing silver (silver-containing metal) and a protective colloid are arranged, an intermediate layer in which a first phase 13 having a high content ratio of silver-containing metal and a second phase 14 having a low content ratio of silver-containing metal are phase-separated is interposed to form a three-layer structure. In contrast, in the state of being discolored by exposure to ultraviolet rays, as shown in FIG. 2(b), a part of the composite nanoparticles arranged on the surface of the silver layer 2 to form the second interface layer 12 (the layer exposed to ultraviolet rays on the surface part of the silver luster film) moves into the intermediate layer and disappears, generating a disappearance region 12a of the composite nanoparticles in a part of the region of the second interface layer 12.

[0035] In contrast, in the present invention, by providing the top coat layer 1 on the silver layer 2 (the second interface layer 12), it is possible to prevent a part of the composite nanoparticles forming the second interface layer 12 from disappearing and the layer structure of the silver layer 2 from changing. That is, the reason why the silver gloss film discolors when exposed to ultraviolet rays is that a part of the composite nanoparticles of the second interface layer 12 disappears and the layer structure of the silver layer changes. By covering the silver layer with the top coat layer formed of a cured epoxy resin having a metaxylylenediamine unit, such a change in the layer structure can be prevented, and it can be inferred that the discoloration of the silver gloss film due to exposure to light such as sunlight is suppressed and the color difference ΔE becomes small.

[0036] [Silver layer] The silver layer has a structure in which a first interface layer (A), an intermediate layer (B), and a second interface layer (C) are sequentially laminated.

[0037] (A) First interface layer The first interface layer (A) is formed of composite nanoparticles (a) of a metal containing silver (silver-containing metal) and a protective colloid. By arranging or orienting the composite nanoparticles (a) at the interface with the substrate, the metal containing silver forms a dense thin film (silver-containing metal thin film). In the present invention, by forming such a first interface layer (A) at the interface with the substrate, the silver gloss property from the back surface can be improved in a transparent substrate or the like.

[0038] The average thickness of the first interface layer (A) may be 300 nm or less, for example, 3 to 300 nm, preferably 5 to 200 nm, more preferably 10 to 100 nm, still more preferably 15 to 50 nm, and most preferably 20 to 40 nm. If the average thickness of the first interface layer (A) is too thick, there is a risk of deterioration in adhesion.

[0039] In the present application, the average thickness of the first interface layer (A) can be measured by observing the cross section of the silver gloss film with a transmission electron microscope (TEM) and is shown as the average value of any three locations.

[0040] (a) Composite nanoparticles In the composite nanoparticle (a), the composite form of the metal containing silver and the protective colloid is not particularly limited, and it may be a composite attached or coordinated to the surface of the metal nanoparticle containing silver (silver-containing metal nanoparticle), or it may be a composite covering the surface of the silver-containing metal nanoparticle. Since the silver-containing metal nanoparticle has a high coordination property with respect to the protective colloid (or dispersant), a composite covering the silver-containing metal nanoparticle may be formed by coordination of the protective colloid to the surface of the silver-containing metal nanoparticle. When the silver-containing metal nanoparticle is complexed with the protective colloid, the dispersion stability of the silver-containing metal nanoparticle can be improved, the affinity with the resin component can be easily adjusted, and a phase separation structure can be formed.

[0041] (Silver-containing metal nanoparticle) The silver-containing metal nanoparticle has a nanometer size. The number average particle diameter (number average primary particle diameter) of the silver-containing metal nanoparticle is, for example, 1 to 100 nm (for example, 2 to 80 nm), preferably 3 to 70 nm (for example, 4 to 50 nm), and more preferably 5 to 40 nm (especially 10 to 30 nm).

[0042] The silver-containing metal nanoparticle has the above-mentioned average particle diameter and shows a wide particle size distribution in the range of 200 nm or less, but may hardly contain coarse particles exceeding 200 nm. Therefore, the maximum primary particle diameter of the silver-containing metal nanoparticle is, for example, 200 nm or less, preferably 150 nm or less, and more preferably 100 nm or less.

[0043] In the silver-containing metal nanoparticle, the proportion of particles having a primary particle diameter of 100 nm or more is, on a mass basis, for example, 10% by mass or less (for example, 0 to 8% by mass), preferably 5% by mass or less (for example, 0.01 to 3% by mass), and more preferably 1% by mass or less (for example, 0.02 to 0.5% by mass).

[0044] In the present application, the particle diameter and particle size distribution of the silver-containing metal nanoparticle can be measured using a transmission electron microscope, and the average particle diameter is shown as the average value of any 10 particles.

[0045] (Metal containing silver) The metal containing silver (silver-containing metal) may be silver alone or an alloy of silver and other metals. The other metals are not particularly limited as long as they can be alloyed with silver. Examples include Cr, Mo, W, Ni, Pd, Pt, Cu, Au, Zn, In, Sn, Pb, etc. These other metals can be used alone or in combination of two or more. Among these other metals, Cu is preferred.

[0046] The proportion of silver may be 50% by mass or more in the silver-containing metal, for example, 90% by mass or more, preferably 95% by mass or more, more preferably 97% by mass or more, still more preferably 99% by mass or more, and most preferably 100% by mass (silver alone). If the proportion of silver is too low, the silver luster may decrease.

[0047] When the silver-containing metal is a combination of silver and other metals (especially copper), the proportion of the other metal is, for example, 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of silver.

[0048] (Protective colloid) The protective colloid may be a dispersant, and is often a non-volatile dispersant. In particular, the protective colloid preferably contains a polymer dispersant having a carboxyl group or a derivative group thereof. In the present application, the carboxyl group includes a carboxyl group in the form of an acid anhydride group.

[0049] The polymer dispersant (or polymer-type dispersant) should have at least a carboxyl group and be capable of dispersing silver-containing metal nanoparticles, and may be an amphiphilic polymer dispersant (or oligomer-type dispersant).

[0050] Examples of the polymer dispersant include polymer dispersants commonly used for dispersing colorants in the fields of paints and inks. Representative polymer dispersants (amphiphilic polymer dispersants) include water-soluble or water-dispersible resins containing hydrophilic units (or hydrophilic blocks) formed from hydrophilic monomers.

[0051] Examples of the hydrophilic monomer include addition polymerizable monomers such as carboxyl group-containing monomers (unsaturated polyvalent carboxylic acids such as (meth)acrylic acid, maleic acid, maleic anhydride or acid anhydrides thereof), monomers having a sulfo group (such as styrene sulfonic acid), and hydroxyl group-containing monomers (hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, vinylphenol, etc.); and condensation polymerizable monomers such as ethylene oxide. The condensation polymerizable monomer may form a hydrophilic unit (or block) by reaction with an active hydrogen such as a hydroxyl group (for example, the hydroxyl group). The hydrophilic monomer may form a hydrophilic unit (or block) alone or in combination of two or more kinds. Preferred hydrophilic monomers are (meth)acrylic acid, maleic acid, maleic anhydride, and ethylene oxide.

[0052] The polymer dispersant only needs to have at least a carboxyl group, and may have a functional group of the hydrophilic monomer, for example, an acid group (sulfo group) or a hydroxyl group. These functional groups may be introduced into the polymer dispersant alone or in combination of two or more kinds.

[0053] The polymer dispersant may contain at least a hydrophilic unit (or hydrophilic block), and may be a homopolymer or copolymer of a hydrophilic monomer (for example, polyacrylic acid or its salt), or a copolymer of a hydrophilic monomer and a hydrophobic monomer. Examples of the hydrophobic monomer (nonionic monomer) include (meth)acrylate esters [C of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate 1-20(Meth)acrylic monomers such as alkyl, cycloalkyl (meth)acrylate (e.g., cyclohexyl (meth)acrylate), aryl (meth)acrylate (e.g., phenyl (meth)acrylate), benzyl (meth)acrylate, aralkyl (meth)acrylate (e.g., 2-phenylethyl (meth)acrylate), etc.; styrenic monomers such as styrene, α-methylstyrene, vinyltoluene, etc.; α-C 2-20 Olefinic monomers such as α-olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-octene, 1-dodecene, etc.); addition polymerizable monomers such as vinyl carboxylate esters (e.g., vinyl acetate, vinyl butyrate); C such as propylene oxide 3-6 Examples of the condensation polymerizable monomers include alkylene oxides. The hydrophobic monomers may form hydrophobic units alone or in combination of two or more.

[0054] The polymeric dispersant of the copolymer (e.g., a copolymer of a hydrophilic monomer and a hydrophobic monomer) may be a random copolymer, an alternating copolymer, a block copolymer (e.g., a copolymer composed of a hydrophilic block formed of a hydrophilic monomer and a hydrophobic block formed of a hydrophobic monomer), a comb copolymer (or a comb graft copolymer), etc. The structure of the block copolymer is not particularly limited and may be a diblock structure, a triblock structure (ABA type, BAB type), etc. In the comb copolymer, the main chain may be formed of the hydrophilic block or the hydrophobic block, or may be formed of the hydrophilic block and the hydrophobic block. The block copolymer of the hydrophilic block and the hydrophobic block can also improve the silver glossiness.

[0055] Incidentally, as described above, the hydrophilic unit can also be formed of a hydrophilic block (such as a polyalkylene oxide such as polyethylene oxide). The hydrophilic block (such as a polyalkylene oxide) and the hydrophobic block (such as a polyolefin block) may be bonded via a linking group such as an ester bond, an amide bond, an ether bond, or a urethane bond. These bonds may be formed, for example, by modifying the hydrophobic block (such as a polyolefin) with a modifier [such as an unsaturated carboxylic acid or its anhydride (such as (anhydrous) maleic acid), a lactam or an aminocarboxylic acid, a hydroxylamine, a diamine, etc.] and then introducing a hydrophilic block. Further, a polymer obtained from a monomer having a hydrophilic group such as a hydroxyl group or a carboxyl group (such as the hydroxyalkyl (meth)acrylate) and the hydrophilic monomer of the condensation type (such as ethylene oxide) may be reacted (or bonded) to form a comb copolymer (a comb copolymer having a hydrophobic block as the main chain).

[0056] Furthermore, the balance between hydrophilicity and hydrophobicity may be adjusted by using a hydrophilic nonionic monomer as a copolymerization component. Examples of such components include monomers or oligomers having an ethyleneoxy unit such as 2-(2-methoxyethoxy)ethyl (meth)acrylate and polyethylene glycol mono(meth)acrylate (for example, number average molecular weight 200 to 1,000). Also, the balance between hydrophilicity and hydrophobicity may be adjusted by modifying a hydrophilic group (such as a carboxyl group) (for example, by esterification).

[0057] In a polymer dispersant having a carboxyl group, the carboxyl group may be a salt or an acid anhydride group. For example, at least a part of the carboxyl groups may form a salt (such as a salt with an amine or a metal salt), but a polymer dispersant in which an acid group such as a carboxyl group does not form a salt [that is, a polymer dispersant having a free carboxyl group] can be preferably used.

[0058] The acid value of the polymer dispersant having a carboxyl group is, for example, 1 mgKOH / g or more (for example, 2 to 100 mgKOH / g), preferably 3 mgKOH / g or more (for example, 4 to 90 mgKOH / g), more preferably 5 mgKOH / g or more (for example, 6 to 80 mgKOH / g), still more preferably 7 mgKOH / g or more (for example, 8 to 50 mgKOH / g), and is usually 3 to 30 mgKOH / g (particularly 5 to 20 mgKOH / g). In such a polymer dispersant, the amine value may be 0 (or almost 0).

[0059] In addition, in the polymer dispersant, the position of the functional group is not particularly limited, and it may be in the main chain, in the side chain, or in both the main chain and the side chain. Such a functional group may be, for example, a functional group derived from a hydrophilic monomer or a hydrophilic unit (for example, a functional group introduced by copolymerization of (meth)acrylic acid, maleic anhydride, ethylene oxide, etc.).

[0060] The polymer dispersant having a carboxyl group may be used alone or in combination of two or more kinds.

[0061] In addition, as the polymer dispersant, a polymer dispersant (high molecular weight pigment dispersant) described in JP-A-2004-207558 or the like may be used. Further, the polymer dispersant may be synthesized or a commercially available product may be used. Hereinafter, specific examples of commercially available polymer dispersants (or dispersants composed of at least amphiphilic dispersants) are Solsperse series such as Solsperse 13240, Solsperse 13940, Solsperse 32550, Solsperse 31845, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 41090 [manufactured by Avecia Co., Ltd.]; Disperbyk series such as DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-170, DISPERBYK-180, DISPERBYK-182, DISPERBYK-184, DISPERBYK-190, DISPERBYK-191, DISPERBYK-192, DISPERBYK-193, DISPERBYK-194, DISPERBYK-2001, DISPERBYK-2015, DISPERBYK-2050 [manufactured by BYK-Chemie Japan Co., Ltd.]; EFKA series such as EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550, Polymer 100, Polymer 120, Polymer 150, Polymer 400, Polymer 401, Polymer 402, Polymer 403, Polymer 450, Polymer 451, Polymer 452, Polymer 453 [manufactured by EFKA Chemical Co., Ltd.]; Ajisper series such as Ajisper PB711, Ajisper PA111, Ajisper PB811, Ajisper PB821, Ajisper PW911 [manufactured by Ajinomoto Co., Inc.]; Floren series such as Floren DOPA-158, Floren DOPA-22, Floren DOPA-17, Floren TG-700, Floren TG-720W, Floren-730W, Floren-740W, Floren-745W [manufactured by Kyoeisha Chemical Co., Ltd.]; Johncryl series such as Johncryl 678, Johncryl 679, Johncryl 62 [manufactured by Johnson Polymer Co., Ltd.], and the like.Typical polymeric dispersants include DISPERBYK-190, DISPERBYK-194, DISPERBYK-2015, etc.

[0062] When the number average molecular weight of the polymeric dispersant is measured by gel permeation chromatography (GPC), in terms of polystyrene conversion, it is, for example, 1,500 to 100,000, preferably 2,000 to 80,000 (e.g., 2,000 to 60,000), more preferably 3,000 to 50,000 (e.g., 5,000 to 30,000), and even more preferably 7,000 to 20,000.

[0063] The polymeric dispersant having a carboxyl group may be a polymeric dispersant having no hydroxyl group.

[0064] The proportion of the protective colloid is, for example, 0.1 to 100 parts by mass (especially 1 to 50 parts by mass) with respect to 100 parts by mass of the silver-containing metal. The proportion of the polymeric dispersant having a carboxyl group can be selected from the range of, for example, about 0.1 to 60 parts by mass (e.g., 1 to 50 parts by mass) with respect to 100 parts by mass of the silver-containing metal, usually 2 to 40 parts by mass (e.g., 2.5 to 30 parts by mass), and more preferably 3 to 25 parts by mass (especially 5 to 20 parts by mass).

[0065] In the present application, the proportion of the protective colloid in the composite nanoparticles (a) can be measured by a conventional method, for example, thermal analysis (such as thermogravimetric / differential thermal simultaneous analysis, etc.).

[0066] If necessary, the protective colloid may contain other dispersants. The other dispersants may be inorganic compounds, but usually they are organic compounds. Examples of the other dispersants include alkanols (C alkanemonoalcohols such as hexanol, octanol, decanol, dodecanol, octadecanol, etc.), aldehydes (C 6-20 such as caprylaldehyde, laurylaldehyde, palmitoaldehyde, etc.) 6-20Examples thereof include aliphatic aldehydes, aliphatic hydroxycarboxylic acids, higher fatty acids or their salts, and sulfonic acids (such as alkanesulfonic acids, benzenesulfonic acids, and arenesulfonic acids such as toluenesulfonic acids). These other dispersants may be used alone or in combination of two or more.

[0067] The proportion of the other dispersant is, for example, 0.1 to 100 parts by mass, preferably 0.5 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymer dispersant.

[0068] The method for producing the composite nanoparticles is not particularly limited, and can be prepared by a conventional method. For example, when the silver-containing metal is silver alone, a silver compound corresponding to silver nanoparticles is reduced in a solvent in the presence of a protective colloid and a reducing agent. Specific production methods include, for example, the methods described in JP-A-2010-80442 and JP-A-2010-229544.

[0069] (B) Intermediate layer The intermediate layer (B) has a phase-separated structure including a first phase containing composite nanoparticles (b1) of a metal containing silver and a protective colloid and a first resin (b2), and composite nanoparticles (b3) of a metal containing silver and a protective colloid and a second resin (b4), and a second phase having a lower content ratio of the silver-containing metal than the first phase. By having a phase-separated structure with different concentrations of the silver-containing metal, even when the proportion of the resin component is increased, the silver glossiness can be improved, and both the silver glossiness and the adhesion and abrasion resistance can be achieved.

[0070] The modes in which the intermediate layer (B) has a phase-separated structure can be classified into a mode in which the first resin and the second resin are the same resin and a mode in which the first resin and the second resin are different resins.

[0071] In the embodiment where the first resin and the second resin are the same resin, for example, when the resin component contains a polyvinyl acetal resin alone, it can be presumed that the molecular structure of the polyvinyl acetal resin is influential. That is, the polyvinyl acetal resin has a hydrophobic group (an acetal group such as a butyral group, an acetyl group) and a hydrophilic group (a hydroxyl group) in the molecular chain. When the resin component is only a polyvinyl acetal resin, the composite nanoparticles are unevenly distributed on either the hydrophobic group or the hydrophilic group, resulting in a part with a relatively large amount of composite nanoparticles and a part with a small amount on the molecular chain of the polyvinyl acetal resin. That is, a structure similar to a phase-separated structure of a dense phase and a sparse phase of composite nanoparticles is formed on the molecular chain of the polyvinyl acetal resin. As a result, the phase containing a relatively large amount of composite nanoparticles (the phase with high shielding property) plays a role of shielding light (not transmitting it), and it can be presumed that a high degree of silver gloss is exhibited.

[0072] On the other hand, in the embodiment where the first resin and the second resin are different resins, it can be presumed that the phase-separated structure between the resins is influential. That is, when a first resin such as a cellulose resin and a second resin such as a (meth)acrylic resin are combined, the first resin and the second resin are phase-separated, and the composite nanoparticles are unevenly distributed in either phase. Therefore, even if the resin amount with respect to the metal containing silver is increased, a light shielding effect (non-transparency) can be obtained, and a high degree of silver gloss can be obtained. Therefore, when combining the first resin and the second resin, a large amount of resin can be blended, and the adhesion and abrasion resistance can be further improved.

[0073] (The first phase) In the first phase, the composite nanoparticles (b1) are the same as the composite nanoparticles (a) described in the section of the interface layer (A), including preferred embodiments, and are usually the same as the composite nanoparticles (a).

[0074] The first resin (b2) is not particularly limited, and examples thereof include polyolefin resins, (meth)acrylic resins, styrene resins, vinyl resins, polyvinyl acetal resins, polyester resins, polyamide resins, polyurethane resins, epoxy resins, silicone resins, cellulose resins, and the like. Among these, (meth)acrylic resins, polyvinyl acetal resins, polyester resins, and cellulose resins are preferable, and (meth)acrylic resins, polyvinyl acetal resins, and cellulose resins are particularly preferable. These first resins can be used alone or in combination of two or more.

[0075] ((meth)acrylic resin) The (meth)acrylic resin [the first (meth)acrylic resin] is not particularly limited, and examples thereof may include a homopolymer or copolymer of a (meth)acrylic monomer, a (meth)acrylic polyol, or a modified (meth)acrylic resin.

[0076] Examples of the (meth)acrylic monomer include (meth)acrylic acid; (meth)acrylic acid C such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate 1-20 alkyl; cycloalkyl (meth)acrylate such as cyclohexyl (meth)acrylate; aryl (meth)acrylate such as phenyl (meth)acrylate; aralkyl (meth)acrylate such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; hydroxy C such as hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate 1-4 alkyl-(meth)acrylate, and the like. These (meth)acrylic monomers can be used alone or in combination of two or more. Among these, (meth)acrylic acid C such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate 1-4 alkyl; hydroxy C such as hydroxyethyl (meth)acrylate 2-3An alkyl (meth)acrylate is preferred.

[0077] (The meth)acrylic resin may be a homopolymer of these monomers, but a copolymer is preferred. As the copolymer, it may be a copolymer of two or more of the above (meth)acrylic monomers, or it may be a copolymer of the (meth)acrylic monomer and a copolymerizable monomer. Examples of the copolymerizable monomer include styrenic monomers such as styrene, α-methylstyrene, vinyltoluene; olefinic monomers such as α-C 2-20 olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-octene, 1-dodecene, etc.); addition-polymerizable monomers such as vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate. These copolymerizable monomers can be used alone or in combination of two or more. Among these, styrenic monomers such as styrene are preferred.

[0078] When the (meth)acrylic resin is a copolymer of a (meth)acrylic monomer and a styrenic monomer (particularly, a copolymer of a methacrylic monomer and a styrenic monomer), the molar ratio of the (meth)acrylic monomer to the styrenic monomer is the former / latter = 95 / 5 to 5 / 95, preferably 90 / 10 to 10 / 90, more preferably 80 / 20 to 20 / 80, and still more preferably 70 / 30 to 30 / 70.

[0079] (The meth)acrylic polyol is not particularly limited as long as it is a (meth)acrylic polymer having two or more hydroxyl groups in the molecule. For example, as the monomer of the (meth)acrylic resin, hydroxy C 2-3 An alkyl (meth)acrylate-containing (meth)acrylic resin may also be used.

[0080] Examples of the modified (meth)acrylic resin include polyester-modified (meth)acrylic resins such as polyester (meth)acrylate, polyurethane-modified (meth)acrylic resins such as urethane (meth)acrylate, epoxy-modified (meth)acrylic resins such as epoxy (meth)acrylate, and silicone-modified (meth)acrylic resins such as silicone (meth)acrylate. These modified (meth)acrylic resins can be used alone or in combination of two or more.

[0081] These (meth)acrylic resins can be used alone or in combination of two or more. Among these, (meth)acrylic resins having a hydroxyl group (particularly, (meth)acrylic resins having a plurality of hydroxyl groups such as isocyanate-curable (meth)acrylic resins) are preferred because of their high affinity for silver-containing metal nanoparticles (especially composite nanoparticles) and their easy curability with a curing agent according to the application. (meth)acrylic resins having a hydroxyl group and a styrene unit (for example, methyl (meth)acrylate-hydroxyalkyl (meth)acrylate-styrene copolymer, etc.) are particularly preferred. The position of the hydroxyl group is not particularly limited and may be in the main chain, in the side chain, or in both the main chain and the side chain.

[0082] The acid value of the (meth)acrylic resin is, for example, 1 mgKOH / g or more (for example, 1 to 200 mgKOH / g), preferably 2 mgKOH / g or more (for example, 2 to 100 mgKOH / g), more preferably 3 mgKOH / g or more (for example, 3 to 50 mgKOH / g), and even more preferably 5 mgKOH / g or more (for example, 5 to 10 mgKOH / g). If the acid value is too small, the silver glossiness and the mechanical properties of the silver gloss film may deteriorate. On the contrary, if it is too large, the silver glossiness may deteriorate.

[0083] In the present application, the acid value of the (meth)acrylic resin can be measured by a conventional method, for example, the neutralization titration method.

[0084] The weight average molecular weight of the (meth)acrylic resin is, for example, from 1,000 to 300,000, preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000, still more preferably from 20,000 to 80,000, and most preferably from 30,000 to 50,000. If the molecular weight is too small, the mechanical properties of the silver gloss film may deteriorate. Conversely, if it is too large, the film-forming property may deteriorate.

[0085] In the present application, the weight average molecular weight of the (meth)acrylic resin is a value calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatography (GPC).

[0086] The glass transition temperature of the (meth)acrylic resin is, for example, from 0 to 120°C, preferably from 20 to 100°C, more preferably from 30 to 80°C, and most preferably from 40 to 60°C. If the glass transition temperature is too low, the mechanical properties of the silver gloss film may deteriorate. Conversely, if it is too high, the film-forming property may deteriorate.

[0087] In the present application, the glass transition temperature of the (meth)acrylic resin can be measured using a differential scanning calorimeter.

[0088] The (meth)acrylic resin may be a (meth)acrylic resin having no carboxyl group or its salt.

[0089] (Polyvinyl acetal resin) The polyvinyl acetal resin is obtained by reacting polyvinyl alcohol saponified from polyvinyl acetate with an aldehyde (particularly, n-butyl aldehyde) (acetalization reaction). In the acetalization reaction, since polyvinyl alcohol cannot be completely acetalized (particularly, butyralized), hydroxyl groups remain, and also a small amount of acetyl groups remain during saponification. Therefore, the polyvinyl acetal resin has acetal groups, hydroxyl groups, and acetyl groups in its structural units.

[0090] That is, the polyvinyl acetal resin contains, as constituent units, a vinyl acetal unit represented by the following formula (1), a vinyl alcohol unit represented by the following formula (2), and a vinyl ester unit represented by the following formula (3).

[0091]

Chemical formula

[0092] (In the formula, R 1 is a hydrogen atom or a hydrocarbon group)

[0093] In the formula (1), the hydrocarbon group represented by R 1 includes an alkyl group, a cycloalkyl group, and an aryl group. Examples of the alkyl group include linear or branched C 1-10 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, 2-ethylbutyl group, octyl group, 2-ethylhexyl group, nonyl group, etc. Examples of the cycloalkyl group include C 5-10 cycloalkyl groups such as cyclohexyl group. Examples of the aryl group include C 6-10 aryl groups such as phenyl group. As R 1 , these hydrocarbon groups and hydrogen atoms can be used alone or in combination of two or more.

[0094] Among these, as R 1 , a hydrogen atom or an alkyl group is preferable, a linear or branched C 1-5 alkyl group is more preferable, a linear C 2-4 alkyl group is even more preferable, and a propyl group is most preferable. That is, as the polyvinyl acetal resin, a polyvinyl formal resin or a polyvinyl butyral resin (butyral resin) is preferable, and a polyvinyl butyral resin is particularly preferable.

[0095] In addition to the structural units represented by the above formulas (1) to (3), the polyvinyl acetal resin may further contain other structural units. The other structural units may be units derived from copolymerizable monomers having a radical polymerizable group.

[0096] Examples of the copolymerizable monomers include vinyl esters of C 3-8 alkanoic acids such as vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate; vinyl ethers of C 1-6 alkyls such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether; α-C 2-6 olefins such as ethylene, propylene, 1-butene, isobutene, 1-hexene; (meth)acrylic acid and its salts; C 1-6 alkyl esters of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate; (meth)acrylamide; unsaturated sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and the like. These copolymerizable monomers can be used alone or in combination of two or more.

[0097] Further, the polyvinyl acetal resin may be a polyvinyl acetal resin modified or denatured by a conventional method.

[0098] The proportion (degree of acetalization) of the unit represented by the formula (1) in the polyvinyl acetal resin is about 5 to 95 mol% (for example, 10 to 90 mol%), and depending on the application, it may be, for example, 20 to 90 mol%, preferably 30 to 85 mol%, and may also be 50 mol% or more (for example, 50 to 90 mol%), preferably 60 mol% or more (for example, 60 to 85 mol%), more preferably 70 mol% or more (for example, 70 to 80 mol%). Further, the degree of acetalization may be, for example, 9 to 98 mass%, preferably 25 to 95 mass%, more preferably 35 to 90 mass%, 55 mass% or more (for example, 55 to 95 mass%), preferably 65 mass% or more (for example, 65 to 90 mass%), more preferably 70 mass% or more (for example, 70 to 80 mass%). If the degree of acetalization is too small, there is a risk of deterioration of silver glossiness, and conversely, if it is too large, there is a risk that the preparation of the polyvinyl acetal resin becomes difficult.

[0099] The proportion of the unit represented by the formula (2) (unit having a hydroxyl group) in the polyvinyl acetal resin may be 10 to 50 mol% (for example, 15 to 40 mol%), preferably 20 to 35 mol%, more preferably 23 to 27 mol%. Further, the proportion of the unit represented by the formula (2) in the polyvinyl acetal resin may be 5 to 40 mass% (for example, 12 to 30 mass%), preferably 15 to 25 mass%, more preferably 18 to 23 mass%. If the proportion of the unit represented by the formula (2) is too small, when the polyvinyl acetal resin is used alone as the resin component, there is a risk of deterioration of silver glossiness, and conversely, the same applies if it is too large. The polyvinyl acetal resin preferably contains a unit having a hydroxyl group because it has a high affinity for silver-containing metal nanoparticles (particularly, composite nanoparticles) and is easily cured by a curing agent depending on the application.

[0100] The proportion of the unit represented by the formula (3) (unit having an acetyl group) in the polyvinyl acetal resin is, for example, 15 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less. Further, the proportion of the unit represented by the formula (3) in the polyvinyl acetal resin is, for example, 20 mass% or less, preferably 10 mass% or less, more preferably 5 mass% or less. If the proportion of the unit represented by the formula (3) is too large, there is a risk of deterioration of silver glossiness.

[0101] The total proportion of the structural units represented by the formulas (1) to (3) in the polyvinyl acetal resin is, for example, 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and more preferably 100 mol%.

[0102] The proportion derived from the copolymerizable monomer in the polyvinyl acetal resin is, for example, 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less.

[0103] In the present application, the degree of acetalization and the proportion of each unit of the polyvinyl acetal resin can be measured using conventional methods, for example, titration method, IR method, NMR method, etc. Further, in the case of a butyral resin, it can be measured by a method conforming to JIS K 6728 "Test Methods for Polyvinyl Butyral".

[0104] The weight average molecular weight of the polyvinyl acetal resin (particularly, butyral resin) is, for example, 5,000 to 100,000, preferably 7,000 to 70,000, more preferably 10,000 to 40,000, and more preferably 12,000 to 20,000. If the molecular weight is too small, there is a risk of deterioration of the mechanical properties of the silver gloss film, and conversely, if it is too large, there is a risk of deterioration of film-forming properties.

[0105] In the present application, the weight-average molecular weight of the polyvinyl acetal resin is a value calculated based on the molecular weight of standard polystyrene from a chromatogram measured by gel permeation chromatography (GPC) in accordance with the method described in JIS K 0124-2011.

[0106] The glass transition temperature of the polyvinyl acetal resin (especially, butyral resin) can be selected from the range of about 50 to 130 °C, for example, 60 to 125 °C, preferably 70 to 120 °C, more preferably 80 to 115 °C, and even more preferably 90 to 110 °C. If the glass transition temperature is too low, the mechanical properties of the silver gloss film may deteriorate, and conversely, if it is too high, the film-forming property may deteriorate.

[0107] In the present application, the glass transition temperature of the polyvinyl acetal resin can be measured using a differential scanning calorimeter (DSC).

[0108] The viscosity of a 10% by mass solution of the polyvinyl acetal resin (especially, butyral resin) (solvent: toluene / ethanol (mass ratio) = 50 / 50) can be selected from the range of about 2 to 20,000 mPa·s (especially 10 to 10,000 mPa·s) when measured by a rotational viscometer (BM type) at a temperature of 20 °C. Depending on the application, for example, it may be 5 to 1,000 mPa·s (for example, 10 to 500 mPa·s), preferably 20 to 400 mPa·s (for example, 25 to 300 mPa·s), more preferably 50 to 250 mPa·s (for example, 70 to 200 mPa·s), or for example, 3 to 150 mPa·s (for example, 5 to 100 mPa·s), preferably 10 to 50 mPa·s (especially 10 to 30 mPa·s). If the viscosity is too low, the mechanical properties of the silver gloss film may deteriorate, and conversely, if it is too high, the film-forming property may deteriorate.

[0109] (Cellulose resin) The cellulose resin is not particularly limited, but may be a cellulose derivative obtained by modifying or denaturing cellulose.

[0110] Examples of the cellulose derivative include cellulose ester, cellulose ether, cellulose ether ester, etc. Examples of the cellulose ester include cellulose inorganic acid esters such as nitrocellulose, cellulose sulfate, and cellulose phosphate; cellulose organic acid esters such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate propionate butyrate. Examples of the cellulose ether include cellulose alkyl ethers such as methyl cellulose, ethyl cellulose, ethyl methyl cellulose, ethyl propyl cellulose, isopropyl cellulose, and butyl cellulose; carboxyalkyl celluloses such as carboxymethyl cellulose; hydroxyalkyl celluloses such as hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose. Examples of the cellulose ether ester include cellulose ether esters such as carboxymethyl cellulose acetate, carboxymethyl cellulose propionate, and carboxymethyl cellulose butyrate.

[0111] These cellulose derivatives can be used alone or in combination of two or more. Among these, cellulose organic acid esters and cellulose alkyl ethers are preferred.

[0112] As the cellulose organic acid ester, cellulose acylates are preferred, cellulose C 2-4 acylates are more preferred, and cellulose acetate C 3-4 acylates are even more preferred. The cellulose organic acid ester may be produced by the reaction of cellulose with an organic acid and / or acid anhydride, and in particular, it may be produced by hydrolyzing cellulose after triesterifying it with an organic acid and / or acid anhydride.

[0113] The degree of ester substitution of cellulose acylate is, for example, 30 to 70% by mass, preferably 35 to 65% by mass, more preferably 40 to 60% by mass, and still more preferably 45 to 55% by mass.

[0114] Cellulose acetate C 3-4 The degree of acetyl substitution of acylate is, for example, 0.5 to 30% by mass, preferably 0.8 to 20% by mass, and more preferably 1 to 10% by mass.

[0115] Cellulose acetate C 3-4 C of acylate 3-4 The degree of acyl substitution is, for example, 15 to 60% by mass, preferably 30 to 55% by mass, and more preferably 40 to 50% by mass.

[0116] In the present application, the degree of ester substitution of cellulose acylate can be measured using conventional methods, such as titration, gas chromatography analysis, IR elemental analysis, NMR method, etc. In particular, it may be measured by gas chromatography analysis.

[0117] The number average molecular weight of cellulose acylate is, for example, 1,000 to 300,000, preferably 5,000 to 100,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000, and most preferably 15,000 to 25,000. If the molecular weight is too small, the mechanical properties of the silver glossy film may deteriorate. Conversely, if it is too large, the film-forming property may deteriorate.

[0118] In the present application, the number average molecular weight of cellulose acylate is a value calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatography (GPC).

[0119] The glass transition temperature of cellulose acetate is, for example, 80 to 180 °C, preferably 90 to 170 °C, more preferably 100 to 160 °C, still more preferably 120 to 150 °C, and most preferably 130 to 140 °C. If the glass transition temperature is too low, the mechanical properties of the silver gloss film may deteriorate. Conversely, if it is too high, the film-forming property may deteriorate.

[0120] In the present application, the glass transition temperature of cellulose acetate can be measured using a differential scanning calorimeter.

[0121] As the cellulose alkyl ether, cellulose C 1-6 alkyl ether is preferred, and cellulose C 1-4 alkyl ether is more preferred, and cellulose C 2-3 alkyl ether is even more preferred. The cellulose alkyl ether may be produced by reacting the alkali cellulose obtained by alkalizing cellulose with an alkyl chloride.

[0122] The degree of ether substitution of the cellulose alkyl ether is, for example, 30 to 70% by mass, preferably 40 to 60% by mass, more preferably 45 to 55% by mass, still more preferably 48 to 50% by mass.

[0123] In the present application, the degree of ether substitution of the cellulose alkyl ether can be measured using conventional methods, such as titration, gas chromatography analysis, IR elemental analysis, NMR method, etc. In particular, it may be measured by gas chromatography analysis.

[0124] The number average molecular weight of the cellulose alkyl ether is, for example, 1,000 to 300,000, preferably 10,000 to 200,000, more preferably 30,000 to 100,000, still more preferably 50,000 to 70,000, and most preferably 60,000 to 65,000. If the molecular weight is too small, the mechanical properties of the silver gloss film may deteriorate. Conversely, if it is too large, the film-forming property may deteriorate.

[0125] In the present application, the number average molecular weight of the cellulose alkyl ether is a value calculated based on the molecular weight of standard polystyrene from the chromatogram measured by gel permeation chromatography (GPC).

[0126] The glass transition temperature of the cellulose alkyl ether is, for example, 80 to 180°C, preferably 100 to 150°C, more preferably 110 to 140°C, still more preferably 120 to 140°C, and most preferably 125 to 135°C. If the glass transition temperature is too low, the mechanical properties of the silver glossy film may deteriorate. Conversely, if it is too high, the film-forming property may deteriorate.

[0127] In the present application, the glass transition temperature of the cellulose alkyl ether can be measured using a differential scanning calorimeter.

[0128] Among these cellulose-based resins, cellulose ether is preferable and cellulose alkyl ether is particularly preferable from the viewpoint that silver gloss can be improved by combination with a different second resin.

[0129] Among them, as the first resin (b2), a cellulose-based resin is most preferable from the viewpoint of excellent silver glossiness and discoloration resistance.

[0130] In the first phase, the ratio of the silver-containing metal is, for example, 20 to 20,000 parts by mass, preferably 50 to 10,000 parts by mass, more preferably 100 to 5,000 parts by mass with respect to 100 parts by mass of the first resin (b2). If the ratio of the silver-containing metal is too small, the shielding property may deteriorate. If it is too large, the adhesion and abrasion resistance may deteriorate.

[0131] (Second phase) In the second phase, the composite nanoparticles (b3) are the same as the composite nanoparticles (a) described in the section of the interface layer (A), including preferred embodiments, and are usually the same as the composite nanoparticles (a).

[0132] The second resin (b4) is not particularly limited, and examples thereof include the resins exemplified as the first resin (b2) of the first phase. Among the resins, as the second resin (b4), (meth)acrylic resins, polyvinyl acetal resins, cellulose resins, and silicone resins are preferable. These second resins can be used alone or in combination of two or more. The second resin (b4) may be the same resin as the first resin (b2) or a different resin. For example, when the first resin (b2) is a (meth)acrylic resin, the second resin (b4) is preferably a silicone resin. When the first resin (b2) is a polyvinyl acetal resin, the second resin (b4) is preferably a polyvinyl acetal resin of the same resin. When the first resin (b2) is a cellulose resin, the second resin (b4) may be the same resin as the first resin (b2) or a different resin, but a (meth)acrylic resin (second (meth)acrylic resin) different from the first resin (b2) is preferable.

[0133] (Silicone resin) The silicone resin is not particularly limited and may be a silicone resin or a silicone oligomer. Among these, a silicone resin is preferable from the viewpoint of improving adhesion and abrasion resistance.

[0134] The silicone resin may be a thermoplastic resin, a curable resin (uncured resin), or a cured resin (crosslinked resin) having a polyorganosiloxane skeleton. The polyorganosiloxane skeleton is a linear, branched, or network compound having an Si—O bond (siloxane bond), and is represented by the formula: R 2 a SiO (4-a) / 2 (In the formula, R 2 represents a substituent, and the coefficient a is a number from 0 to 3) and is composed of units represented by the formula. As the silicone resin, a monofunctional M unit which is each unit represented by the above formula (generally R 2 3SiO 1 / 2 represented by the unit), a bifunctional D unit (generally R 2 2SiO 2 / 2units represented by), trifunctional T units (generally R 2 SiO 3 / 2 units represented by), tetrafunctional Q units (generally SiO 4 / 2 units represented by), among them, polyorganosiloxanes containing T units as the main units are usually used.

[0135] In the above formula, the substituent R 2 includes, for example, C such as methyl group, ethyl group, propyl group, butyl group 1-10 alkyl groups, halogenated C such as 3-chloropropyl group, 3,3,3-trifluoropropyl group 1-10 alkyl groups, C such as vinyl group, allyl group, butenyl group 2-10 alkenyl groups, C such as phenyl group, tolyl group, naphthyl group 6-20 aryl groups, C such as cyclopentyl group, cyclohexyl group 3-10 cycloalkyl groups, C such as benzyl group, phenethyl group 6-12 aryl-C 1-4 alkyl groups and the like. These substituents can be used alone or in combination of two or more.

[0136] Among these, R 2 includes, preferably, C such as methyl group, propyl group 1-4 alkyl groups, C such as phenyl group, naphthyl group 6-10 aryl groups, more preferably C 1-3 alkyl groups, C 6-8 aryl groups, most preferably methyl group and phenyl group. Further, R 2 is preferably used in combination of two or more from the viewpoint of improving the compatibility with (meth)acrylic resins rather than being used alone, and C 1-4 alkyl group and C 6-10 aryl group are more preferable, and C 1-3 alkyl group and C 6-8 aryl group combination is more preferable, and the combination of methyl group and phenyl group is most preferable.

[0137] C 1-4 alkyl group and C6-10 When combined with an aryl group, the molar ratio of the two can be selected from the range of about alkyl group / C 1-4 alkyl group / C 6-10 aryl group = about 30 / 1 to 1 / 30, for example, 20 / 1 to 1 / 10, preferably 10 / 1 to 1 / 5, more preferably 8 / 1 to 1 / 1, still more preferably 5 / 1 to 1.5 / 1, and most preferably 3 / 1 to 2 / 1.

[0138] The silicone resin may be a straight silicone resin (unmodified silicone resin) or a modified silicone resin. Examples of the modified silicone resin include silicone resins modified with other resins such as alkyd resins, phenolic resins, urea resins, melamine resins, and epoxy resins.

[0139] Specifically preferred silicone resins include those in which the substituent R 2 is a C 1-4 alkyl group such as a methyl group, C 1-4 alkyl-based silicone resin (for example, C 1-3 alkyl-based silicone resin such as methyl-based silicone resin, etc.), those in which the substituent R 2 is a C 6-10 aryl group such as a phenyl group, C 6-10 aryl-based silicone resin (for example, C 6-8 aryl-based silicone resin such as phenyl-based silicone resin, etc.), those in which the substituent R 2 is a combination of a C 1-4 alkyl group and a C 6-10 aryl group, C 1-4 alkyl C 6-10 aryl-based silicone resin (for example, C 1-3 alkyl C 6-8 aryl-based silicone resin such as methylphenyl-based silicone resin, propylphenyl-based silicone resin, etc.), etc. These silicone resins can be used alone or in combination of two or more. From the viewpoint of improving adhesion and abrasion resistance, C 1-4 alkyl C 6-10Alkylaryl silicone resins such as aryl silicone resins are preferred, and C 1-2 alkyl C 6-8 Aryl silicone resins are particularly preferred.

[0140] (Second (meth)acrylic resin) (Meth)acrylic resin [second (meth)acrylic resin] is not particularly limited, and can be selected from the (meth)acrylic resins exemplified as the first (meth)acrylic resin, including preferred embodiments.

[0141] Among them, as the second resin (b4), (meth)acrylic resin is most preferred in terms of excellent silver glossiness and discoloration resistance.

[0142] In particular, when combining the cellulose-based resin as the first resin (b2) and the (meth)acrylic resin as the second resin (b4), since the repulsive force of the phase separation of the silver layer is large, the phase separation structure of the intermediate layer (B) appears strongly (the shading of silver is clear), and it can be estimated that the glossiness can be improved by the uniform and disorder-free alignment of the composite nanoparticles (c) in the second interface layer (C). Furthermore, since the segregation force of the phase separation of the silver layer is large, the alignment of the composite nanoparticles (c) in the second interface layer (C) is difficult to collapse, and even when exposed to ultraviolet rays, the composite nanoparticles (c) are difficult to move from the second interface layer (C) to the intermediate layer (B), so it can be estimated that the change of the silver layer is difficult to occur (the disappearance region of the composite nanoparticles (c) is difficult to occur in the second interface layer (C)), and the discoloration resistance can also be improved.

[0143] In the intermediate layer (B), in the second resin (b4), the content ratio of the second phase is smaller than that of the first phase in the silver-containing metal (especially silver-containing metal nanoparticles) compared to the first resin (b2).

[0144] In the second phase, the proportion of the silver-containing metal may be 10,000 parts by mass or less, for example, 0 to 5,000 parts by mass, preferably 0 to 3,000 parts by mass, more preferably 0 to 2,000 parts by mass, based on 100 parts by mass of the second resin (b4). If the proportion of the silver-containing metal is too high, there is a risk that the adhesion and abrasion resistance will decrease.

[0145] (Composition of the intermediate layer (B)) The proportion of the first resin (b2) is, in terms of solid content, for example, 1 to 50 parts by mass, preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, still more preferably 10 to 25 parts by mass, most preferably 15 to 20 parts by mass, based on 100 parts by mass of the silver-containing metal in the silver gloss film [that is, the total amount of the silver-containing metal contained in the composite nanoparticles (a), (b1), (b3) and (c), and the same applies hereinafter]. If the proportion of the first resin (b2) is too small, there is a risk that the adhesion and abrasion resistance will decrease, and if it is too large, there is a risk that the silver glossiness will decrease.

[0146] The mass ratio of the first resin (b2) (especially a cellulose-based resin) to the second resin (b4) (especially a (meth)acrylic-based resin) (especially the mass ratio when both resins are different resins) can be selected from the range of about former / latter = 97 / 3 to 3 / 97 in terms of solid content, for example, 95 / 5 to 5 / 95, preferably 90 / 10 to 10 / 90 (for example, 80 / 20 to 30 / 70), more preferably 80 / 20 to 20 / 80 (for example, 75 / 25 to 40 / 60), still more preferably 70 / 30 to 30 / 70 (especially 60 / 40 to 40 / 60). If the proportion of the first resin (b2) is too small, there is a risk that the silver glossiness and adhesion will decrease, and the same risk exists if it is too large.

[0147] The total proportion of the first resin (b2) and the second resin (b4) (particularly, the total proportion of cellulose and (meth)acrylic resin) can be selected from the range of about 1 to 500 parts by mass, for example, 5 to 300 parts by mass (e.g., 10 to 250 parts by mass), preferably 5 to 200 parts by mass (e.g., 10 to 200 parts by mass), more preferably 10 to 100 parts by mass (e.g., 10 to 50 parts by mass), and still more preferably 20 to 50 parts by mass (particularly 25 to 35 parts by mass) with respect to 100 parts by mass of the silver-containing metal in the silver glossy film. If the total proportion is too small, there is a risk of deterioration in adhesion and abrasion resistance, and if it is too large, there is a risk of deterioration in silver glossiness.

[0148] (b5) Other components The intermediate layer (B) may contain other metal nanoparticles, conventional additives, etc. as other components (b5) as long as the effects of the present invention are not impaired. Examples of conventional additives include curing agents, surface modifiers, plasticizers (or film-forming aids), gloss imparting agents, metal corrosion inhibitors (rust preventives), stabilizers (such as antioxidants, ultraviolet absorbers, and light stabilizers), surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, particularly, anionic surfactants and / or nonionic surfactants), dispersion stabilizers, thickeners or viscosity modifiers, moisturizing agents, thixotropy imparting agents, leveling agents, penetrants, defoaming agents, pH adjusters, chelating agents, surface tension adjusters, colorants (such as dyes and pigments), hue improvers, dye fixatives, bactericides, fungicides, preservatives, oxygen absorbers, etc. Note that the surfactant may be an acetylene glycol-based surfactant, a polysiloxane-based surfactant, a fluorine-based surfactant, etc. These additives can be used alone or in combination of two or more.

[0149] The proportion of other components (b5) is 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the silver-containing metal in the silver glossy film.

[0150] (Structure of the intermediate layer (B)) The intermediate layer (B) may have a phase-separated structure in which it is phase-separated into a first phase and a second phase having a lower content ratio of the silver-containing metal than this first phase.

[0151] The ratio between the first phase and the second phase (area ratio in the cross-section) can be selected from the range of about the first phase / the second phase = 97 / 3 to 10 / 90, for example, 95 / 5 to 20 / 80, preferably 90 / 10 to 30 / 70, more preferably 80 / 20 to 40 / 60, still more preferably 70 / 30 to 50 / 50, and most preferably 65 / 35 to 55 / 45. If the proportion of the first phase is too small, there is a risk of deterioration in silver glossiness and adhesion, and the same risk exists if it is too large.

[0152] In the present application, the ratio can be measured based on a transmission electron microscope (TEM) image of the cross-section of the silver gloss film.

[0153] The phase separation structure may be a sea-island structure or a co-continuous structure. Among these, a sea-island structure is preferred.

[0154] When the intermediate layer (B) has a sea-island structure, the continuous phase (matrix phase) constituting the sea portion may be the first phase or the second phase. Among these, it is preferable that the second phase is the continuous phase. By forming the continuous phase with the second phase having a lower content ratio of the silver-containing metal than the first phase, the composite nanoparticles (b1) can be aggregated in the dispersed phase to improve the shielding property.

[0155] In the sea-island structure, the average diameter of the dispersed phase is, for example, 5 to 3,000 nm, preferably 10 to 1,000 nm, more preferably 100 to 800 nm, still more preferably 300 to 600 nm, and most preferably 400 to 500 nm. If the average diameter of the dispersed phase is too small, there is a risk of deterioration in the shielding property, and if it is too large, there is a risk of deterioration in adhesion and abrasion resistance. In the present application, when the shape of the dispersed phase is an anisotropic shape, the average value of the major axis and the minor axis is taken as the diameter of each dispersed phase.

[0156] The average pitch of the dispersed phase (the average value of the distance between the centers of adjacent dispersed phases) is, for example, 5 to 2,500 nm, preferably 10 to 2,000 nm, more preferably 100 to 1,500 nm, still more preferably 300 to 1,000 nm, and most preferably 500 to 700 nm. If the average pitch of the dispersed phase is too small, there is a risk that the adhesion and abrasion resistance will decrease. If it is too large, there is a risk that the shielding property will decrease.

[0157] The method for observing the cross-section of the silver gloss film is not particularly limited, and a method used for ordinary structural analysis can be used. Examples of the observation method include morphological and structural observation by a transmission electron microscope (TEM), a scanning electron microscope (SEM), an electron probe microanalyzer (EPMA), a scanning probe microscope (SPM), etc.; analysis of constituent elements by X-ray fluorescence, energy-dispersive X-ray spectroscopy (EDX), wavelength-dispersive X-ray spectroscopy (WDX), electron energy-loss spectroscopy (Electron Energy-Loss Spectroscopy (EELS)), etc. Among these, observation by a transmission electron microscope (TEM) is preferred because it can observe even fine structures. The sample for observation can be appropriately processed and used so as to be suitable for observation and analysis. For example, a thin slice sample may be prepared using a microtome or the like.

[0158] Therefore, in the present application, the structure, size, and distribution state of the island structure in the cross-section of the silver gloss film can be observed and measured based on the TEM image of the cross-section of the silver gloss film. The size is the average value of any 10 locations. Furthermore, in the TEM image, since the silver-containing metal nanoparticles are dark in color, they can be easily confirmed. In the intermediate layer, the aggregated portion of the silver-containing metal nanoparticles is used as the dispersed phase.

[0159] The average thickness of the intermediate layer (B) is, for example, 0.05 to 30 μm, preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, still more preferably 0.5 to 3 μm, and most preferably 0.8 to 1.5 μm. If the average thickness of the intermediate layer (B) is too thin, there is a risk that the light shielding property, adhesion, and abrasion resistance will decrease. If it is too thick, there is a risk that the silver gloss property will decrease.

[0160] The average thickness of the intermediate layer (B) may be 2 times or more (for example, 3 to 1,000 times) the average thickness of the second interface layer (C), for example, 5 to 500 times, preferably 10 to 300 times, more preferably 25 to 250 times, still more preferably 25 to 100 times, and most preferably 30 to 50 times. If the thickness ratio of the intermediate layer (B) is too small, there is a risk of deterioration in adhesion and abrasion resistance. If it is too large, there is a risk of deterioration in silver glossiness.

[0161] In the present application, the average thickness of the intermediate layer (B) can be measured by observing the cross-section of the silver gloss film with a transmission electron microscope (TEM), and is shown as the average value of any three locations.

[0162] (C) Second interface layer The second interface layer (C) is formed of composite nanoparticles (c) of a silver-containing metal and a protective colloid. By arranging or orienting the composite nanoparticles (c) on the surface portion of the silver gloss film, the silver-containing metal forms a dense thin film (silver thin film). In the present invention, by forming such a second interface layer (C) on the surface of the silver gloss film, the silver glossiness can be improved.

[0163] The composite nanoparticles (c) are the same as the composite nanoparticles (a) described in the section of the first interface layer (A), including preferred embodiments, and are usually the same as the composite nanoparticles (a).

[0164] The average thickness of the second interface layer (C) is, for example, 3 to 300 nm (for example, 10 to 250 nm), preferably 5 to 200 nm, more preferably 10 to 100 nm, still more preferably 15 to 50 nm, and most preferably 20 to 40 nm. If the average thickness of the second interface layer (C) is too thin, there is a risk of deterioration in silver glossiness. If it is too thick, there is a risk of deterioration in abrasion resistance.

[0165] In the present application, the average thickness of the second interface layer (C) can be measured by observing the cross-section of the silver gloss film with a transmission electron microscope (TEM), and is shown as the average value of any three locations.

[0166] (Average thickness of the silver layer) The average thickness of the silver layer is, for example, 0.05 to 30 μm, preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, still more preferably 0.5 to 3 μm, and most preferably 1 to 1.5 μm.

[0167] [Top coat layer] The top coat layer is formed of a cured product of a curable composition containing an epoxy resin and a curing agent. In the present invention, the cured product contains a metaxylylenediamine unit (structure or skeleton derived from metaxylylenediamine) as a constitutional unit, whereby discoloration of the silver layer can be suppressed.

[0168] (Epoxy resin) The epoxy resin (first epoxy resin) may be any compound having an epoxy group in the molecule, and a compound having two or more epoxy groups in the molecule is preferred. The epoxy resin includes an epoxy resin having a glycidyl group, an epoxy resin having an alicyclic epoxy group, etc., but an epoxy resin having a glycidyl group is preferred.

[0169] Examples of the epoxy resin having a glycidyl group include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc.

[0170] Examples of the glycidyl ether type epoxy resin include biphenyl type epoxy resins, naphthalene type epoxy resins, bisphenol type epoxy resins [for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, etc., bis(hydroxyphenyl)C 1-10Epoxy resins having an alkane skeleton; tetrabromobisphenol A type resin; bisphenol S type epoxy resin, etc., novolac type epoxy resins (for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, etc.), aliphatic type epoxy resins (for example, hydrogenated bisphenol A type epoxy resin, propylene glycol mono- or diglycidyl ether, pentaerythritol mono- or tetraglycidyl ether, etc.), monocyclic epoxy resins (for example, resorcin diglycidyl ether, etc.), heterocyclic epoxy resins (for example, triglycidyl isocyanurate having a triazine ring, hydantoin type epoxy resin having a hydantoin ring, etc.), tetrakis(glycidyloxyphenyl)ethane, etc. can be mentioned.

[0171] The glycidylamine type epoxy resin may be an epoxy resin derived from amines (particularly polyamines such as aromatic polyamines), and in particular, may be a reaction product of amines (particularly polyamines) and epichlorohydrin. Examples of the reaction product of amines and epichlorohydrin include, for example, aromatic glycidylamine type epoxy resins (for example, glycidyl aromatic diamines such as mono- to tetraglycidyl diaminodiphenylmethane, mono- to tetraglycidyl metaxylylenediamine, mono- to tetraglycidyl paraxylylenediamine; glycidyl anilines such as mono- or diglycidylaniline, mono- or diglycidyltoluidine, N,N-mono- or diglycidyl-2,4,6-tribromoaniline, mono- to triglycidyl-p-aminophenol, mono- to triglycidyl-m-aminophenol, etc.), aliphatic glycidylamine type epoxy resins [for example, mono- to tetraglycidyl hydrogenated metaxylylenediamine (mono- to tetraglycidyl 1,3-bis(aminomethyl)cyclohexane), mono- to tetraglycidyl hydrogenated paraxylylenediamine, etc., mono- to tetraglycidyl diamines, etc.], compounds in which the glycidyl group in these compounds is a 2-methylglycidyl group, etc. can be mentioned.

[0172] The glycidyl ester type epoxy resin may be a glycidyl ester of a carboxylic acid (particularly, a polyvalent carboxylic acid). Examples of the glycidyl ester type epoxy resin include aromatic glycidyl ester type epoxy resins (for example, diglycidyl phthalate, diglycidyl terephthalate, dimethyl glycidyl phthalate, etc.), aliphatic glycidyl ester type epoxy resins (for example, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, etc.).

[0173] These epoxy resins can be used alone or in combination of two or more. Among these, from the viewpoint of suppressing the discoloration of the silver layer, epoxy resins having an aromatic skeleton, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, glycidyl aromatic diamines such as tetraglycidyl metaxylylenediamine and tetraglycidyl paraxylylenediamine are preferable, and epoxy resins having a metaxylylenediamine unit, for example, glycidyl aromatic diamines such as tetraglycidyl metaxylylenediamine are particularly preferable.

[0174] The epoxy equivalent of the epoxy resin is, for example, 40 to 1000 g / eq, preferably 50 to 300 g / eq, more preferably 70 to 150 g / eq, and still more preferably 80 to 120 g / eq. If the epoxy equivalent of the epoxy resin is too small, the mechanical properties of the silver gloss film may deteriorate, and conversely, if it is too large, the silver gloss property may deteriorate.

[0175] In the present application, the epoxy equivalent is defined as "the mass of an epoxy resin containing 1 equivalent of epoxy groups" and can be measured in accordance with JIS K 7236.

[0176] The proportion of the epoxy resin may be 5% by mass or more in the top coat layer (in the solid content of the top coat layer), for example, 5 to 90% by mass, preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and still more preferably 20 to 30% by mass.

[0177] (Hardener) As the curing agent (first curing agent), for example, amine-based curing agents or modified products thereof [e.g., aliphatic polyamines (ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, etc.), alicyclic polyamines (isophoronediamine, etc.), aromatic polyamines (xylenediamine, etc.) and other amine-based curing agents; modified products of the amine-based curing agents (epoxy adducts, acrylonitrile adducts, ethylene oxide adducts, Mannich reaction products, Michael reaction products, thiourea reaction products, etc.), etc.], polyaminoamide-based curing agents (e.g., condensates of polyethylene polyamine and fatty acids, etc.), acid and acid anhydride-based curing agents [e.g., aliphatic carboxylic acid anhydrides (dodecenyl succinic anhydride, etc.), alicyclic carboxylic acid anhydrides (methyltetrahydrophthalic anhydride, etc.), aromatic carboxylic acid anhydrides (phthalic anhydride, etc.), etc.] and the like can be mentioned.

[0178] These curing agents can be used alone or in combination of two or more. Among these curing agents, amine-based curing agents or modified products thereof, and polyaminoamide-based curing agents are preferred. From the viewpoint of suppressing discoloration of the silver layer, amine-based curing agents or modified products thereof having an aromatic skeleton (e.g., aromatic polyamines or modified products thereof), and polyaminoamide-based curing agents having an aromatic skeleton are more preferred, and amine-based curing agents or modified products thereof having a metaxylylenediamine unit (particularly, metaxylylenediamine or its epoxy adduct) are more preferred.

[0179] The ratio of the curing agent can be selected from the range of about 1 to 1000 parts by mass with respect to 100 parts by mass of the epoxy resin, for example, 10 to 900 parts by mass, preferably 50 to 800 parts by mass, more preferably 70 to 500 parts by mass, still more preferably 100 to 300 parts by mass, and most preferably 150 to 250 parts by mass. If the ratio of the curing agent is too small, the mechanical properties of the silver gloss film may deteriorate. Conversely, if it is too high, the mechanical properties of the silver gloss film may also deteriorate.

[0180] (Properties of the top coat layer) The top coat layer contains a metaxylylenediamine unit as a constituent unit from the viewpoint of suppressing discoloration of the silver layer. The metaxylylenediamine unit only needs to be contained in the cured product, but is preferably contained in at least one of the epoxy resin and the curing agent. Among these, it is preferable that at least the curing agent contains a (meth)xylylenediamine unit, and from the viewpoint of highly suppressing discoloration of the silver layer, it is more preferable that both the epoxy resin and the curing agent contain a metaxylylenediamine unit.

[0181] In addition to the epoxy resin and the curing agent, the top coat layer may further contain a conventional additive. Examples of the conventional additive include a curing agent, a surface conditioner, a plasticizer (or a film-forming aid), a gloss agent, a metal corrosion inhibitor (rust preventive agent), a stabilizer (such as an antioxidant, an ultraviolet absorber, a light stabilizer, etc.), a surfactant (an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant), a dispersion stabilizer, a thickener or a viscosity modifier, a moisturizer, a thixotropy-imparting agent, a leveling agent, a penetrant, an antifoaming agent, a pH adjuster, a chelating agent, a surface tension adjuster, a colorant (such as a dye or a pigment), a hue improver, a dye fixing agent, a bactericide, a fungicide, a preservative, an oxygen absorber, etc.

[0182] The proportion of the conventional additive is 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass in total of the epoxy resin and the curing agent in the top coat layer.

[0183] The top coat layer may have an oxygen permeability of 50 mL / m 2 / day / atm or less (particularly 30 mL / m 2 / day / atm or less), for example, 0.1 to 30 mL / m 2 / day / atm, preferably 0.5 to 25 mL / m 2 / day / atm, more preferably 1 to 20 mL / m 2 / day / atm, still more preferably 3 to 15 mL / m 2 / day / atm, and most preferably 5 to 10 mL / m 2 / day / atm. If the oxygen permeability is too low, the thickness of the top coat layer may increase. Conversely, if it is too high, there is a risk that the discoloration of the silver layer cannot be suppressed.

[0184] In the present application, the oxygen permeability of the top coat layer can be measured in accordance with JIS K 7126-2:2006. Specifically, it can be measured by the method described in the examples below.

[0185] The average thickness of the top coat layer may be 0.5 to 30 μm (for example, 0.8 to 25 μm), but for example, 0.5 to 20 μm (especially 0.8 to 10 μm), preferably 0.8 to 15 μm (for example, 0.8 to 5 μm), more preferably 1 to 20 μm (for example, 1 to 10 μm), still more preferably 1.5 to 10 μm (for example, 1.5 to 5 μm), and most preferably 2 to 4 μm (especially 2.5 to 3.5 μm). If the average thickness of the top coat layer is too thin, light interference may occur due to the top coat layer, making it difficult to manufacture a silver gloss film having high glossiness. Conversely, if it is too thick, there is a risk that the top coat layer will discolor.

[0186] [Undercoat layer] In order to suppress the discoloration of the silver layer, the silver gloss film of the present invention may have an undercoat layer laminated on the first interface layer (A) of the silver layer. For example, as shown in FIG. 3, it may be formed by an undercoat layer 24 laminated on a decorated body (substrate) 23, a silver layer 22 laminated on this undercoat layer 24, and a top coat layer 21 laminated on this silver layer 22. In the present invention, the undercoat layer 24 laminated on the decorated body (substrate) 23 is formed of a cured product of a curable composition containing an epoxy resin and a curing agent. Since the cured product contains a metaxylylenediamine unit, discoloration due to ultraviolet rays from the decorated body (substrate) 23 side can be suppressed. Therefore, when the substrate is made of a material with low gas barrier properties (for example, resins such as polyester-based resins and polycarbonate-based resins), the silver gloss film of the present invention preferably includes an undercoat layer.

[0187] As the epoxy resin (second epoxy resin), it can be selected from the epoxy resins exemplified as the first epoxy resin of the top coat layer, including preferred embodiments.

[0188] As the curing agent (second curing agent), it can be selected from the first curing agent of the top coat layer, including preferred embodiments.

[0189] The undercoat layer may further contain conventional additives in addition to the epoxy resin and the curing agent. Examples of the conventional additives include the additives exemplified as the conventional additives of the top coat layer. The ratio of the conventional additives can also be selected from the range of the ratios described as the ratio of the conventional additives of the top coat layer, including preferred embodiments.

[0190] The oxygen permeability and the average thickness of the undercoat layer can be selected from the range of the oxygen permeability and the range of the average thickness described as the oxygen permeability and the average thickness of the top coat layer, including preferred embodiments.

[0191] The average thickness of the undercoat layer may be 0.5 μm or more, for example, 0.5 to 200 μm, preferably 1 to 150 μm, more preferably 10 to 120 μm, still more preferably 20 to 100 μm, and most preferably 25 to 50 μm. If the average thickness of the undercoat layer is too thin, there is a risk that discoloration from the substrate side cannot be suppressed, and if it is too thick, there is a risk that the design property of the silver gloss film will deteriorate.

[0192] [Properties of the silver gloss film] The silver gloss film of the present invention is excellent in discoloration resistance, and the color difference ΔE before and after the weather resistance test with an irradiance of 120 W / m 2 , a black panel temperature of 63 °C, and an irradiation time of 100 hours may be less than 5, for example, 0.1 to 4.8, preferably 0.2 to 4.7, more preferably 0.3 to 4.5. From the point that the thickness of the silver gloss film does not become too large and it is also excellent in discoloration resistance, it is preferably 0.5 to 4, more preferably 1 to 3.5, and most preferably 2 to 3.

[0193] In the present application, the color difference ΔE can be measured by the method described in the examples to be described later in detail.

[0194] [Method for manufacturing silver gloss film] The silver gloss film of the present invention is obtained by sequentially laminating a silver layer and a top coat layer on a substrate.

[0195] (Substrate) The type of the substrate is not particularly limited, and a resin substrate, a metal substrate, a glass substrate, a ceramic substrate, paper, etc. can be used according to the application. Among these, resin substrates and glass substrates are widely used, and a glass substrate is preferable in terms of being easy to suppress discoloration of the silver gloss film. In the present invention, even if the substrate is a resin substrate, discoloration of the silver gloss film can be suppressed by forming an undercoat layer.

[0196] Examples of the resin substrate include substrates formed of polyolefin resins, (meth)acrylic resins, styrene resins, polycarbonate resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, cellulose resins, etc. Among these, even a resin substrate with low gas barrier properties, for example, a substrate formed of an amorphous resin such as a polycarbonate resin (such as bisphenol A type polycarbonate) or a polystyrene resin (such as polystyrene), or a (meth)acrylic resin (such as polymethyl methacrylate), can suppress discoloration of the silver gloss film by forming an undercoat layer. Among these, a resin substrate formed of a crystalline resin is preferable in terms of being easy to suppress discoloration of the silver gloss film, and a resin substrate formed of a polyester resin such as polyethylene terephthalate is particularly preferable.

[0197] (Manufacturing process of silver layer) The silver layer is obtained through a coating step of applying a liquid composition containing composite nanoparticles of a silver-containing metal and a protective colloid, a first resin, a second resin, and a solvent onto a decorated object (substrate), and a phase separation step of drying the coating film formed of the liquid composition to obtain a silver layer having a phase separation structure.

[0198] (Coating step of silver layer) In the step of applying the silver layer, the liquid composition can be prepared by mixing the composite nanoparticles, the first resin, the second resin, and the solvent in a conventional manner. As the mixing method, a conventional stirring device can be used, for example, a stirring and defoaming device may be used. By incorporating a solvent into the liquid composition, phase separation can be promoted and film-forming properties can also be improved.

[0199] The solvent (first solvent) preferably contains a polar organic solvent. Examples of the polar organic solvent include monoalcohols (C alkanols such as methanol, ethanol, propanol, isopropanol, etc., 3-methoxy-3-methyl-1-butanol, etc.), polyhydric alcohols (alkanediols such as ethylene glycol, propylene glycol, etc., alkanetriols such as glycerin, trimethylolpropane, etc., alkanetetraols such as pentaerythritol, etc.), amides (acylamides such as formamide, acetamide, etc., mono- or di-C acylamides such as N-methylformamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, diacetone alcohol, methyl ethyl ketone, isophorone, etc.), ethers (dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, etc.), alkylene glycol monoalkyl ethers (C alkylene glycol monoalkyl ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, etc.), dialkylene glycol monoalkyl ethers (di-C alkylene glycol monoalkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), cellosolve acetates (C cellosolve acetates such as ethyl cellosolve acetate, etc.) 1-4 alkyl, 3-methoxy-3-methyl-1-butanol, etc.), polyhydric alcohols (alkanediols such as ethylene glycol, propylene glycol, etc., alkanetriols such as glycerin, trimethylolpropane, etc., alkanetetraols such as pentaerythritol, etc.), amides (acylamides such as formamide, acetamide, etc., mono- or di-C acylamides such as N-methylformamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, diacetone alcohol, methyl ethyl ketone, isophorone, etc.), ethers (dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, etc.), alkylene glycol monoalkyl ethers (C alkylene glycol monoalkyl ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, etc.), dialkylene glycol monoalkyl ethers (di-C alkylene glycol monoalkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), cellosolve acetates (C cellosolve acetates such as ethyl cellosolve acetate, etc.) 1-4 alkyl, 3-methoxy-3-methyl-1-butanol, etc.), polyhydric alcohols (alkanediols such as ethylene glycol, propylene glycol, etc., alkanetriols such as glycerin, trimethylolpropane, etc., alkanetetraols such as pentaerythritol, etc.), amides (acylamides such as formamide, acetamide, etc., mono- or di-C acylamides such as N-methylformamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, diacetone alcohol, methyl ethyl ketone, isophorone, etc.), ethers (dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, etc.), alkylene glycol monoalkyl ethers (C alkylene glycol monoalkyl ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, etc.), dialkylene glycol monoalkyl ethers (di-C alkylene glycol monoalkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), cellosolve acetates (C cellosolve acetates such as ethyl cellosolve acetate, etc.) 2-6 alkyl, 3-methoxy-3-methyl-1-butanol, etc.), polyhydric alcohols (alkanediols such as ethylene glycol, propylene glycol, etc., alkanetriols such as glycerin, trimethylolpropane, etc., alkanetetraols such as pentaerythritol, etc.), amides (acylamides such as formamide, acetamide, etc., mono- or di-C acylamides such as N-methylformamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, diacetone alcohol, methyl ethyl ketone, isophorone, etc.), ethers (dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, etc.), alkylene glycol monoalkyl ethers (C alkylene glycol monoalkyl ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, etc.), dialkylene glycol monoalkyl ethers (di-C alkylene glycol monoalkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), cellosolve acetates (C cellosolve acetates such as ethyl cellosolve acetate, etc.) 1-4 alkyl, 3-methoxy-3-methyl-1-butanol, etc.), polyhydric alcohols (alkanediols such as ethylene glycol, propylene glycol, etc., alkanetriols such as glycerin, trimethylolpropane, etc., alkanetetraols such as pentaerythritol, etc.), amides (acylamides such as formamide, acetamide, etc., mono- or di-C acylamides such as N-methylformamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, diacetone alcohol, methyl ethyl ketone, isophorone, etc.), ethers (dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, etc.), alkylene glycol monoalkyl ethers (C alkylene glycol monoalkyl ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, etc.), dialkylene glycol monoalkyl ethers (di-C alkylene glycol monoalkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), cellosolve acetates (C cellosolve acetates such as ethyl cellosolve acetate, etc.) 2-6 alkyl, 3-methoxy-3-methyl-1-butanol, etc.), polyhydric alcohols (alkanediols such as ethylene glycol, propylene glycol, etc., alkanetriols such as glycerin, trimethylolpropane, etc., alkanetetraols such as pentaerythritol, etc.), amides (acylamides such as formamide, acetamide, etc., mono- or di-C acylamides such as N-methylformamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, diacetone alcohol, methyl ethyl ketone, isophorone, etc.), ethers (dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, etc.), alkylene glycol monoalkyl ethers (C alkylene glycol monoalkyl ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, etc.), dialkylene glycol monoalkyl ethers (di-C alkylene glycol monoalkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), cellosolve acetates (C cellosolve acetates such as ethyl cellosolve acetate, etc.) 1-4 alkyl, 3-methoxy-3-methyl-1-butanol, etc.), polyhydric alcohols (alkanediols such as ethylene glycol, propylene glycol, etc., alkanetriols such as glycerin, trimethylolpropane, etc., alkanetetraols such as pentaerythritol, etc.), amides (acylamides such as formamide, acetamide, etc., mono- or di-C acylamides such as N-methylformamide, N-methylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.), pyrrolidones (2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-methyl-3-pyrrolidone, etc.), ketones (acetone, diacetone alcohol, methyl ethyl ketone, isophorone, etc.), ethers (dioxane, tetrahydrofuran, etc.), organic carboxylic acids (acetic acid, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, etc.), alkylene glycol monoalkyl ethers (C alkylene glycol monoalkyl ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol methyl ether, 3-methoxy-3-methyl-1-butanol, etc.), dialkylene glycol monoalkyl ethers (di-C alkylene glycol monoalkyl ethers such as methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, etc.), cellosolve acetates (C cellosolve acetates such as ethyl cellosolve acetate, etc.)1-4 alkyl - cellosolve acetates), carbitol acetates (such as methyl carbitol acetate, butyl carbitol acetate, etc., C 1-4 alkyl - carbitol acetates, etc.), dimethyl sulfoxide, etc. These polar organic solvents can be used alone or in combination of two or more.

[0200] The proportion of the polar organic solvent may be 50% by mass or more in the solvent, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass.

[0201] In addition to the polar organic solvent, the solvent may further contain a non - polar organic solvent. Examples of the non - polar organic solvent include aliphatic hydrocarbons such as hexane, octane, and decane, and alicyclic hydrocarbons such as cyclohexane and tetralin. The proportion of the non - polar organic solvent may be 50 parts by mass or less (for example, about 0.1 to 50 parts by mass) with respect to 100 parts by mass of the polar organic solvent, preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

[0202] Among these solvents, it is preferable to contain one or more selected from alcohols, esters, alkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ethers, and it is more preferable to contain one or more selected from aliphatic carboxylic acid C 1-6 alkyl esters, alkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ethers. Among them, the solvent preferably comprises a combination of an alkylene glycol monoalkyl ether and a dialkylene glycol monoalkyl ether, and C 2-6 alkylene glycol mono C 1-3 alkyl ether and di C 2-6 alkylene glycol mono C 1-3 alkyl ether and di C 4-6 alkylene glycol mono C 1-2 alkyl ether and di C 2-4An alkylene glycol mono C 1-2 A combination with an alkyl ether is most preferred.

[0203] When the solvent is a combination of an alkylene glycol monoalkyl ether and a dialkylene glycol monoalkyl ether, the composite nanoparticles may be mixed with a first resin, a second resin, and an alkylene glycol monoalkyl ether in the form of a dispersion dispersed in the dialkylene glycol monoalkyl ether.

[0204] When the solvent is a combination of an alkylene glycol monoalkyl ether and a dialkylene glycol monoalkyl ether, the proportion of the dialkylene glycol monoalkyl ether may be 100 parts by mass or less with respect to 100 parts by mass of the alkylene glycol monoalkyl ether, for example, 0.01 to 50 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 1 to 15 parts by mass, and most preferably 2 to 10 parts by mass. If the proportion of the dialkylene glycol monoalkyl ether is too large, the effect of promoting phase separation may decrease. The dialkylene glycol monoalkyl ether may be a polar solvent derived from a dispersion medium for dispersing the composite nanoparticles as a raw material.

[0205] The proportion of the solvent is, for example, 50 to 500 parts by mass, preferably 80 to 400 parts by mass, more preferably 100 to 300 parts by mass, still more preferably 120 to 250 parts by mass, and most preferably 150 to 200 parts by mass with respect to 100 parts by mass of the silver-containing metal of the composite nanoparticles. If the proportion of the solvent is too small, it becomes difficult to form a phase separation structure and the film-forming property may decrease. If it is too large, the productivity and the film-forming property may decrease.

[0206] The coating method is not particularly limited, and conventional coating methods can be used, such as flow coating method, dispenser coating method, spin coating method, spray coating method, screen printing method, flexographic printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method, photolithography method, inkjet method, offset printing method, etc.

[0207] The average thickness (dry thickness) of the coating film is, for example, 0.05 to 100 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 10 μm, and even more preferably 1 to 5 μm.

[0208] In the present invention, it is possible to achieve both silver glossiness, adhesion, and abrasion resistance without forming an undercoat layer and a topcoat layer. However, depending on the application, an undercoat layer and / or a topcoat layer may be used in combination.

[0209] (Phase separation process of silver layer) In the phase separation process of the silver layer, by drying the coating film, as the solvent volatilizes, it phase-separates into a first phase containing a large amount of silver-containing metal and a second phase containing a small amount of silver-containing metal. When the first resin and the second resin are different resins, phase separation may occur by spinodal decomposition.

[0210] As the drying method of the coating film, a method of heating and drying is preferred. From the viewpoint of easily forming a phase separation structure, a method of heat treatment in two steps by combining preheating treatment and main heat treatment is preferred.

[0211] In the preheating treatment, the preheating temperature is, for example, 40 to 80 °C, preferably 45 to 70 °C, more preferably 45 to 60 °C, and even more preferably 45 to 55 °C. The preheating time is, for example, 1 to 100 minutes, preferably 3 to 60 minutes, more preferably 5 to 30 minutes.

[0212] In this heat treatment, the heat treatment temperature is, for example, 60 to 150 °C, preferably 65 to 120 °C, more preferably 70 to 90 °C, and even more preferably 75 to 85 °C. The heat treatment time is, for example, 30 to 240 minutes, preferably 80 to 180 minutes, and more preferably 100 to 150 minutes.

[0213] (Manufacturing process of the top coat layer) The top coat layer is obtained through a coating step of applying a liquid composition containing a first epoxy resin, a first curing agent, and a solvent (second solvent) onto the silver layer, and a curing step of heating and curing the coating film formed from the liquid composition to obtain the top coat layer.

[0214] In the coating step of the top coat layer, the liquid composition can be prepared by mixing the first epoxy resin, the first curing agent, and the solvent in a conventional manner. As the mixing method, a conventional stirring device can be used, for example, a stirring and defoaming device may be used.

[0215] The solvent preferably contains a polar organic solvent. Examples of the polar organic solvent include the polar organic solvents exemplified in the coating step of the silver layer. Among the polar organic solvents, it is preferable to contain one or more selected from alcohols, esters, alkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ethers, and C 2-6 Alkylene glycol mono C 1-3 Alkyl ether is more preferable, and C 4-6 Alkylene glycol mono C 1-2 Alkyl ether is most preferable.

[0216] The proportion of the solvent is, for example, 5 to 1000 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, even more preferably 30 to 70 parts by mass, and most preferably 40 to 60 parts by mass with respect to a total of 100 parts by mass of the first epoxy resin and the first curing agent.

[0217] The coating method is not particularly limited, and a conventional coating method exemplified in the coating step of the silver layer can be used.

[0218] The average thickness (dry thickness) of the coating film is, for example, 0.05 to 100 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 10 μm, and even more preferably 1 to 5 μm.

[0219] In the curing step of the top coat layer, the top coat layer is formed by heating and curing the coating film.

[0220] The heating temperature of the coating film is, for example, 60 to 150 °C, preferably 65 to 120 °C, more preferably 70 to 90 °C, and even more preferably 75 to 85 °C. The heating time is, for example, 5 to 120 minutes, preferably 10 to 60 minutes, and more preferably 20 to 40 minutes.

[0221] (Manufacturing process of the undercoat layer) When the silver gloss film of the present invention includes an undercoat layer, as a pretreatment step of applying a silver layer on a substrate, a coating step of applying a liquid composition containing a second epoxy resin, a second curing agent, and a solvent (third solvent) on the substrate, and a curing step of obtaining an undercoat layer by heating and curing the coating film formed from the liquid composition are carried out.

[0222] In the coating step of the undercoat layer, the liquid composition can be prepared by mixing the second epoxy resin, the second curing agent, and the solvent in a conventional manner. As the mixing method, a conventional stirring device can be used, for example, a stirring and defoaming device may be used.

[0223] As the solvent, it can be selected from the solvents exemplified in the section of the top coat layer, including preferred embodiments. The proportion of the solvent can also be selected from the range of the proportions described in the section of the top coat layer, including preferred embodiments.

[0224] The average thickness (dry thickness), heating temperature, and heating time of the coating film can also be selected from the average thickness (dry thickness), heating temperature, and heating time described in the section of the top coat layer, respectively.

Examples

[0225] The present invention will be described in more detail based on the following examples, but the present invention is not limited by these examples. In the following examples, the materials used and the measurement methods of the evaluation tests are shown below.

[0226] [Materials Used] (Resin Components) Cellulose-based resin: Cellulose acetate butyrate "CAB-553-0.4" sold by Yaba Kogyo Co., Ltd. Acrylic resin: "WXU-880" manufactured by DIC Corporation, isocyanate-curable acrylic resin, non-volatile content 50% by mass, hydroxyl value 10 mg KOH / g, glass transition temperature 90 °C Silicone resin: "KR211" manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl silicone resin Polyvinyl butyral resin: "Esrec KS-10" manufactured by Sekisui Chemical Co., Ltd., degree of acetalization 74 mol% or more, acetyl group 3 mol% or less, hydroxyl group 25 mol%, 10% by mass solution viscosity (temperature 20 °C, rotational viscosity type (BM type), solvent = toluene / ethanol = 50 / 50 (mass ratio)) 10 - 30 mPa·s, glass transition temperature 106 °C, weight average molecular weight 17,000 Epoxy resin A: "Maxceleb M-100" manufactured by Mitsubishi Gas Chemical Company, Inc., containing metaxylylenediamine units Epoxy resin B: "jER827" manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 180 - 190, non-containing metaxylylenediamine units Epoxy resin C: "jER806H" manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, epoxy equivalent 165 - 175, non-containing metaxylylenediamine units Epoxy resin D: "TETRAD-C" manufactured by Mitsubishi Gas Chemical Company, Inc., polyfunctional epoxy resin, non-containing metaxylylenediamine units Epoxy resin E: "jER604" manufactured by Mitsubishi Chemical Corporation, diaminodiphenylmethane type epoxy resin, non-containing metaxylylenediamine units

[0227] (Hardener) Polyamine curing agent: "Maxceeve C-93" manufactured by Mitsubishi Gas Chemical Company, Inc., containing a metaxylylenediamine unit Modified amine resin curing agent: "Fujicure FXR-1020" manufactured by T&K TOKA Co., Ltd., not containing a metaxylylenediamine unit Isocyanate curing agent: "Takenate D-170N" manufactured by Mitsui Chemicals, Inc.

[0228] (Additives and solvents) Polymeric dispersant having a carboxyl group: "Disperbyk 190" manufactured by BYK-Chemie GmbH, solution of a high molecular weight block copolymer having a pigment affinity group, solvent: water, non-volatile content 40% by mass, acid value 10 mg KOH / g, amine value 0 Ultraviolet absorber: "Tinuvin 479" manufactured by BASF Japan Ltd. 3-Methoxy-3-methyl-1-butanol: "Solfit" manufactured by Kuraray Co., Ltd., boiling point 174°C

[0229] (Substrate) Glass substrate: "Water-repellent release S9224" manufactured by Matsunami Glass Industry Co., Ltd., 1.5 mm thick Polyester substrate: Polyethylene terephthalate (PET) substrate, "Sunday PET PG1" manufactured by Acrysand Co., Ltd., 3.0 mm thick

[0230] [Oxygen permeability of the topcoat layer] Using an oxygen permeability measuring device ("OX-TRAN 2 / 22" manufactured by MOCON Inc.), after forming a topcoat layer similar to the test specimens obtained in each example on a glass substrate, the topcoat layer was peeled off from the glass substrate, and based on the method conforming to JIS K 7126-2:2006, the oxygen permeability of the topcoat layer was measured under the measurement conditions of 23°C and 60% RH.

[0231] [Evaluation and determination] For each test specimen (test specimens of examples, comparative examples, and reference examples), in order to determine whether a silver glossy film capable of solving the problems of the present application was obtained, glossiness, weather resistance (color change resistance), adhesion, and abrasion resistance were verified.

[0232] [Glossiness] For each of the test specimens obtained in each example (a composite in which a silver gloss film was laminated on a base material), using an ultraviolet-visible-near-infrared spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation) and an integrating sphere ("ISR-3100" manufactured by Shimadzu Corporation), the glossiness (L value) was calculated from the intensity of the reflected light in the wavelength range of 380 to 780 nm. As the standard sample, an aluminum-deposited mirror with a glossiness of 100.0 ("Product number: 202-35988" manufactured by Shimadzu Corporation) was used. It can be said that a silver gloss film with a higher L value is superior in glossiness. Regarding the glossiness (L value) of each of the obtained test specimens, it was judged according to the criteria shown below, and from the viewpoint of glossiness in practical use, a c judgment or higher was regarded as passing.

[0233] (Glossiness judgment criteria) a judgment: Glossiness (L value) is 65 or more (pass) b judgment: Glossiness (L value) is 60 or more and less than 65 (pass) c judgment: Glossiness (L value) is 50 or more and less than 60 (pass) d judgment: Glossiness (L value) is less than 50 (fail)

[0234] [Weather resistance (color change resistance) of silver gloss film] For each of the test specimens obtained in each example (a composite in which a silver gloss film was laminated on a base material), the color difference ΔE before and after the weather resistance test using a xenon weather meter was evaluated, and from the viewpoint of weather resistance (color change resistance), a silver gloss film with a c judgment or higher was regarded as passing.

[0235] Specifically, it was evaluated by the following method. Regarding the weather resistance test, using a xenon weather meter ("SC750-W" manufactured by Suga Test Instruments Co., Ltd.), the test specimen was processed under the conditions of irradiance: 120 W / m 2 , black panel temperature: 63 °C, irradiation time: 100 hours.

[0236] Regarding the color difference ΔE, using an ultraviolet-visible-near-infrared spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation) and an integrating sphere ("ISR-3100" manufactured by Shimadzu Corporation), from the reflected light in the wavelength range of 380 to 780 nm, lightness (L * ) and chromaticity (a * , b *) was obtained. The difference in lightness (ΔL * ) and the difference in chromaticity (Δa * , Δb * ) of the specimens before and after the weather resistance test were used to calculate the color difference (ΔE) based on the following formula. Since a smaller color difference (ΔE) before and after the weather resistance test indicates less discoloration in an environment exposed to ultraviolet light, it can be said that the silver gloss film is suitable for long-term use.

[0237] ΔE = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 1 / 2

[0238] Regarding the ΔE of each obtained specimen, the following criteria were used for judgment. From the perspective of the practical weather resistance (color fastness) of the silver gloss film for long-term use, silver gloss films with a c judgment or higher were considered qualified.

[0239] (Judgment criteria for weather resistance (color fastness)) a judgment: The color difference ΔE before and after the weather resistance test is less than 2.0 (qualified) b judgment: The color difference ΔE before and after the weather resistance test is 2.0 or more and less than 3.0 (qualified) c judgment: The color difference ΔE before and after the weather resistance test is 3.0 or more and less than 5.0 (qualified) d judgment: The color difference ΔE before and after the weather resistance test is 5.0 or more (unqualified)

[0240] [Adhesion] For the cured film, an adhesion test was carried out by sticking cellophane tape (registered trademark) and peeling it off forcefully, and it was visually confirmed whether there was peeling on the film. The adhesion was judged according to the following criteria. From the perspective of the practical adhesion of the silver gloss film, silver gloss films with an a judgment were considered qualified.

[0241] (Judgment criteria for adhesion) a judgment: There is no peeling on the film (qualified) d judgment: There is peeling on the film (unqualified)

[0242] [Scratch resistance] ​For the cured film, a friction test was conducted using a friction and wear tester with dry cotton under a load of 500 g for 10 reciprocations. The glossiness (L value) of the cured film before and after the friction test was measured, and the reduction rate of the glossiness before and after the friction test was calculated using the following formula, and the scratch resistance was determined according to the following criteria. From the perspective of the practical scratch resistance of the silver gloss film, the silver gloss film with an a judgment was considered qualified.

[0243] Reduction rate of glossiness (L value) (%) = [(Glossiness (L value) after the test - Glossiness (L value) before the test) / (Glossiness (L value) before the test)] × 100

[0244] (Scratch resistance judgment criteria) a judgment: Reduction rate of glossiness (L value) is less than 20% (qualified) d judgment: Reduction rate of glossiness (L value) is 20% or more (unqualified)

[0245] [Comprehensive judgment] Based on the judgment of each evaluation item (glossiness, weather resistance (color change resistance), adhesion, scratch resistance), the superiority and inferiority were judged according to the judgment criteria shown in Table 1, and a comprehensive evaluation was made. The silver gloss films of ranks A, B, and C were considered qualified.

[0246]

Table 1

[0247] [Observation of film cross-section] A sample was cut out from the obtained silver gloss film, embedded in an epoxy resin, which is a general-purpose embedding resin, and the cutting cross-section was exposed with a microtome for TEM observation. Further, in order to observe the fine structure, after the cutting cross-section was exposed with a microtome, an ultra-thin section with a thickness of about 100 nm or less was prepared and TEM observation was carried out, and the size (average diameter and average pitch) of the dispersed phase was measured by the following method. As described later, the cross-section observation was performed on each test body before and after the weather resistance test.

[0248] (Preparation method of composite nanoparticle dispersion) 66.8 g of silver nitrate and 7.2 g of a polymer dispersant having a carboxyl group were added to 100 g of ion-exchanged water and stirred vigorously to obtain a suspension. To this suspension, 100 g of dimethylaminoethanol (manufactured by Fujifilm Wako Pure Chemical Corporation) was gradually added so that the water temperature did not exceed 50°C, and then heated and stirred in a water bath at 50°C for 4 hours to obtain a composite nanoparticle dispersion.

[0249] An excessive amount of methanol was added to the obtained composite nanoparticle dispersion and stirred, and then the composite nanoparticles were precipitated by centrifugation to remove the supernatant. Again, methanol was added and stirred, and then the composite nanoparticles were precipitated by centrifugation to remove the supernatant. Diethylene glycol monobutyl ether was added to the methanol solution containing the obtained precipitate, and the methanol mixed therein was removed by an evaporator to obtain a composite nanoparticle dispersion having a silver content of 70% by mass in the dispersion. Regarding this dispersion, when the particle size of the silver nanoparticles constituting the composite nanoparticles was confirmed with a transmission electron microscope (manufactured by JEOL Ltd.), the number-average particle diameter of the primary particles was about 20 nm.

[0250] (Method for preparing the composition for silver layer) (Examples 1 to 14, Comparative Examples 1 to 5, Reference Examples 1 to 2) The obtained composite nanoparticle dispersion, resin component, and solvent were stirred and mixed using a stirring and defoaming device ("Mazel Star" manufactured by Kurabo Industries Ltd.) at the ratios shown in Table 2 to prepare a composition for silver layer.

[0251]

Table 2

[0252] In Tables 2, 3, and 7, the mass ratio of the acrylic resin in the composition is the mass ratio based on the solid content (non-volatile content).

[0253] (Examples 15 to 17) In Examples 15 to 17, the composition for silver layer was prepared in the same manner except that the formulation of the composition for silver layer was changed to the composition shown in Table 7.

[0254] (Formation of silver layer) On the glass substrate (Tables 3 to 5 and 7) or various substrates shown in Table 6, using a 10 μm bar coater, after applying the composition for the silver layer, it was dried in an oven at 80 °C for 2 hours to form a silver layer. The average thickness (dry thickness) of the silver layer was 1.2 μm. The cross-sectional photograph by TEM of the silver gloss film (before the weather resistance test) obtained in Example 1 is shown in Fig. 4, and the cross-sectional photograph by TEM of the silver gloss film (before the weather resistance test) obtained in Comparative Example 2 is shown in Fig. 5. When the cross-section of each obtained silver layer was confirmed by TEM, inside the film, it was phase-separated into a region where the composite nanoparticles aggregated (dispersed phase) and a region where the aggregation of the composite nanoparticles was small (continuous phase). That is, both silver gloss films (Example 1 and Comparative Example 2) had an intermediate layer (B) with a phase-separated structure that was phase-separated into a region where the composite nanoparticles aggregated (first phase) and a region where the aggregation of the composite nanoparticles was small (second phase) inside the film (the composite nanoparticles had a structure unevenly distributed in the dispersed phase). The phase-separated structure was a sea-island structure, the first phase where the composite nanoparticles aggregated formed the dispersed phase, and the second phase where the aggregation of the composite nanoparticles was small formed the continuous phase. Furthermore, at the surface and the interface with the substrate, the composite nanoparticles were aligned to form a thin continuous layer (thin layer), that is, a first interface layer (A) on the interface side with the substrate and a second interface layer (C) on the surface side.

[0255] (Formation of top coat layer) The respective components were stirred and mixed using a stirring and defoaming device at the ratios shown in Tables 3 to 7 to prepare a composition for the top coat layer.

[0256] On the silver layer, using a bar coater, after applying the composition for the top coat layer, it was dried in an oven at 80 °C for 30 minutes to form a top coat layer, and a test body (a laminate in which a silver gloss film was laminated on a substrate) having the structure shown in Fig. 1 or 3 was obtained.

[0257] The average thickness (dry thickness) of the top coat layer of each test specimen was adjusted respectively by adjusting the coating conditions of the bar coater, and the average thickness (μm) of each was as shown in Tables 3 to 7. No top coat layer was provided in Comparative Example 1.

[0258] (Formation of undercoat layer) In Examples 10 and 12 to 14, an undercoat layer composition was prepared at the ratio shown in Table 6 in the same manner as the top coat layer composition. After applying the undercoat layer composition on the substrate under the same conditions as the top coat layer and then drying, an undercoat layer was formed on the substrate. Then, a silver layer and a top coat layer were laminated on the undercoat layer to obtain a test specimen having the structure shown in Figure 3 (a laminate in which a silver gloss film was laminated on the substrate via an undercoat layer).

[0259] The average thickness (dry thickness) of the undercoat layer of each test specimen was adjusted respectively by adjusting the coating conditions of the bar coater, and the average thickness (μm) of each was as shown in Table 6.

[0260] [Verification results and discussion] The evaluation results of the obtained test specimens are shown in Tables 3 to 7 respectively.

[0261] Table 3 shows the comparison results with the conventionally widely used top coat layer.

[0262]

Table 3

[0263] (Comparative Example 1) Comparative Example 1 is an example of a silver gloss film without a top coat layer. In Comparative Example 1, discoloration of the silver layer occurred due to exposure to ultraviolet rays in the weather resistance test, and the color difference ΔE before and after the weather resistance test was as large as 23.8. Since it was considered not practical for long-term use from the viewpoint of weather resistance (color change resistance), it was judged as d (failed) in the evaluation of weather resistance (color change resistance) and ranked D in the comprehensive judgment.

[0264] (Comparative Examples 2 and 3) Comparative Example 2 is an example of a silver gloss film in which a cured acrylic resin, which is commonly used for protecting paints, is formed (laminated) as a top coat layer on top of the silver layer. In Comparative Example 2, the color difference ΔE before and after the weather resistance test was still as large as 20.1, and almost no improvement was seen in the discoloration of the silver layer. Therefore, in the evaluation of weather resistance (color change resistance), it was judged as d (failed), and in the comprehensive evaluation, it was ranked D.

[0265] Also, in Comparative Example 3, as a conventional method, a top coat layer in which an ultraviolet absorber was added to the cured acrylic resin of Comparative Example 2 was formed (laminated) on top of the silver layer to protect the silver layer from ultraviolet rays, attempting to improve the weather resistance (color change resistance). In Comparative Example 3, although there was a slight improvement in weather resistance (color change resistance), the color difference ΔE before and after the weather resistance test was still as large as 7.9, and it was insufficient as a countermeasure against the discoloration of the silver layer. Therefore, in the evaluation of weather resistance (color change resistance), it was judged as d (failed), and in the comprehensive evaluation, it was ranked D.

[0266] (Example 1) Example 1 is an example of a silver gloss film in which a cured epoxy resin composition containing a metaxylylenediamine unit is formed (laminated) as a top coat layer on top of the silver layer. In Example 1, compared with Comparative Examples 1 to 3, a remarkable improvement in weather resistance (color change resistance) was seen. Since the color difference ΔE before and after the weather resistance test was improved to a practically problem - free level of 2.5, in the evaluation of weather resistance (color change resistance), it was judged as b (passed). Furthermore, since Example 1 was also excellent with an a judgment in the evaluations of glossiness, adhesion, and abrasion resistance, a silver gloss film that can achieve both glossiness, weather resistance (color change resistance), adhesion, and abrasion resistance was obtained, and in the comprehensive evaluation, it was ranked B.

[0267] Further, the cross-sectional photographs by TEM after the weather resistance test of Example 1 are shown in FIG. 6, and the cross-sectional photographs by TEM after the weather resistance test of Comparative Example 2 are shown in FIG. 7. In FIG. 6 (Example 1), even after the weather resistance test, similar to before the weather resistance test, there are a first interface layer (A) and a second interface layer (C) in which the composite nanoparticles are aligned, and in the film interior, there is a phase-separated structure in which the region where the composite nanoparticles aggregate (first phase) and the region where the aggregation of the composite nanoparticles is small (second phase) are phase-separated to form an intermediate layer (B). On the other hand, in FIG. 7 (Comparative Example 2), it was observed that after the weather resistance test, the alignment of the composite nanoparticles in the second interface layer (C) on the surface side was partially disrupted and disappeared. That is, in Comparative Example 2 without weather resistance (color change resistance), the composite nanoparticles in the second interface layer (C) exposed to ultraviolet rays by the weather resistance test partially moved to the intermediate layer (B), and the structure of the silver layer changed, resulting in color change of the silver gloss film. On the other hand, in Example 1 with weather resistance (color change resistance), by laminating a top coat layer containing a metaxylylenediamine unit on the silver layer, the movement of the composite nanoparticles in the second interface layer (C) due to the weather resistance test can be prevented. Therefore, it is presumed that the change in the structure of the silver layer is small and the color change (color difference ΔE) before and after the weather resistance test is small.

[0268] Table 4 shows the comparison results when the composition of the cured product of the epoxy resin of the top coat layer was changed.

[0269]

Table 4

[0270] (Examples 1 to 5, Comparative Examples 4 to 5) Example 2 is an example in which, based on Example 1, the curing agent is changed from "a polyamine curing agent containing a metaxylylenediamine unit" to "a modified aliphatic amine resin curing agent not containing a metaxylylenediamine unit". In Example 2, since the curing agent does not contain a metaxylylenediamine unit, the weather resistance (discoloration resistance) decreased slightly. However, since the epoxy resin contains a metaxylylenediamine unit, the top coat layer formed of the cured epoxy resin contains a metaxylylenediamine unit, so the weather resistance (discoloration resistance) was judged to be at a practically acceptable level of c, and thus it was ranked C in the comprehensive judgment.

[0271] Examples 3 to 5 are examples in which, based on Example 1, the epoxy resin is changed to "an epoxy resin not containing a metaxylylenediamine unit" respectively. In Examples 3 to 5, since the epoxy resin does not contain a metaxylylenediamine unit, the weather resistance (discoloration resistance) decreased slightly. However, since the curing agent contains a metaxylylenediamine unit, the top coat layer formed of the cured epoxy resin contains a metaxylylenediamine unit, so the weather resistance (discoloration resistance) was judged to be at a practically acceptable level of c, and thus it was ranked C in the comprehensive judgment.

[0272] Comparative Examples 4 to 5 are examples in which both the epoxy resin and the curing agent are changed to those not containing a metaxylylenediamine unit. In Comparative Examples 4 to 5, since neither the epoxy resin nor the curing agent contains a metaxylylenediamine unit, the top coat layer formed of the cured epoxy resin does not contain a metaxylylenediamine unit. Therefore, in Comparative Examples 4 to 5, perhaps because the change in the structure of the silver layer due to exposure to ultraviolet rays in the weather resistance test could not be suppressed, the color difference ΔE before and after the weather resistance test became larger than 5, and from the viewpoint of weather resistance (color change resistance), it was judged (failed) at a practically unacceptable level and ranked D in the comprehensive judgment. From the above results, in the top coat layer, when at least one of the epoxy resin and the curing agent contains a metaxylylenediamine unit, the top coat layer formed of the cured epoxy resin contains a metaxylylenediamine unit, and as a result, it was found that discoloration of the silver layer before and after the weather resistance test can be prevented, and a silver glossy film with high weather resistance (color change resistance) can be obtained. Furthermore, since all of the test specimens of Examples 2 to 5 were excellent with an A judgment in the evaluation of glossiness, adhesion, and abrasion resistance, it was found that a silver glossy film capable of achieving both glossiness, weather resistance (color change resistance), adhesion, and abrasion resistance was obtained.

[0273] On the other hand, in Example 1 in which both the epoxy resin and the curing agent contain a metaxylylenediamine unit, the oxygen permeability of the top coat layer was 30 mL / m 2 / day / atm or less, while in Examples 2 to 5 in which only one of the epoxy resin or the curing agent contains a metaxylylenediamine unit, the oxygen permeability of the top coat layer was greater than 30 mL / m 2 / day / atm. From this result, by setting the oxygen permeability of the top coat layer to 30 mL / m 2 / day / atm or less, the weather resistance (color change resistance) can be further improved, and it was found that a silver glossy film (ranked B) with a balance in all items of glossiness, weather resistance (color change resistance), adhesion, and abrasion resistance can be obtained.

[0274] Also, Table 5 shows the comparison results when the average thickness of the top coat layer was changed.

[0275]

Table 5

[0276] (Example 1, Examples 6 - 9, Comparative Examples 1 - 2) Examples 1, 6 - 9, and Comparative Examples 1 - 2 are examples in which the average thickness of the topcoat layer is changed based on Example 1. In Examples 6 and 7 where the average thickness of the topcoat layer was made smaller than that of Example 1, a silver - gloss film having weather resistance (color change resistance) equal to or better than that of Example 1 was obtained, and thus it was ranked A or B in the comprehensive judgment. On the other hand, in Examples 8 - 9 and Comparative Examples 1 - 2 where the average thickness of the topcoat layer was made larger than that of Example 1, due to the significant discoloration of the topcoat layer before and after the weather resistance test as the thickness of the topcoat layer increased, discoloration occurred in the entire silver - gloss film. It can be seen that the weather resistance (color change resistance) tends to decrease as the average thickness increases. When the average thickness is in the range of 0.5 - 20 μm, the weather resistance (color change resistance) is at a practically acceptable level of c judgment or higher. From these results, it was found that for a silver - gloss film with excellent weather resistance (color change resistance) suitable for long - term use, the average thickness of the topcoat layer should be 0.5 - 20 μm. In any case, it was also excellent in gloss, adhesion, and abrasion resistance. Furthermore, in Example 6 where the average thickness of the topcoat layer was 3 μm, the discoloration of the silver - gloss film could be minimized by minimizing the discoloration of the silver layer and the topcoat layer, so it was judged at level a with the most excellent weather resistance (color change resistance). Since it was judged at level a in all evaluations of gloss, weather resistance (color change resistance), adhesion, and abrasion resistance, it can be said that it is the silver - gloss film with the most excellent balance (rank A) from the viewpoints of gloss, weather resistance (color change resistance), adhesion, and abrasion resistance.

[0277] Also, the comparison results regarding the substrate and the undercoat layer are shown in Table 6.

[0278]

Table 6

[0279] (Example 1, Examples 10 - 14) Example 10 is an example in which an undercoat layer having the same composition and average thickness as the topcoat layer is further provided between the silver layer and the base material of Example 1. In Example 10, there was no significant difference from Example 1 in each evaluation.

[0280] Example 11 is an example in which the base material of Example 1 is changed from a glass substrate to a PET substrate. In Example 11, by using a PET substrate with relatively low gas barrier properties as the base material, the protection of the silver layer on the base material side was slightly reduced, resulting in discoloration of the silver layer. Therefore, the color difference ΔE before and after the weather resistance test was slightly larger, and the weather resistance (color change resistance) was judged as c. On the other hand, in Examples 12 to 14 in which an undercoat layer was further provided in Example 11, the weather resistance (color change resistance) could be improved by protecting the silver layer from the base material side. Therefore, the color difference ΔE became smaller and the weather resistance (color change resistance) was improved. Furthermore, there was a tendency that the weather resistance (color change resistance) became better as the average thickness increased in Examples 12 (1 μm), 13 (4 μm), and 14 (30 μm). In Example 14 with an average thickness of 30 μm of the undercoat layer, weather resistance (color change resistance) at a practically problem-free level (b judgment) equivalent to that of Example 1 using a glass substrate for the base material was obtained.

[0281] From the above results, by providing an undercoat layer of a cured epoxy resin containing a metaxylylenediamine unit between the base material and the silver layer (the first interface layer) and setting its average thickness to 20 μm or more, even when using a base material with relatively low gas barrier properties, a silver gloss film excellent in glossiness, weather resistance (color change resistance), adhesion, and abrasion resistance can be obtained. Also, while the suitable average thickness of the topcoat layer is 0.5 to 20 μm, the suitable average thickness of the undercoat layer is 20 μm or more, and it was an unexpected result that the suitable average thickness ranges were different.

[0282] Also, Table 7 shows the comparison results when the resin component of the silver layer (intermediate layer) is changed.

Table 7

[0283] (Example 1, 15 to 17) Examples 15 to 17 are examples in which the resin components of the composition for the silver layer are changed based on Example 1. In Examples 15 to 17, in all cases, the glossiness and weather resistance (discoloration resistance) were slightly reduced, resulting in a c judgment. The reason for this is that, compared with Example 15 using an acrylic resin and a silicone resin in the composition for the silver layer, Example 16 using a cellulose resin alone, and Example 17 using a polyvinyl butyral resin alone, in Example 1 using a cellulose-based resin and an acrylic resin in the composition for the silver layer, in the phase separation process of the silver layer, a segregation force (separation action) that causes phase separation into a first phase containing a large amount of composite nanoparticles in the intermediate layer and a second phase containing a small amount of composite nanoparticles strongly acts, so that the contrast between the phases of the intermediate layer (B) becomes strong. Furthermore, the composite nanoparticles are relatively uniformly (without disorder) aligned in the first interface layer (A) and the second interface layer (C). As a result, in Example 1 using a cellulose-based resin and an acrylic resin compared with examples using other resin components in the composition for the silver layer, the shielding effect in the silver layer strongly acts, so the mirror surface property of the silver layer is high and the glossiness is high. Furthermore, in Example 1 using a cellulose-based resin and an acrylic resin in the composition for the silver layer, the composite nanoparticles in the second interface layer (C) are relatively disorder-free aligned even after the weather resistance test. Furthermore, because the repulsive force (separation action) of the phase separation of the intermediate layer (B) is strong, the phenomenon that the composite nanoparticles in the second interface layer (C) disappear partially and move to the intermediate layer (B) hardly occurs according to the above mechanism, and the structural change of the silver layer can be suppressed relatively slightly. Therefore, it is considered that the discoloration (color difference ΔE) before and after the weather resistance test is relatively small, and the weather resistance (discoloration resistance) of the silver gloss film can be enhanced.

[0284] From the above results, by using a cellulose-based resin and an acrylic resin in the composition for the silver layer, and making the first resin of the intermediate layer (B) of the silver layer a cellulose-based resin and the second resin an acrylic resin, it was found that the glossiness and weather resistance (discoloration resistance) can be enhanced, and a silver gloss film with a well-balanced (B-rank) glossiness, weather resistance (discoloration resistance), adhesion, and abrasion resistance suitable for long-term use can be obtained.

[0285] (Obtained effects) From the above verification results, it was confirmed that the silver gloss film includes a silver layer laminated on a substrate and a top coat layer laminated on the silver layer, the top coat layer is formed of a cured product of a curable composition containing an epoxy resin and a curing agent, and when the cured product contains a meta-xylylenediamine unit, a silver gloss film capable of improving silver glossiness, adhesion, abrasion resistance and weather resistance (discoloration resistance) can be obtained.

Industrial Applicability

[0286] The silver gloss film of the present invention can be used to improve the decorativeness of various decorated objects (molded articles), for example, it can be used for decoration and painting applications such as interior and exterior parts of automobiles, emblems, mobile phones, notebook computers, shafts of golf clubs, containers for cosmetics, etc.

Explanation of Signs

[0287] 1... Top coat layer 2... Silver layer 3... Substrate

Claims

1. A silver gloss film laminated on a substrate, wherein the silver gloss film includes a silver layer laminated on the substrate and a top coat layer laminated on the silver layer, the silver layer includes a first interface layer (A) on the substrate side formed of composite nanoparticles (a) of a metal containing silver and a protective colloid, a first phase including composite nanoparticles (b1) of a metal containing silver and a protective colloid and a first resin (b2) laminated on the first interface layer (A), and a second phase including composite nanoparticles (b3) of a metal containing silver and a protective colloid and a second resin (b4) and having a lower content ratio of the metal containing silver than the first phase, and having a phase-separated structure in which the intermediate layer (B) is phase-separated, formed by a second interface layer (C) laminated on the intermediate layer (B) and formed of composite nanoparticles (c) of a metal containing silver and a protective colloid, the top coat layer is formed of a cured product of a curable composition containing an epoxy resin and a curing agent, the cured product contains a metaxylylenediamine unit, and the silver gloss film.

2. Irradiance of 120 W / m ２ The silver gloss film according to claim 1, wherein the color difference ΔE before and after the weather resistance test with an irradiance of 120 W / m, a black panel temperature of 63°C, and an irradiation time of 100 hours is less than 5.

3. The silver gloss film according to claim 1 or 2, wherein the average thickness of the top coat layer is 0.5 to 20 μm.

4. The oxygen permeability of the topcoat layer is 30 mL / m ２ / day / atm or less, and the silver gloss film according to claim 1 or 2.

5. The silver gloss film according to claim 1 or 2, wherein at least one of the epoxy resin and the curing agent in the top coat layer contains a metaxylylenediamine unit.

6. The silver gloss film according to claim 1 or 2, further including an undercoat layer interposed between the substrate and the first interface layer (A), the undercoat layer being formed of a cured product of a curable composition containing an epoxy resin and a curing agent, the cured product containing a metaxylylenediamine unit, and the average thickness of the undercoat layer being 20 to 100 μm.

7. The silver gloss film according to claim 1 or 2, wherein the first resin (b2) is at least one selected from the group consisting of (meth)acrylic resins, polyvinyl acetal resins, and cellulose resins, and the second resin (b4) is at least one selected from the group consisting of (meth)acrylic resins, polyvinyl acetal resins, cellulose resins, and silicone resins.

8. The silver gloss film according to claim 1 or 2, wherein the first resin (b2) is a cellulose resin and the second resin (b4) is a (meth)acrylic resin.

9. A method for manufacturing the silver gloss film according to claim 1 or 2, wherein a silver layer and a top coat layer are laminated on a substrate.

10. The manufacturing method according to claim 9, obtained through a coating step of applying, onto a substrate, a liquid composition containing composite nanoparticles of a metal containing silver, a protective colloid, a first resin, a second resin, and a solvent, and a phase separation step of drying a coating film formed from the liquid composition to obtain a silver layer having a phase separation structure.

11. A decorated body having the silver gloss film according to claim 1 or 2 laminated on a substrate.

12. A method of decorating a decorated object as a substrate by laminating the silver gloss film according to claim 1 or 2 on the decorated object.

Images