JP2014133403A - Mirror film, production method of the same, and reflecting mirror using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mirror film which has good adhesiveness between a substrate and a reflective metal film, is hardly influenced by oxygen or moisture, and has excellent durability enough to be used at outdoors for a long period of time, while maintaining such characteristics that the film is lightweight and hardly broken.SOLUTION: The mirror film is formed by laminating, in the following order, a support 12, a plating undercoat polymer layer 14 comprising reduced metal particles, a reflective layer 16 containing silver, and a resin coating layer 18. The plating undercoat polymer layer 14 comprising reduced metal particles and the reflective layer 16 containing silver are disposed in a region excluding a peripheral portion of the support. The peripheral portion of the support 12 and the resin coating layer 18 are in close contact with each other.

Description

  The present invention relates to a mirror film, a reflecting mirror using the mirror film, and a method for manufacturing the mirror film.

In recent years, research on alternative energy alternatives to fossil fuel energy typified by petroleum energy has begun to be actively studied. Wind power generation, geothermal power generation, solar power generation, solar power generation, etc. are clean natural energies, and are said to hold the key to future energy development. Among them, those that use solar energy are considered to be particularly effective because they are stable and have a large amount.
However, although solar energy is a very powerful alternative energy, when trying to utilize it, there are problems such as low energy density of solar energy, difficulty in storing and transferring energy, and so difficult to use at night. It is said that there is.
In recent years, concentrating solar power generation and concentrating solar power generation have been proposed to solve these problems. These methods are trying to solve the problem of low solar energy density by collecting sunlight with a reflector.
These reflectors are exposed to ultraviolet rays and heat rays from sunlight, wind and rain such as sea breeze and acid rain, and chemical impacts, and physical impacts such as dust, dust, and sandstorms. Conventionally, reflectors made of glass have been used. However, although glass mirrors are highly durable to the environment, they are heavy and easily damaged, so there is a concern that they will be damaged during transportation. The construction cost increases due to the need to build a heavy mirror installation base. There is a problem that a large amount of energy is required to drive the motor.

On the other hand, it is conceivable to use a plastic mirror as a method for solving the above problem. For example, a plastic mirror using Al as a reflection layer has been proposed (see, for example, Patent Document 1). However, since the aluminum layer has a low light reflectance, a mirror with a large area is required for necessary light collection. There is a problem that the installation area and the construction cost become large.
The reflectance can be increased by using Ag for the reflective layer, and such plastic mirrors have also been proposed (see, for example, Patent Document 2), but the Ag metal layer has poor adhesion to the resin support. There is a problem that the flatness is lowered and an effective reflectance cannot be obtained.
A conductive polypyrrole underlayer and an Ag layer are formed in a region excluding the end of the resin support, and an inorganic gas barrier layer is formed by applying the coating liquid so as to cover the Ag layer, the underlayer and the end. A resin mirror film in which the Ag layer and the underlayer are protected to improve weather resistance has been proposed (see, for example, FIG. 2 of Patent Document 3).

These metal layers have the problem that the oxidation progresses over time and discolors or corrodes. Usually, the surface of the metal layer is covered with a resin layer for protecting the metal layer. In order to suppress the penetration of air, it is common to provide a protective layer at the end.
FIG. 3A is a plan view showing an embodiment of a conventional mirror film, and FIG. 3B is a schematic cross-sectional view thereof. In the conventional mirror film 30, a laminate including a resin base material 15 and a metal layer 17 formed on the surface thereof is disposed on the support 12, and the resin surface is disposed on the surface via an adhesive layer 22. The layer 18 adheres and suppresses the penetration of oxygen and moisture from the surface. Moreover, the edge part is coat | covered with the protective tape 24, and the permeation | transmission of oxygen and a water | moisture content from an edge part is suppressed. However, as shown in FIG. 4B, the covering with the protective tape 24 has a problem that bubbles or the like easily enter when the protective tape 24 is covered, and a highly reliable gas and moisture barrier property can be obtained. There wasn't.

JP-A-2005-59382. JP-A-6-38860. International publication WO2010 / 150570 pamphlet

For example, the method described in Patent Document 3 requires a step of heating or drying after applying a base layer for forming Ag, so that patterning is difficult and adhesion between adjacent layers is good. For this reason, when patterning, it is difficult to physically remove the region to be removed by scribing or the like. For this reason, there is a problem that it is difficult to form a structure that completely seals the end portion.
Furthermore, even if it takes the structure which does not have a metal layer in a peripheral part, there exists a limit in the shape followability of protective tape 24 itself. FIG. 4A shows a schematic diagram of a mirror film having a polypyrrole coating layer 19, a light reflecting layer 20 and a protective tape 24 on the support 12. As shown in FIG. 4A, it was difficult to completely remove the voids, and there was still room for improvement in terms of gas and moisture barrier properties.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to maintain the property of being lightweight and difficult to break, while maintaining good adhesion between the substrate and the reflective metal film, and oxygen and moisture. An object of the present invention is to provide a mirror film excellent in durability that is not easily affected by long-term outdoor use.
Further, another object of the present invention is a lightweight and durable reflector using the mirror film, and a manufacturing method of the mirror film that is simple and capable of large area and mass production. Is to provide.

As a result of intensive studies, the inventors of the present invention have used a photosensitive polymer to form a metal layer having excellent adhesion to the support only in a region excluding the peripheral portion of the support, thereby forming a metal on the peripheral portion of the support. A mirror film with excellent durability while suppressing the permeation of oxygen and moisture from the peripheral part and maintaining the characteristics of lightweight and flexible by making the area not having a layer and making the area a sealing area. It came to offer.
The configuration of the present invention is as follows.
<1> A plating comprising a support, a plating undercoat polymer layer containing reduced metal particles, a reflective layer containing silver, and a resin coating layer in this order, and containing the reduced metal particles The undercoat polymer layer and the reflective layer containing silver are provided in a region excluding the peripheral portion of the support, and the peripheral portion of the support and the resin coating layer are in close contact with each other.
Hereinafter, the reflective layer containing silver is appropriately referred to as a silver-containing metal layer.

<2> The mirror film according to <1>, wherein the plating undercoat polymer layer includes a polymer having at least a carbonyl group.
<3> The plating undercoat polymer layer includes an acrylic polymer having an acidic group and a polymerizable group in a side chain, and the acrylic polymer is energized in the plating undercoat polymer layer, or the polymerizable groups are combined with each other, or The mirror film according to <1> or <2>, wherein a cross-linked structure or a chemical bond is formed between the polymerizable group and the support.
<4> The mirror film according to <3>, wherein the energy application includes UV exposure.
<5> The reflective layer containing silver is a layer including a metal multilayer film having at least a metal film containing silver on the resin coating layer forming side, according to any one of <1> to <4>. Mirror film.
<6> The mirror film according to any one of <1> to <5>, wherein the support is a polyester film or a polyimide film.
<7> The resin coating layer includes a resin composition containing one or more resins selected from the group consisting of polycarbonate resins, polyester resins, norbornene resins, urethane resins, acrylic resins, and olefin resins. <1> to the mirror film of any one of <6>.
<8> The mirror film according to any one of <1> to <7>, wherein a peripheral portion of the support and the resin coating layer are in close contact with each other via an adhesive layer.
<9> The mirror film according to <8>, wherein the resin coating layer and the reflective layer containing silver are in close contact with each other via an adhesive layer.
<10> mirror film according to the periphery of the support and said resin coating layer, any one of <7> to <1> which is in close contact with a straight or direct contact with each other.
<11> A reflecting mirror including the mirror film according to any one of <1> to <10> on a rigid housing.
<12> a step of forming a plating undercoat polymer layer in a region excluding the peripheral portion on the support;
Applying a metal precursor to the plating undercoat polymer layer;
Reducing the applied metal precursor;
Forming a reflective layer containing silver by electroplating in a region excluding the peripheral edge on the support; and
The manufacturing method of the mirror film of any one of <1> to <10> including the process of forming a resin coating layer so that the reflection layer containing the said silver and the peripheral part of the said support body may be covered. .
<13> A step of forming a plating undercoat polymer layer in a region excluding the peripheral portion on the support, and a step of contacting a composition for forming a plating undercoat polymer layer containing a plating undercoat polymer on the support; <12> The manufacturing method of the mirror film as described in <12> including the process of providing energy only to the area | region except the peripheral part on the said support body, and fixing a plating undercoat polymer layer on the said support body.
<14> The step of forming a plating undercoat polymer layer in a region excluding the peripheral portion on the support includes the step of forming a plating undercoat polymer layer on the entire surface of the support, and the step in the peripheral portion of the support. The method for producing a mirror film according to <12> or <13>, including a step of removing the plating undercoat polymer layer.
<15> The method for producing a mirror film according to <13>, wherein the energy application includes UV exposure.
<16> The plating undercoat polymer includes an interactive group-containing unit composed of a polymerizable group-containing unit represented by the following formula (A) and a non-dissociable functional group represented by the following formula (B), and the following formula (C ), A copolymer containing an interactive group-containing unit composed of an ionic polar group, a co-polymer containing a unit represented by the following formula (A) and a unit represented by the following formula (B) The mirror film according to any one of <13> to <15>, comprising a coalescence or a copolymer comprising a unit represented by the following formula (A) and a unit represented by the following formula (C): Production method.

In the above formulas (A) to (C), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and X, Y, Z, and U independently represents a single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ , L ² , and L ³ each independently represent Represents a single bond or a substituted or unsubstituted divalent organic group, W represents a non-dissociative functional group that interacts with the plating catalyst or a precursor thereof, and V interacts with the plating catalyst or a precursor thereof. It represents an ionic polar group that forms an action.
<17> The step of forming a plating undercoat polymer layer in a region excluding the peripheral portion on the support includes the step of applying a polymer layer forming composition containing a material that generates active species to the support < 12. The method for producing a mirror film according to any one of <12> to <16>.
<18> The step of forming the resin coating layer so as to cover the reflective layer containing silver and the peripheral portion of the support is formed on the support on which the reflective layer containing silver is formed. Applying the resin material for forming dissolved in a solvent, drying and forming a layer made of the resin material for forming the resin coating layer; and curing the layer made of the resin material for forming the resin coating layer The manufacturing method of the mirror film of any one of <12> to <17> containing these.
<19> The step of forming a resin coating layer so as to cover the reflective layer containing silver and the peripheral portion of the support is formed of a resin film and a reflective layer containing silver via an adhesive layer. <12> to <17> The manufacturing method of the mirror film of any one of <12> including the process made to closely_contact | adhere on the made support body

According to the present invention, while maintaining the characteristics of being lightweight and difficult to break, the adhesion between the base material and the reflective metal film is good, and is hardly affected by oxygen and moisture, and can withstand long-term outdoor use. A mirror film having excellent durability can be provided.
In addition, according to the present invention, there is provided a lightweight and durable reflector using the mirror film, and a simple manufacturing method of the mirror film capable of increasing the area and mass production. Provided.

(A) is a top view which shows the one aspect | mode of the mirror film of this invention, (B) is the schematic sectional drawing. (A) is a top view which shows another aspect of the mirror film of this invention, (B) is the schematic sectional drawing. (A) is a top view which shows the one aspect | mode of the conventional mirror film which sealed the edge part with the protective tape, (B) is the schematic sectional drawing. (A) is a schematic sectional drawing which shows the state of the edge part in the conventional mirror film, (B) is a schematic sectional drawing which shows the aspect which has a bubble between a support body and a protective tape.

Preferred embodiments of the film mirror of the present invention will be described below with reference to the drawings.
FIG. 1A is a plan view showing an embodiment of the mirror film 10 of the present invention, and FIG. 1B is a schematic sectional view thereof.
The mirror film 10 includes a plating undercoat polymer layer 14 and a reflective layer 16 containing silver (hereinafter referred to as a “silver-containing metal layer” as appropriate) 16 at the central portion excluding the peripheral portion of the support 12. The surface of the peripheral region of the support in which the layer 16 and the silver-containing metal layer 16 are not formed is coated with the resin coating layer 18, and in the region in which the metal layer 16 is not formed, the support 12 and the resin coating layer 18 are formed. Are in close contact with each other, and penetration of oxygen and moisture from the end of the mirror film 10 is suppressed.
“Adhesion” refers to “adhering tightly”, but “adhesion” in the present embodiment further refers to fusion bonding of the resin constituting the support 12 and the resin coating layer 18 by thermocompression bonding. Bonding between components constituting the support 12 and the resin coating layer 18, formation of interaction by molecular-molecular force, and resin components obtained by dissolving the components constituting the support 12 and the resin coating layer 18 in the solvent It is used in the meaning of including the state of having adhesion at the laminated interface between the support 12 and the resin coating layer 18 due to the entanglement of the substrate.

FIG. 2A is a plan view showing another embodiment of the mirror film 20 of the present invention, and FIG. 2B is a schematic sectional view thereof. In the present embodiment, the support 12 and the resin coating layer 18 are in close contact with each other via the adhesive layer 22. By selecting a material having excellent adhesion to the support 12 and the resin coating layer 18 as the adhesive layer 22, the effect of suppressing the penetration of oxygen and moisture from the end of the mirror film 20 is further improved.
As “adhesion” in the present embodiment, the support 12 and the adhesive layer 22, and the adhesive layer 22 and the resin coating layer 18, the cohesive force of the adhesive or pressure-sensitive adhesive constituting the adhesive layer 22, anchor effect, molecule The laminated interface between the support 12 and the adhesive layer 22, and between the adhesive layer 22 and the resin coating layer 18 due to, for example, the formation of a bond with the adhesive layer (here, the support 12 or the resin coating layer 18). It is used to include a state having adhesion at the laminated interface.

In any embodiment, since the silver-containing metal layer 16 is not formed on the peripheral portion of the mirror films 10 and 20, the resin coating layer 18 itself or the region where the resin coating layer 18 and the adhesive layer 22 are formed has oxygen or It becomes a moisture permeation suppression region. Here, by forming the resin coating layer 18 by a coating method or the like, adhesion is ensured, and for example, there is almost no possibility that bubbles or the like are generated at the interface between the support 12 and the resin coating layer 18. The properties are very good. Moreover, when using a film-like thing as the resin coating layer 18, in order to suppress that a space | gap generate | occur | produces between the support bodies 12, it is preferable to interpose the contact bonding layer 22. FIG.
As a material for forming the resin coating layer 18, it is preferable to use a resin capable of forming a film having a high oxygen barrier property.

Hereinafter, the material which comprises the mirror film which concerns on this invention is demonstrated with the formation process.
As shown in FIG. 1, the mirror film of the present invention comprises a support 12, a plating undercoat polymer layer 14 containing reduced metal particles, a reflective layer 16 containing silver, and a resin coating layer 18. The plated undercoat polymer layer 14 containing the reduced metal particles and the reflective layer 16 containing silver are provided in a region excluding the peripheral portion of the support 12, and the peripheral portion of the support 12. And the resin coating layer 18 are in close contact with each other.
The method for producing a mirror film of the present invention includes a step of forming a plating undercoat polymer layer in a region excluding the peripheral portion on a support, a step of applying a metal precursor to the plating undercoat polymer layer, and a metal precursor applied thereto. The step of reducing, the step of forming a reflective layer containing silver in the region excluding the peripheral portion on the support by electroplating, and the reflective layer containing silver and the peripheral portion of the support are covered The step of forming a resin coating layer is included.
In the present invention, the formation of the silver-containing metal layer 16 is characterized by providing a “plating undercoat polymer layer 14 containing reduced metal particles” having high plating acceptability.
The adhesion between the metal and the resin film is poor, and in order to improve the adhesion, the resin film surface is made uneven, and the adhesion is increased by the anchor effect between the metal and the film substrate, or in the film substrate For example, a method such as sputtering or ion implantation is applied to the metal, and the adhesion is improved by forcibly implanting metal. However, in the method of increasing the adhesion by the anchor effect, when the metal film thickness is thin, the formed metal layer surface reflects the unevenness of the resin support, and there is a problem that the reflectivity decreases due to poor smoothness. If the film thickness is increased so as not to reflect the unevenness of the resin surface, the amount of the metal material used increases, and there is a concern that lightness and flexibility are reduced. In addition, the method of forcing metal into the resin film by sputtering or ion implantation requires high energy, so it is not productive and supports low-cost general-purpose plastic films due to problems such as heat generation. There was a problem that it was difficult to use as a body. In the present invention, these problems are solved by using a plating undercoat polymer layer described later.

(1) Step of forming a plating undercoat polymer layer in a region excluding the peripheral edge on the support <(A) Support>
In the present invention, (A) the film base material used as the support is a film of glass epoxy, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, liquid crystal polymer, etc., from the viewpoint of flexibility and weight reduction. A resin film, paper, or the like molded into a shape can be used.
Examples of the resin include phenol resin, epoxy resin, imide resin, bismaleimide triazine (BT) resin, polyphenylene ether (PPE) resin, tetrafluoroethylene resin, liquid crystal resin, polyester resin, polyethylene naphthalate (PEN), aramid resin, polyamide Resin, polyether sulfone, triacetyl cellulose, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polystyrene, polybutadiene, polyacetylene, and the like are suitable, and any resin that can be molded into a film can be used.
A particularly suitable support includes a polyester film or a polyimide film.
The shape of the support may be any shape as long as it is a shape required for a film substrate in various mirror films such as a flat surface, a diffusion surface, a concave surface, and a convex surface.
The thickness of the support is preferably about 10 μm to 5 mm. If it is thinner than this, handling during production becomes difficult, and if it is thicker than this, molding becomes difficult. More preferably, it is 20 micrometers-1 mm, More preferably, it is the range of 25 micrometers-500 micrometers.

  In addition, the support may be subjected to surface treatment in advance in order to easily form a plating undercoat polymer layer containing (B) reduced metal particles provided on the support. Surface treatments include UV irradiation, ozone treatment, plasma treatment, corona treatment, flame treatment, and other surface-decomposing and activating processes such as hydrazine, N-methylpyrrolidone, sodium hydroxide solution, and potassium hydroxide solution. Treatment with an alkaline solution, treatment with a strong acid solution such as sulfuric acid, hydrochloric acid or nitric acid, and treatment to clean the surface of the support with an organic solvent such as methanol, ethanol, toluene, ethyl acetate, or acetone. May be. Of course, water washing or the like may be performed to remove the attached dust. Moreover, in order to form the plating undercoat polymer layer containing the reduced metal particles, another undercoat layer different from the plating undercoat polymer layer containing the reduced metal particles may be provided on the support.

  For the purpose of improving the reflectivity of the mirror film, it is preferable to use a support having an average roughness (Rz) measured by JIS B 0601 (1994), 10-point average height method of 3 μm or less, Rz is more preferably 1 μm or less. More preferably, the average roughness (Rz) is 0.5 μm or less.

The support preferably contains an ultraviolet absorber.
Moreover, you may contain the plasticizer for maintaining a softness | flexibility, the antioxidant which prevents deterioration of the film itself, a radical scavenger, etc.

(Antioxidant)
As the antioxidant, it is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, and a phosphite-based antioxidant.

Examples of phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-t-). Butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 2,6-di-t-butyl-p-cresol, 4,4 '-Thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 1,3,5-tris (3', 5'-di-t -Butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ,bird Tylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 3,9-bis [1,1-di-methyl-2- [β- (3-t-butyl- 4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene and the like.
In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

Examples of the thiol antioxidant include distearyl-3,3′-thiodipropionate and pentaerythritol-tetrakis- (β-lauryl-thiopropionate).
Examples of the phosphite antioxidant include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6
-Di-t-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butyl) Phenyl) -4,4′-biphenylenediphosphonite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, and the like.
As content in the case of using antioxidant for a support body, it is preferable that it is the range of 0.1 mass part-10 mass parts with respect to 100 mass parts of resin used as the base material of a support body.

(UV absorber)
As the ultraviolet absorber, at least one of ultraviolet absorbers such as benzotriazole, benzophenone, triazine, phenyl salicylate, hindered amine, cyanoacrylate, and inorganic particle type ultraviolet absorbers such as titanium oxide. It is preferable to contain.

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4′-tetra And hydroxy-benzophenone.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole and the like.

Examples of the phenyl salicylate ultraviolet absorber include phenylsulcylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.
Examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazi 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine and the like.

In addition to the above, the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy or the like. Furthermore, those that exhibit an effect when used in combination with an antioxidant, a colorant, or the like, or a light stabilizer that acts as a light energy conversion agent, called a quencher, can be used in combination.
The content in the case of using an ultraviolet absorber for the support is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin serving as the substrate of the support.

<(B) Plating undercoat polymer layer containing reduced metal particles>
The (B) plating undercoat polymer layer containing reduced metal particles in the present invention has at least reduced metal particles and a plating undercoat polymer described below.
In the present invention, using a composition containing a metal precursor and a plating undercoat polymer described later, a plating undercoat polymer layer containing the metal precursor is formed on the support by a method such as coating, or the plating described below is used. A layer is formed on the support using the composition containing the undercoat polymer, and then the metal precursor is brought into contact with the layer provided on the support by a method such as dipping. After forming the polymer layer containing the body, the plating precursor polymer layer containing the reduced metal particles of the present invention is reduced by reducing the metal precursor of the plating primer polymer layer containing the metal precursor. Is preferably formed.

(Plating undercoat polymer)
First, the plating undercoat polymer used in the composition for forming a plating undercoat polymer layer will be described.
The plating undercoat polymer used in the composition for forming a plating undercoat polymer layer in the present invention has at least a polymerizable group and a functional group that interacts with the metal precursor (hereinafter referred to as “interactive group” as appropriate).
The main skeleton of the plating undercoat polymer is preferably an acrylic polymer, polyether, acrylamide, polyamide, polyimide, acrylic polymer, polyester, or the like, and more preferably an acrylic polymer.

The plating undercoat polymer only needs to have the polymerizable group and the interactive group in the molecule, and the polymerizable group only needs to be at least one of the main chain terminal and the side chain of the polymer. For example, a polymer composed of the structural unit having the polymerizable group and the structural unit having the interactive group can be mentioned, and the same structural unit includes the polymerizable group and the interactive group. May be. Moreover, 2 or more types of polymeric groups may be included, and 2 or more types of interactive groups may be included. Moreover, a polymeric group may be introduce | transduced by polymer reaction after preparation of a polymer.
Moreover, the plating undercoat polymer may contain structural units other than the structural unit containing a polymeric group and the structural unit containing an interactive group according to the objective. When a plating undercoat composition is formed by including a structural unit containing a polymerizable group and a structural unit other than the structural unit containing an interactive group (hereinafter, referred to as “other structural unit” as appropriate) Alternatively, it is excellent in solubility in an organic solvent, and a uniform plating undercoat layer can be formed.

As a preferable embodiment of the plating undercoat polymer, an acrylic polymer having an acidic group and a polymerizable group as an interactive group in the side chain can be mentioned.
Hereinafter, a polymerizable group, an interactive group, and characteristics of the plating undercoat polymer will be described in detail.

(Polymerizable group)
The polymerizable group of the plating undercoat polymer is a functional group capable of forming a chemical bond between the polymers or between the polymer and the base layer (undercoat layer provided on the support) by applying energy. I just need it. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. Of these, a radical polymerizable group is preferable from the viewpoint of reactivity.
Examples of the radical polymerizable group include a methacryloyl group, an acryloyl group, an itaconic acid ester group, a crotonic acid ester group, an isocrotonic acid ester group, a maleic acid ester group, a styryl group, a vinyl group, an acrylamide group, and a methacrylamide group. It is done. Of these, a methacryloyl group, an acryloyl group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable. Among them, a methacryloyl group, an acryloyl group, an acrylamide group, and a methacrylamide group are preferable from the viewpoint of radical polymerization reactivity and synthesis versatility. An acrylamide group and a methacrylamide group are more preferable from the viewpoint of alkali resistance.
Details of the polymerizable group will be described in detail below.

The polymerizable group that can be introduced into the undercoat polymer according to the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the following general formulas (A-5) to (A-7) The polymerizable group represented by these is preferable.
Hereinafter, a preferable structure of the polymerizable group contained in the acrylic polymer and a method for introducing the same will be described in detail.

In general formulas (A-5) to (A-7), R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ¹² —. Z represents an oxygen atom, a sulfur atom, —N—R ¹³ —, or a phenylene group. R ¹² and R ¹³ each independently represent a hydrogen atom or a monovalent organic group.

In the general formula (A-5), as R ¹ , for example, a hydrogen atom or an alkyl group which may have a substituent is preferable, and a hydrogen atom or a methyl group is more preferable because of high radical reactivity. .
R ² and R ³ are each independently, for example, a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, including a hydrogen atom, a carboxyl group, an alkoxycarbonyl group and a substituent. An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.

The -N-R 12 in which X represents ^- As R ¹² in, for example, hydrogen atom, or an alkyl group and the like are preferable, which may have a substituent, because of high radical reactivity, hydrogen atom, a methyl group, An ethyl group or an isopropyl group is more preferable.
Examples of the substituent that can be introduced into these groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, Examples include an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formula (A-6), examples of R ^{4 to} R ⁸ include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and a substituent. An alkyl group that may have a group, an aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, and a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc. are preferable, a hydrogen atom, a carboxyl group , An alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
Examples of the substituent that can be introduced into these groups are the same as those exemplified in the general formula (A-5).
^{-N-R 12} wherein Y represents - As ^{R 12} in include the same ones as mentioned in ^{R 12} in the general formula (A-5).

In the general formula (A-7), as R ⁹ , for example, a hydrogen atom or an alkyl group which may have a substituent is preferable, and a hydrogen atom or a methyl group is more preferable because of high radical reactivity. .
Further, each of R ¹⁰ and R ¹¹ has, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino which may have a substituent Group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like are preferable, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include those listed in the general formula (A-5).
Z represents an oxygen atom, a sulfur atom, —NR ¹³ —, or a phenylene group which may have a substituent. R ¹³ is preferably a hydrogen atom or an optionally substituted alkyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.

  Among the polymerizable groups represented by the general formulas (A-5) to (A-7), those represented by the general formula (A-5) are high in polymerization reactivity and high in sensitivity. More preferable.

Although there is no restriction | limiting in particular in content of the polymeric group in a plating undercoat polymer, 0.1 meq / g-3.0 meq / g are preferable, 0.3 meq / g-3.0 meq / g are more preferable. 5 meq / g to 2.5 meq / g is particularly preferable. By setting the content in this range, a sufficient amount of curing reaction can be obtained, a desired sensitivity can be obtained, and the sensitivity can be further improved and the storage stability can be further improved.
Here, content (meq / g) of a polymeric group can be measured by iodine value titration, for example.

The method for introducing a polymerizable group into the side chain of the plating undercoat polymer is not particularly limited, and a known method may be applied. The polymerizable group represented by the general formula (A-5) may be used as a plating undercoat. If the method of introducing into the side chain of the polymer is described as an example, for example, there is a method in which a polymer compound containing a carboxyl group in the side chain is added with a compound having a polymerizable group and an epoxy group.
The polymer compound containing a carboxyl group in the side chain is usually composed of, for example, one or more radical polymerizable compounds containing a carboxyl group and, if necessary, one or more other radical polymerizable compounds as a copolymerization component. The radical polymerization method includes, for example, suspension polymerization method, solution polymerization method and the like.

  The compound having a polymerizable group and an epoxy group is not particularly limited as long as it has these, and for example, a compound represented by the following general formula (A-8) and a general formula (A-9) Are preferred.

In General Formula (A-8), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a divalent organic group.

In the general formula (A-9), R ² represents a hydrogen atom or a methyl group. L ² represents a divalent organic group. W represents an aliphatic hydrocarbon group that forms a 4- to 10-membered ring with two adjacent carbon atoms.

Of the compound represented by the general formula (A-8) and the compound represented by the general formula (A-9), the compound represented by the general formula (A-8) is preferable, and the general formula (A- In 8), L ¹ is more preferably an alkylene group having 1 to 4 carbon atoms.

  The compound represented by the general formula (A-8) or the compound represented by the general formula (A-9) is not particularly limited, and examples thereof include the following exemplified compounds (31) to (40). It is done.

  Examples of the radical polymerizable compound containing a carboxylic acid group used in this method include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxylstyrene, and the like, which are particularly preferable. Examples thereof include acrylic acid and methacrylic acid.

  Examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, triphenylphosphine, and the like. The reaction can be carried out in an organic solvent at a reaction temperature of 50 ° C. to 150 ° C. for several hours to several tens of hours.

  The structural unit having a polymerizable group in the side chain is not particularly limited. For example, the structure represented by the following general formula (A-10), the structure represented by the general formula (A-11), and What is represented by mixing these is preferable.

In the general formula (A-10) and general formula (A-11), R ^{a to} R ^c each independently represent a hydrogen atom or a monovalent organic group. R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a divalent organic group which may have a substituent.

  The content of the structural unit represented by the general formula (A-10) and the structural unit represented by the general formula (A-11) in the plating undercoat polymer is preferably 20 mol% or more, and 20 mol% to 50 mol%. More preferably, 25 mol% to 45 mol% is particularly preferable. By setting the content in this range, the sensitivity becomes higher and the storage stability becomes better.

(Interactive group)
The interaction group of the plating undercoat polymer is a functional group that interacts with the metal precursor (for example, coordination group, metal ion adsorbing group, etc.), and can form an electrostatic interaction with the metal precursor. A functional group, or a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group or the like that can form a coordination with a metal precursor can be used.
The interactive group may be a non-dissociative functional group or an ionic polar group, and these may be contained at the same time, but an ionic polar group is preferred.

  More specifically, as an interactive group, amino group, amide group, imide group, urea group, tertiary amino group, ammonium group, amidino group, triazole group, benzotriazole group, imidazole group, benzimidazole group, quinoline Group, pyridine group, pyrimidine group, pyrazine group, nazoline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, group containing isocyanuric structure Nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group (-O-CN) and other nitrogen-containing functional groups; ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, carbonate group, carbonyl Group, ester group, N-oxide structure-containing group, S-oxide structure-containing Group, oxygen-containing functional group such as a group containing N-hydroxy structure; thiophene group, thiol group, thiourea group, thiocyanuric acid group, benzthiazole group, mercaptotriazine group, thioether group, thioxy group, sulfoxide group, sulfo group, monkey Sulfur-containing functional groups such as phyto groups, groups containing sulfoxyimine structures, groups containing sulfoxynium salt structures, groups containing sulfonate ester structures; groups containing phosphate groups, phosphoramide groups, phosphine groups, phosphate ester structures Phosphorus-containing functional groups such as: groups containing halogen atoms such as chlorine and bromine, and the like. In functional groups capable of taking a salt structure, salts thereof can also be used.

(Interactive group consisting of non-dissociable functional groups)
As the interactive group comprising a non-dissociative functional group, among the above interactive groups, an ether group or a cyano group is particularly preferable because of its high polarity and high adsorption ability to a plating catalyst, etc., and a cyano group Is most preferred.
Generally, the higher the polarity, the higher the water absorption rate. However, the cyano group interacts so as to cancel each other's polarity in the plating undercoat polymer layer, so that the film becomes dense and the plating Since the polarity of the undercoat polymer layer as a whole is lowered, the water absorption is lowered despite the high polarity. Further, by adsorbing the catalyst with a good solvent for the plating undercoat polymer layer, the cyano group is solvated, the interaction between the cyano groups is eliminated, and the plating catalyst can interact. From the above, the plating undercoat polymer layer having a cyano group is preferable in that it exhibits low performance while exhibiting a contradictory performance that interacts well with the plating catalyst.
Further, the interactive group in the present invention is more preferably a cyano group or an alkyl cyano group among the aforementioned substituents. This is because the aromatic cyano group attracts electrons to the aromatic ring and lowers the donation of unpaired electrons, which is important for adsorptivity to the plating catalyst, but the alkyl cyano group is bonded to this aromatic ring. Therefore, it is preferable in terms of adsorptivity to the plating catalyst.

(Interactive group consisting of ionic polar groups)
In addition, as an interactive group composed of an ionic polar group, among the above interactive groups, from the viewpoint of adhesion of the plating undercoat polymer to the substrate, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a boronic acid group In particular, it has moderate acidity (does not decompose other functional groups), has few concerns about affecting other functional groups, has excellent compatibility with the plating layer, and is easily available In view of the above, a carboxylic acid group is particularly preferable.

The ionic polar group such as the carboxylic acid group can be introduced into the plating undercoat polymer by copolymerizing a radical polymerizable compound having an acidic group. Hereinafter, the carboxylic acid group will be described as an example.
There is no restriction | limiting in particular as a radically polymerizable compound which has a carboxylic acid group used for introduction | transduction of a carboxylic acid group, According to the objective, it can select suitably, For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid , Isocrotonic acid, maleic acid, p-carboxylstyrene, and the like. Among these, acrylic acid, methacrylic acid, and p-carboxylstyrene are preferable. These may be used individually by 1 type and may use 2 or more types together.
Hereinafter, the suitable structure of the plating undercoat polymer used in the present invention will be described in detail.

The acrylic polymer suitably used as the plating undercoat polymer in the present invention will be described more specifically. An acrylic resin containing a carboxylic acid group as an acidic group is added to a cyclic ether group-containing polymerizable compound such as glycidyl acrylate or glycidyl methacrylate. Epoxy group-containing polymerizable compounds such as glycidyl esters of unsaturated fatty acids such as cinnamic acid, and compounds having an alicyclic epoxy group (for example, an epoxy group such as cyclohexene oxide in the same molecule) and a (meth) acryloyl group Examples thereof include compounds obtained by addition. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. Moreover, the compound etc. which copolymerize cyclic ether group containing polymeric compounds, such as glycidyl methacrylate, and vinyl monomers, such as (meth) acryloyl alkyl ester, and add (meth) acrylic acid to the epoxy group of a side chain, etc. are mentioned. It is done.
Specific examples of these polymers are described in Japanese Patent Publication Nos. 2763775, 3-172301, 2000-232264, and the like, and the polymers described herein can be suitably used in the present invention. .

  Among these, the acrylic polymer is obtained by adding a polymerizable compound containing a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) to a part of the acidic group of the polymer compound. It is more preferable that the polymer compound be selected from any of those obtained by adding a carboxyl group-containing polymerizable compound to part or all of the cyclic ether group of the molecular compound. In this case, the addition reaction between the acidic group and the compound having a cyclic ether group is preferably carried out in the presence of a catalyst. In particular, the catalyst is preferably selected from an acidic compound and a neutral compound.

The acidic group represented by the carboxylic acid group can be imparted to the plating undercoat polymer by copolymerizing a radical polymerizable compound having an acidic group.
The radical polymerizable compound having a carboxylic acid group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p -Carboxylstyrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxylstyrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

  The content of the acidic group such as the carboxylic acid group in the plating undercoat polymer is 1.0 meq / g to 10.0 meq / g, preferably 2.0 meq / g to 9.0 meq / g, and 2.5 meq / g. g to 8.0 meq / g is more preferable. By setting the content of the carboxylic acid group within this range, the affinity with the plating layer is sufficient, and damage on the plating surface due to “post-treatment” using alkaline water or the like can be further reduced.

(Unit composition of plating undercoat polymer)
As described above, the plating undercoat polymer in the present invention has a polymerizable group and an interactive group that forms an interaction with the plating catalyst or a precursor thereof. It may be a group or an ionic polar group, and is a polymer having at least one of these. Among these, as described above, it is preferable to have a carboxylic acid group that is an ionic polar group.
As a preferred embodiment of the plating undercoat polymer, an interactive group-containing unit comprising a polymerizable group-containing unit represented by the formula (A) and a non-dissociable functional group represented by the formula (B) and the formula (C) A copolymer containing an interactive group-containing unit composed of an ionic polar group represented by the formula: a copolymer comprising a unit represented by the formula (A) and a unit represented by the formula (B): And a copolymer containing a unit represented by (A) and a unit represented by formula (C).

In the above formulas (A) to (C), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and X, Y, Z, and U independently represents a single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ , L ² , and L ³ each independently represent Represents a single bond or a substituted or unsubstituted divalent organic group, W represents a non-dissociative functional group that interacts with the plating catalyst or a precursor thereof, and V interacts with the plating catalyst or a precursor thereof. It represents an ionic polar group that forms an action.
In the present invention, the organic group refers to a substituent containing a carbon atom.

In the unit represented by the formula (A), Y and Z are preferably each independently an ester group, an amide group, or a phenylene group (—C ₆ H ₄ —). L ¹ is preferably a substituted or unsubstituted divalent organic group having 1 to 10 carbon atoms.
The unit represented by the formula (A) is a unit having a polymerizable group represented by the general formula (A-5).
In the unit represented by the formula (B), W is preferably a cyano group or an ether group. Moreover, X and L ² are preferably both a single bond.
In the unit represented by the formula (C), V is preferably a carboxylic acid group, V is a carboxylic acid group, and L ³ is 4 to 8 members in the portion where V is connected to V. An embodiment including the ring structure is preferable, and an embodiment in which V is a carboxylic acid group and a chain length of L ³ is 6 to 18 atoms is also preferable.
Furthermore, in the unit represented by the formula (C), it is also one of preferable embodiments that V is a carboxylic acid group and U and L ³ are single bonds. Among these, an embodiment in which V is a carboxylic acid group and both U and L ³ are single bonds is most preferable.

The plating undercoat polymer in the present invention is composed of a polymerizable group-containing unit (unit represented by the formula (A)) and an interactive group-containing unit comprising the non-dissociable functional group (formula (B)) with respect to the entire copolymer unit. The ratio of the interactive group-containing unit (unit represented by formula (C)) composed of an ionic polar group is preferably in the following range.
The following mol% range is appropriately selected so that the whole is 100 mol%.
That is, in the case of a copolymer including a unit represented by the formula (A), a unit represented by the formula (B), and a unit represented by the formula (C), the copolymer is represented by the formula (A). Unit: Unit represented by formula (B): Unit represented by formula (C) = 5-50 mol%: 5-40 mol%: 20-70 mol%, preferably 10-40 mol%: 10-35 mol %: More preferably, it is 20-60 mol%.
In the case of a copolymer containing a unit represented by the formula (A) and a unit represented by the formula (B), a unit represented by the formula (A): represented by the formula (B) Unit = 5 to 50 mol%: 50 to 95 mol% is preferable, and 10 to 40 mol%: 60 to 90 mol% is more preferable.
Furthermore, in the case of a copolymer containing a unit represented by the formula (A) and a unit represented by the formula (C), a unit represented by the formula (A): a unit represented by the formula (C) = 5 to 50 mol%: 50 to 95 mol% is preferable, and 10 to 40 mol%: 60 to 90 mol% is more preferable.
Among these, a unit comprising the unit represented by the formula (A) and the unit represented by the formula (C) included in the acrylic polymer having the acidic group and the polymerizable group mentioned above in the side chain. A polymer is more preferred.
Within this range, it is possible to improve the polymerizability of the plating undercoat polymer with respect to UV exposure, decrease the resistance value of the plating undercoat polymer containing the reduced metal particles after reduction of the metal precursor, and improve the moisture adhesion resistance. it can.

For the purpose of improving various properties such as image strength, the plating undercoat polymer is used in addition to the above-mentioned units having a polymerizable group and units having an acidic group, that is, both of a polymerizable group and an acidic group. It is preferable to copolymerize a radically polymerizable compound not contained.
Examples of the other radical polymerizable compounds include (meth) acrylic acid esters such as alkyl (meth) acrylate and aryl (meth) acrylate, styrenes such as styrene, alkylstyrene, alkoxystyrene and halogen styrene, alkyl ( Examples thereof include radically polymerizable compounds selected from (meth) acrylamides, vinyl ethers, N-substituted maleimides, vinyl cyanos and the like.

Other radical polymerizable compounds will be described in detail.
As the alkyl (meth) acrylate, those having 1 to 20 carbon atoms in the alkyl group are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic acid Butyl, (meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid amyl, (meth) acrylic acid hexyl, (meth) acrylic acid ethylhexyl, (meth) acrylic acid -N-octyl, (meth) acrylic acid-t-octyl, (meth) acrylic acid-i-octyl, (meth) acrylic acid-i-decyl, (meth) acrylic acid lauryl, chloroethyl (meth) acrylate, 2, 2-dimethylhydroxypropyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, trimethylolpropa Mono (meth) acrylate, pentaerythritol mono (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, cyanoethyl (meth) acrylate, cyanopropyl (meth) acrylate, cyanobenzyl (meth) ), (Meth) acrylic acid esters having an alkyl group having 1 to 25 carbon atoms, such as acrylate, furfuryl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Among them, (meth) acrylic acid esters having an alkyl group having 2 to 15 carbon atoms are preferable, and acrylic acid esters are more preferable.

  Examples of the aryl (meth) acrylate include aryl (meth) acrylates having an alkyl group having 1 to 25 carbon atoms such as phenyl (meth) acrylate, cresyl (meth) acrylate, and naphthyl (meth) acrylate. Of these, phenyl acrylate is preferred.

  Examples of styrenes include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene. , Ethoxymethyl styrene, acetoxymethyl styrene, cyano styrene, etc., as alkoxy styrenes, methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc., as halogen styrene, for example, chlorostyrene, dichlorostyrene, trichlorostyrene, Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene Down, 2-bromo-4-trifluoromethyl styrene, and 4-fluoro-3-trifluoromethyl styrene, include styrenes having 1 to 25 carbon atoms. Of these, styrene and methoxystyrene are preferable.

  Examples of alkyl (meth) acrylamides include methyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dibutyl (meth) acrylamide, t-butyl (meth) acrylamide, octyl (meth) acrylamide, and dodecyl. Examples include (meth) acrylamide having an alkyl group having 1 to 22 carbon atoms, such as (meth) acrylamide. Of these, acrylamide and isopropylacrylamide are preferable.

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl. Methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, Trahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, and the like. Of these, phenyl vinyl ether and butyl vinyl ether are preferable.

Examples of N-substituted maleimides include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, N- Examples include n-hexylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-1-naphthylmaleimide and the like. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are preferable, and N-phenylmaleimide is more preferable.
Examples of the vinyl cyano compounds include (meth) acrylonitrile, cyanopropene, dicyanoethylene, and the like.

  These other radically polymerizable compounds may be used alone as other radically polymerizable compounds, or two or more of them may be used in combination.

  In the present invention, the solvent used in synthesizing the plating undercoat polymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol , Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide Dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These may be used alone or in combination of two or more.

  In the present invention, the plating undercoat polymer may contain an unreacted monomer. In this case, the content of the unreacted monomer in the plating undercoat polymer is preferably 15% by mass or less.

  In this invention, a plating undercoat polymer may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may mix and use the other high molecular compound from which a structure differs from a plating undercoat polymer. In this case, the content of the other polymer compound in the total of the plating undercoat polymer and the other polymer compound is preferably less than 50% by mass, and more preferably 30% by mass or less.

The weight average molecular weight of the plating undercoat polymer in the present invention is preferably from 1,000 to 700,000, more preferably from 2,000 to 200,000, and even more preferably from 10,000 to 100,000. By setting the weight average molecular weight within this range, higher adhesion strength can be obtained, resistance to a treatment solution such as alkaline water can be obtained, and storage stability with time can be further improved. In particular, from the viewpoint of polymerization sensitivity, the weight average molecular weight of the plating undercoat polymer in the present invention is preferably 20000 or more. In addition, it is preferable that the upper limit of molecular weight is 150,000 from a viewpoint of gelatinization suppression during a synthesis | combination, More preferably, it is 100,000 or less.
In addition, the weight average molecular weight described here is a value measured by polystyrene conversion using GPC (used solvent: N-methylpyrrolidone), and can be measured, for example, under the following conditions.
・ Column: Guard column TOSOH TSKguardcolum Super AW-H
Separation column TOSOH TSKgel Super AWM-H (3 size 6.0 mm x 15 cm connected)
Eluent: N-methylpyrrolidone (containing LiBr 10 mM)
・ Flow rate: 0.35 mL / min
・ Detection method: RI
-Temperature: Column 40 ° C, inlet 40 ° C, RI 40 ° C
Sample concentration: 0.1 wt%
・ Injection volume: 60 μL
Moreover, as a polymerization degree of the plating undercoat polymer in this invention, it is preferable to use a 10-mer or more thing, More preferably, it is a 20-mer or more thing. Moreover, 1500-mer or less is preferable and 1000-mer or less is more preferable.

  Specific examples of the plating undercoat polymer include polymers described in paragraphs [0106] to [0112] of JP-A-2009-007540 as a polymer having an interactive group composed of a radical polymerizable group and a non-dissociable functional group. Can be used. As the polymer having a radical polymerizable group and an interactive group composed of an ionic polar group, polymers described in paragraphs [0065] to [0070] of JP-A-2006-135271 can be used. Examples of the polymer having a radical polymerizable group, an interactive group composed of a non-dissociative functional group, and an interactive group composed of an ionic polar group include paragraphs [0010] to [0010] of [2010] -248464. [0128], polymers described in paragraphs [0030] to [0108] of JP 2010-84196 A and US Patent Application Publication No. 2010-080964 may be used.

  Although the plating undercoat polymer used especially suitably in this invention is mentioned below, it is not limited to these. In addition, the number of a subscript represents a composition ratio (molar ratio).

  In order to form the plating undercoat polymer layer, the plating undercoat polymer layer forming composition may be brought into contact with the support or the support having the undercoat layer to impart energy. The contact of the plating undercoat polymer layer forming composition on the support is preferably carried out by applying a coating solution containing the plating undercoat polymer layer forming composition on the substrate.

(Composition for forming plating undercoat polymer layer)
The composition for forming a plating undercoat polymer layer contains the plating undercoat polymer.
The content of the plating undercoat polymer in the composition for forming a plating undercoat polymer layer is not particularly limited, but is preferably 2% by mass to 50% by mass and more preferably 5% by mass to 30% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a polymer layer.

  When the plating undercoat polymer is an acrylic polymer, the content of the plating undercoat polymer with respect to the solid content of the composition for forming a plating undercoat polymer layer is preferably 1% by mass to 80% by mass, and more preferably 2% by mass to 70% by mass. preferable. By setting the content in this range, the surface shape of the coating film becomes better, and the coating liquid does not increase in viscosity, and it is easier to obtain a desired coating film thickness.

  In addition, the metal precursor mentioned later may be provided after the plating undercoat polymer layer is formed, or may be contained in the composition for the plating undercoat polymer layer from the beginning. When the metal precursor is contained in the plating undercoat polymer layer forming composition, the content of the metal precursor is preferably 0.5% by mass to 80% by mass with respect to the total amount of the composition, and 1% by mass. More preferably, it is -50 mass%. Within this range, when a plating undercoat polymer layer containing reduced metal particles is used as an electrode, conductivity is good and energy loss is small.

〔solvent〕
The composition for forming a plating undercoat polymer layer according to the present invention preferably contains a solvent capable of dissolving the plating undercoat polymer in addition to the above-described plating undercoat polymer.
The solvent that can be used in the composition for forming a plating undercoat polymer layer is not particularly limited, and examples thereof include a solvent that is used in normal coating and the like. For example, alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, 1-methoxy-2-propanol, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, formamide, dimethylacetamide, N-methyl Amide solvents such as pyrrolidone, nitrile solvents such as acetonitrile and propyronitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, ether solvents, glycols Examples of the solvent include amine solvents, amine solvents, thiol solvents, and halogen solvents. In addition, these solvents may be used alone or in combination.
Although content in particular of the solvent in the composition for plating undercoat polymer layer formation is not restrict | limited, 50 mass%-95 mass% are preferable with respect to the composition whole quantity, and 70 mass%-90 mass% are more preferable. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the film thickness of a plating undercoat polymer layer.

In the composition for forming a plating undercoat polymer layer according to the present invention, water can be used as a solvent by neutralizing an ionic polar group with a base to increase hydrophilicity. In consideration of applicability at the time of application, it is preferable to use water and a water-soluble organic solvent in combination, and the content of the organic solvent at that time is 20% by mass to 90% by mass with respect to the total solvent. Preferably there is. Here, the water-soluble organic solvent means a solvent that can be dissolved in water within the above-mentioned content range. If it is an organic solvent which has such a property, it will not specifically limit, It can use as a solvent of a composition. As the water-soluble organic solvent, for example, ketone solvents, ester solvents, alcohol solvents, ether solvents, amine solvents, thiol solvents, halogen solvents and the like are preferably used.
Specific examples of organic solvents suitable for use in the present invention are listed below.

  Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, γ-butyrolactone, and hydroxyacetone. As ester solvents, 2- (2-ethoxyethoxy) ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methyl cellosolve acetate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl glycolate, glycol Examples include ethyl acid.

  Examples of alcohol solvents include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 3-acetyl-1-propanol, 2- (allyloxy) ethanol, 2-aminoethanol, 2-amino-2-methyl-1-propanol, ( S)-(+)-2-amino-1-propanol, (S)-(−)-2-amino-1-propanol, 3-amino-1-propanol, 2-dimethylaminoethanol, 2,3-epoxy -1-propanol, ethylene glycol, 2-fluoroethanol, diacetone alcohol, 2-methylcyclohexanol, 4-hydroxy-4-methyl-2-pentanone, glycerin, 2,2 ′, 2 ″ -nitrilotriethanol, 2- Pyridinemethanol, 2,2,3,3-tetrafluoro- -Propanol, 2- (2-aminoethoxy) ethanol, 2- [2- (benzyloxy) ethoxy] ethanol, 2,3-butanediol, 2-butoxyethanol, 2,2'-thiodiethanol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-2,4-pentanediol, 1,3-propanediol, diglycerin, 2,2′-methyliminodiethanol, 1,2 -Pentanediol and the like.

  Examples of ether solvents include bis (2-ethoxyethyl) ether, bis [2- (2-hydroxyethoxy) ethyl] ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxy). Ethoxy) ethyl] ether, bis (2-methoxyethyl) ether, 2- (2-butoxyethoxy) ethanol, 2- [2- (2-chloroethoxy) ethoxy] ethanol, 2-ethoxyethanol, 2- (2- Ethoxyethoxy) ethanol, 2-isobutoxyethanol, 2- (2-isobutoxyethoxy) ethanol, 2-isopropoxyethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, 2- (2-methoxyethoxy) ) Ethanol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol, Polypropylene glycol monomethyl ether, methoxy acetic acid and 2-methoxy ethanol.

Examples of glycol solvents include diethylene glycol, triethylene glycol, ethylene glycol, hexaethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
Examples of the amine solvent include N-methyl-2-pyrrolidone and N, N-dimethylformamide.
Examples of the thiol-based solvent include mercaptoacetic acid and 2-mercaptoethanol.
Examples of the halogen solvent include 3-bromobenzyl alcohol, 2-chloroethanol, 3-chloro-1,2-propanediol and the like.

  In addition, the solvents listed in Tables 1 and 2 below can also be used as the water-soluble organic solvent.

The boiling point of the water-soluble organic solvent in the present invention is preferably 70 ° C to 150 ° C, more preferably 65 ° C to 120 ° C, from the viewpoint of easiness of evaporation. Examples of such water-soluble organic solvents include ethanol (boiling point: 78 ° C.), isopropyl alcohol (boiling point: 82 ° C.), n-propyl alcohol (boiling point: 97 ° C.), THF (boiling point: 66 ° C.), 1- Preferred are methoxy-2-propanol (boiling point: 119 ° C.), MEK (boiling point: 80 ° C.) and the like.
In addition, as described above, when using a mixed solution of water and a water-soluble organic solvent, the flash point is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of ease of work. More preferably, it is at least ° C.
In addition, the flash point in this invention means the measured value obtained by the tag sealing type based on JIS-K2265.

-Water-
The water used in the composition for forming a plating undercoat polymer layer according to the present invention preferably contains no impurities, preferably RO water, deionized water, distilled water, purified water, etc., and deionized water or distilled water. More preferred.

-Additives to increase the solubility of the plating primer polymer-
In the case of using a mixed solution of water and a water-soluble organic solvent in the composition for forming a plating undercoat polymer layer according to the present invention, an additive can be used to increase the solubility of the plating undercoat polymer.
For example, when the plating undercoat polymer which is a solute has an acidic group such as a carboxylic acid group, the plating undercoat polymer can be mixed with water and a water-soluble organic solvent by converting the acidic group into a salt such as sodium carboxylate. It becomes easy to dissolve in the mixed solution. As an additive used for converting a carboxylic acid group to sodium carboxylate, a basic compound can be used. Specifically, sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, tetramethylammonium hydroxy Potassium carbonate, potassium carbonate, potassium hydroxide, lithium bicarbonate, lithium carbonate, lithium hydroxide, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ammonia, 1, 8-Diazabicyclo [5,4,0] -7-undecene (DBU), diazabicyclononene (DBN) and the like can be used. Particularly preferred are sodium hydrogen carbonate, sodium carbonate, and sodium hydroxide from the viewpoint of water solubility and optimum basicity.

[Material that can generate active species]
The composition for forming a plating undercoat polymer layer according to the present invention preferably contains a material capable of generating active species in order to increase sensitivity to energy application.

  As the radical initiator, a thermal polymerization initiator, a photopolymerization initiator or the like is used. As the thermal polymerization initiator, a peroxide initiator such as benzoyl peroxide or azoisobutyronitrile, and an azo-based initiator are used. An agent or the like can be used.

The photopolymerization initiator may be a low molecular compound or a high molecular compound, and generally known ones are used.
Examples of the low molecular weight photopolymerization initiator include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzophenone, benzophenones such as (4,4'-bisdimethylaminobenzophenone; benzylketals such as benzyldimethyl ketal and hydroxycyclohexyl phenyl ketone; Ketone; Benzoylbenzoate; Benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2-chlorothioxanthone, 2-methylthio Thioxanthones such as Sandton, 2-ethylthioxanthone, 2-isopropylthioxanthone; and other known photopolymerization initiators such as α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine, etc. can be used. Since sulfonium salts and iodonium salts used as photoacid generators also act as radical generators upon irradiation with light, these may be used in the present invention.

  As a polymer photopolymerization initiator, a polymer compound having an active carbonyl group in the side chain described in JP-A-9-77891 and JP-A-10-45927, and polymerization described in JP-A-2004-161995 A polymer in which an initiating group is pendant on a side chain can also be used by mixing with a plating undercoat polymer. Specifically, this polymer is a polymer having a functional group (polymerization initiating group) having a polymerization initiating ability in the side chain and a crosslinkable group, and this polymer has a polymerization initiating group bonded to the polymer chain, And the form by which the polymer chain was fix | immobilized by the crosslinking reaction can be formed. Specific examples include those described in paragraph numbers [0011] to [0158] of JP-A No. 2004-161995. Moreover, the high molecular compound which has the above-mentioned low molecular photoinitiator in the frame | skeleton can also be used.

  In addition, these radical initiators may be used alone or in combination.

Further, when the plating undercoat polymer can generate an active site that interacts with the support or the support having the undercoat layer by applying energy, that is, a polymer having a polymerization initiation site in the skeleton of the plating undercoat polymer is used. In such a case, it is not necessary to add these active species.
In addition, a material capable of generating these active species may be included in the resin film forming the support or the undercoat layer on the support. In such a case, not only the plating undercoat polymers but also the plating The interaction between the undercoat polymer and the support is more favorably formed, and the bond between the reflective layer containing silver and the support becomes stronger. As described above, when the resin forming the support is a resin having a polymerization initiation site in the polymer skeleton, it is not always necessary to add a material capable of generating active species.

The amount of the polymerization initiator to be contained in the plating undercoat polymer layer forming composition is selected according to the composition of the plating undercoat polymer layer forming composition. On the other hand, it is preferable that it is about 0.05-30 mass%, and it is more preferable that it is about 0.1-10.0 mass%.
Further, the content when the polymerization initiator is contained in the resin film substrate constituting the support is preferably about 0.05 to 30% by mass with respect to the solid content of the resin film substrate, More preferably, it is about 0.1-10.0 mass%.

[Sensitizer]
In the composition for forming a plating undercoat polymer layer according to the present invention, when energy is applied by exposure, a sensitizer can be contained in addition to the radical generator for the purpose of further increasing sensitivity to the exposure. .
The sensitizer is excited by active energy rays, and can promote the generation of radicals by interacting with the radical generator (for example, energy transfer, electron transfer, etc.).

There is no restriction | limiting in particular as a sensitizer which can be used for this invention, According to an exposure wavelength, it can select suitably from well-known sensitizers.
Specifically, for example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, Thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (E.g., anthraquinone), squalium (e.g., squalium), acridone (e.g., acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroa) Lidon etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 '-Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7- Methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 , 7-dipropoxycoumarin, etc. In addition, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, And coumarin compounds described in JP-A-2002-363209 and the like. In addition, n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone derivatives and the like are included.

  As a combination of a radical generator and a sensitizer, for example, an electron transfer type initiation system described in JP-A No. 2001-305734 [(1) an electron donating type initiator and a sensitizing dye, (2) an electron accepting type Initiators and sensitizing dyes, (3) electron-donating initiators, sensitizing dyes and electron-accepting initiators (ternary initiation system)] and the like.

  In addition, as a sensitizer, a sensitizer having a basic nucleus, a sensitizer having an acidic nucleus, a sensitizer having a fluorescent whitening agent, and the like can be used.

  These sensitizers are preferably contained in the composition for forming a plating undercoat polymer layer according to the present invention in an amount of about 1% by mass to 30% by mass with respect to the mass of the plating undercoat polymer.

[Surfactant]
The composition for forming a plating undercoat polymer layer according to the present invention may contain a surfactant.
The surfactant used in the present invention is not particularly limited as long as it is soluble in the aforementioned solvent. Examples of such a surfactant include an anionic surfactant such as sodium n-dodecylbenzenesulfonate, n- Cationic surfactants such as dodecyltrimethylammonium chloride, and polyoxyethylene nonylphenol ether (commercially available products such as “Emulgen 910” manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available) Examples of the product include a trade name “Tween 20” and the like, and nonionic surfactants such as polyoxyethylene lauryl ether.

[Plasticizer]
Moreover, a plasticizer can also be added to the composition for forming a plating undercoat polymer layer according to the present invention, if necessary. Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, diethyl ester, dibutyl ester, di-2-ethylhexyl ester, dinormal octyl ester, diisononyl ester, dinonyl ester, diisodecyl ester). Ester, butyl benzyl ester), adipic acid ester (dioctyl ester, diisononyl ester), azelain san dioctyl, sebacin sun ester (dibutyl ester, dioctyl ester), tricresyl phosphate, acetyl tributyl citrate, epoxidized soybean oil, tri High-boiling solvents such as trioctyl melitrate, chlorinated paraffin, dimethylacetamide, and N-methylpyrrolidone can also be used.

(Polymerization inhibitor)
A polymerization inhibitor can also be added to the composition for forming a plating undercoat polymer layer according to the present invention, if necessary. As the polymerization inhibitor that can be used, hydroquinones such as hydroquinone, ditertiary butyl hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, phenols such as p-methoxyphenol and phenol, Benzoquinones, TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) free radical), free radicals such as 4-hydroxy TEMPO, phenothiazines, N-nitrosophenylhydroxyamine, aluminum salts thereof Nitrosamines such as catechol can be used.

[Curing agent, curing accelerator]
In addition, as will be described later, when the plating undercoat polymer layer is formed on the adhesion auxiliary layer using the plating undercoat polymer layer forming composition according to the present invention, the plating undercoat polymer layer is used in order to promote curing of the adhesion auxiliary layer. Curing agents and / or curing accelerators can be added to the forming composition. For example, as a curing agent and / or a curing accelerator when an epoxy compound is contained in the adhesion auxiliary layer, in the polyaddition type, aliphatic polyamine, alicyclic polyamine, aromatic polyamine, polyamide, acid anhydride, phenol, phenol Examples of catalyst types such as novolak, polymercaptan, compounds having two or more active hydrogens include aliphatic tertiary amines, aromatic tertiary amines, imidazole compounds, and Lewis acid complexes.

Also, those that start curing by heat, light, moisture, pressure, acid, base, etc. include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyamidoamine, mensendiamine, isophoronediamine, N-amino. Ethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4 -Aminocyclohexyl) methane, m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylteto Hydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate), Methylcyclohexene tetracarboxylic acid anhydride, trimellitic anhydride, polyazeline acid anhydride, phenol novolak, xylylene novolak, bisphenol A novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadiene phenol novolak, terpene phenol novolak, polymercaptan , Polysulfide, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol-tri-2- Tylhexylate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1- Benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-S-triazine, BF ₃ monoethylamine complex, Lewis Acid complexes, organic acid hydrazides, diaminomaleonitrile, melamine derivatives, imidazole derivatives, polyamine salts, amine imide compounds, aromatic diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, triaryl selenium salts, ketimine compounds, etc. Can be mentioned.

These curing agents and / or curing accelerators are from 0 to 50 mass of the remaining non-volatile components from which the solvent has been removed from the viewpoints of applicability of the composition for forming a plating undercoat polymer layer, adhesion to a substrate and a plating film, and the like. It is preferable to add up to about%.
The curing agent and / or curing accelerator may be added to the adhesion auxiliary layer. In that case, the above range is the amount added to the adhesion auxiliary layer and the total amount added in the composition for forming the plating undercoat polymer layer. It is preferable to satisfy.

[Other additives]
The composition for forming a plating undercoat polymer layer according to the present invention further includes a rubber component (for example, CTBN), a flame retardant (for example, a phosphorus flame retardant), a diluent, a thixotropic agent, a pigment, Add foaming agents, leveling agents, coupling agents, water-soluble substances (for example, mineral components such as calcium oxide and magnesium oxide), soluble low-molecular substances (for example, polyalkyl glycols such as ε-caprolactam and polyethylene glycol), etc. May be. Moreover, you may add antioxidant as illustrated by the term of the support body.

  As a composition for forming a plating undercoat polymer layer according to the present invention, by using a composition in which a plating undercoat polymer and various additives are appropriately mixed, physical properties of the formed plating undercoat polymer layer, for example, a thermal expansion coefficient, The glass transition temperature, Young's modulus, Poisson's ratio, breaking stress, yield stress, thermal decomposition temperature, etc. can be set optimally. In particular, it is preferable that the breaking stress, yield stress, and thermal decomposition temperature be higher.

[Method of forming plating undercoat polymer layer]
Hereinafter, a material for the mirror film and a method for producing a plating undercoat polymer layer using the material will be briefly described.
Moreover, the manufacturing method of a mirror film is explained in full detail after that.

(Contact of the composition for forming the plating undercoat polymer layer to the support)
The method for bringing the obtained composition for forming a plating undercoat polymer layer into contact with the film substrate for forming the support is not particularly limited, and a method for immersing the film substrate in the composition for forming a plating undercoat polymer layer (for example, A dip coater) and a method of applying a coating undercoat polymer layer forming composition on a support.

(Granting energy)
After bringing the composition for forming a plating undercoat polymer layer into contact with the support, by applying energy, the polymerizable groups of the polymer in the energy application region, or between the polymerizable group of the polymer and the support In this way, a plating undercoat polymer layer immobilized on the support is formed.

(Removal of unreacted plating undercoat polymer)
Furthermore, you may perform the process of removing an unreacted polymer suitably after energy provision.

(Physical properties of plating undercoat polymer layer)
The thickness of the plating undercoat polymer layer thus formed is not particularly limited, but is preferably 0.05 to 10 μm, preferably 0.3 to 5 μm from the viewpoint of adhesion with a metal film to be a reflection layer to be formed later. Is more preferable.
Also preferably 0.05 to 10 g / ^{m 2} by dry weight, in particular 0.3 to 5 g / ^{m 2} is preferred.

The surface roughness Ra of the plating undercoat polymer layer is preferably 20 nm or less, more preferably 10 nm or less, and still more preferably 5 nm or less. Within this range, the Ag surface after plating becomes smooth and the reflectivity is good.
The surface roughness is measured using an atomic force microscope (AFM) (manufactured by Seiko Instruments, SPA-400).

(Reduced metal particles)
The plating undercoat polymer layer of the present invention contains reduced metal particles. The reduced metal particles contained in the plating undercoat polymer layer are obtained by applying a metal precursor to the above-described plating undercoat polymer layer formed on the support and reducing the metal precursor. When the metal precursor is applied to the plating undercoat polymer layer, the metal precursor adheres to the interactive group by interaction.
The metal precursor contained in the plating undercoat polymer layer will be described below.

(Metal precursor)
The metal precursor used in the present invention can be used without particular limitation as long as it functions as an electrode by being changed to a metal by a reduction reaction. Moreover, as a metal precursor, what functions as an electrode of plating in the formation process of a silver containing metal layer is mentioned preferably. Therefore, what functions as an electrode by reducing a metal precursor to a metal is preferable.
Specifically, metal ions such as Au, Pt, Pd, Ag, Cu, Ni, Al, Fe, and Co are used. Metal ions that are metal precursors are contained in a composition containing a plating undercoat polymer (a composition for forming a plating undercoat polymer layer). After forming a layer on the support, zero-valent metal particles are formed by a reduction reaction. It becomes.
It is preferable that the metal ion which is a metal precursor is contained in the composition for forming a plating undercoat polymer layer as a metal salt.
The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. For example, Ag ion, Cu ion, Al ion, Ni ion, Co ion, Fe ion, and Pd ion can be mentioned. Among them, those capable of multidentate coordination are preferable, and in particular, the type and number of functional groups capable of coordination. From the viewpoint of catalytic ability, Ag ions, Cu ions, and Pd ions are preferable.

One preferred example of the metal precursor used in the present invention is silver ion.
When silver ions are used, those obtained by dissociating silver compounds as shown below can be suitably used. Specific examples of the silver compound include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, silver diethyldithiocarbamate, Examples thereof include silver diethyldithiocarbamate and silver p-toluenesulfonate. Among these, silver nitrate is preferable from the viewpoint of water solubility.
Moreover, as a metal precursor, a copper ion is mentioned as another preferable example. When using copper ion, the thing which the copper compound as shown below dissociated can be used suitably. Specific examples of copper compounds include copper nitrate, copper acetate, copper sulfate, copper cyanide, copper thiocyanate, copper chloride, copper bromide, copper chromate, copper chloranilate, copper salicylate, copper diethyldithiocarbamate, diethyldithiol. Examples thereof include copper carbamate and copper p-toluenesulfonate. Among these, copper sulfate is preferable from the viewpoint of water solubility.

The metal precursor shown above is preferably applied to the plating undercoat polymer layer as a dispersion or solution (metal precursor liquid).
As a method for the application, a layer is formed on a support using the composition containing the plating undercoat polymer, and then a composition (dispersion liquid or metal precursor liquid) containing a metal precursor is immersed in the layer. The method of forming the plating undercoat polymer layer containing a metal precursor by making it contact is mentioned.
Water and organic solvents are used as the solvent used in the metal precursor dispersion and the solvent used in the solution. By containing water or an organic solvent, the permeability of the metal precursor to the polymer layer is improved, and the metal precursor can be efficiently adsorbed to the interactive group.

In order to apply the metal precursor to the plating undercoat polymer layer, the particle diameter of the metal precursor in the case of using the dispersion is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and more preferably 1 nm to 60 nm. More preferably. By setting this particle size, the particle size of the reduced metal particles can be controlled to a desired size.
In addition, a particle diameter is an average primary particle diameter (volume conversion) here, and the measuring method is the same as the method described in the term of a metal particle.

  The water used for the metal precursor liquid preferably contains no impurities. From such a viewpoint, it is preferable to use RO water, deionized water, distilled water, purified water or the like, and it is particularly preferable to use deionized water or distilled water. There is no restriction | limiting in particular as an organic solvent used for a metal precursor liquid, if it is a solvent which can osmose | permeate a polymer layer. For example, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone , Dimethyl carbonate, dimethyl cellosolve, etc. can be used.

In particular, from the viewpoint of compatibility with the metal precursor and permeability to the polymer layer, water or a water-soluble organic solvent is preferable, and acetone, dimethyl carbonate, dimethyl cellosolve, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether is preferred.
Further, the dispersion or solution may contain other additives depending on the purpose. Examples of other additives include swelling agents and surfactants.

  The particle diameter of the reduced metal particles contained in the plating undercoat polymer layer is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and still more preferably 1 nm to 60 nm. By being in this range, the reflectance after plating becomes good.

  In addition, a particle diameter is an average primary particle diameter (volume conversion) here, and is read from a SEM (Hitachi High-Tech Manufacturing & Service Co., Ltd. S-5200) image.

<(C) Reflective layer containing silver>
The silver-containing reflective layer (silver-containing metal layer) in the present invention is a reflective layer composed of a silver-containing metal film, and is the outermost surface, that is, the surface on the side where the (D) resin coating layer described later is provided. The roughness Ra is preferably 20 nm or less. The reflective layer may be a single-layer metal layer or may have a laminated structure of a plurality of metal layers having different metal compositions, but since silver is excellent in reflectivity, the outermost surface layer contains silver. It is preferable that it is a metal layer.
The silver-containing metal layer in the present invention can be obtained by forming a silver-containing metal film on the plating undercoat polymer layer containing the reduced metal particles by an electroplating method or the like.
As a method other than electroplating, a method such as vapor deposition or sputtering may be used.

  The metal forming the silver-containing metal layer in the present invention is silver or an alloy containing silver because of light reflection performance. Silver or an alloy containing silver increases the reflectance in the visible light region of the mirror film, and can reduce the dependency of the reflectance on the incident angle. The visible light region means a wavelength region of 400 nm to 700 nm. Here, the incident angle means an angle with respect to a line perpendicular to the film surface.

As the silver alloy, silver and one or more metals selected from the group consisting of gold, palladium, tin, gallium, indium, copper, titanium, and bismuth are used because the durability of the silver-containing metal layer is improved. An alloy is preferred. In particular, an alloy of silver and gold is preferable from the viewpoint of high-temperature humidity resistance and reflectance.
When the silver-containing metal layer is a film made of a silver alloy, the silver content is preferably 90 to 99.8 atomic% in the total (100 atomic%) of silver and other metals in the silver-containing metal layer. . Further, the content of other metals is preferably 0.2 to 10 atomic% from the viewpoint of durability.

The surface roughness (Ra) of the silver-containing metal layer in the present invention is preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. By making it within this range, the reflectance of the obtained mirror film is improved, and solar energy / light is efficiently collected / condensed, and energy efficiency when used in a solar thermal power generation device is increased.
The surface roughness is measured using an atomic force microscope (AFM) (manufactured by Seiko Instruments, SPA-400).

Hereinafter, the case where a silver containing metal layer is formed by the method by electroplating is demonstrated.
As a method of electroplating, a conventionally known method can be used.
In the present invention, when the plating undercoat polymer layer containing the reduced metal particles has a function as an electrode, the silver-containing metal layer can be formed by electroplating the plating undercoat polymer layer.
In addition, between the plating undercoat polymer layer and the silver-containing metal layer, for example, a metal layer containing another metal such as copper, nickel, chromium, or iron may be provided as the base metal layer.
In addition, the film thickness of the silver-containing metal layer obtained by electroplating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like. By adding a base metal layer having an appropriate thickness, it is possible to improve reflectance and reduce pinholes by smoothing the surface.
The film thickness of the silver-containing metal layer is 0.05 μm or more and 2.0 μm or less from the viewpoint of forming a reflective film without pinholes and not forming irregularities that scatter light on the surface of the silver-containing metal layer. It is preferable that it is 0.08 to 0.5 μm.

  Alternatively, a silver-containing metal layer may be formed by performing dry plating such as vacuum deposition using a plating undercoat polymer layer containing reduced metal particles obtained by reducing a metal precursor. In this case, since the surface is covered with a metal, it is possible to form a silver-containing metal layer that has better adhesion than ordinary vapor deposition and is strong against heat.

  Furthermore, after electroplating, in order to improve the reflection performance of the silver-containing metal layer or to improve the durability of the silver-containing metal layer, the silver-containing metal layer may be treated with a strong acid or strong alkali. Good. Further, an inorganic film or a metal oxide film may be formed on the metal surface. Moreover, you may process with a discoloration prevention agent and provide a discoloration prevention agent layer.

  The discoloration preventing agent layer functions as discoloration prevention for the silver-containing metal layer. Examples of the discoloration inhibitor include thioether, thiol, Ni organic compound, benzotriazole, imidazole, oxazole, tetrazaindene, pyrimidine, and thiadiazole.

  The anti-discoloring agent layer is roughly classified into those having an adsorption group with silver and an antioxidant. Specific examples will be given below.

(Anti-discoloration agent having an adsorption group with silver)
Examples of the discoloration inhibitor having an adsorption group with silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring, compounds having a pyrazole ring, compounds having a thiazole ring, compounds having an imidazole ring, and indazole It is desirable to select at least one of a ring-containing compound, a copper chelate compound, a thiourea, a mercapto group-containing compound, a naphthalene-based compound, or a mixture thereof.

  Examples of amines and derivatives thereof include ethylamine, laurylamine, tri-n-butylamine, o-toluidine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, monoethanolamine, diethanolamine, triethanolamine, 2N- Dimethylethanolamine, 2-amino-2-methyl-1,3-propanediol, acetamide, acrylamide, benzamide, p-ethoxychrysidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolaminebenzoate, dicyclohexylammonium benzoate, diisopropyl Ammonium benzoate, diisopropylammonium nitrite, Black hexylamine carbamate, nitronaphthalene nitrite, cyclohexylamine benzoate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylamine cyclohexane carboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate, or mixtures thereof.

  Examples of the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, N-phenyl-3, 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.

Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t) ert-butylphenyl) benzotriazole, 2- (2′-hydroxy 3′5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-4-octoxyphenyl) benzotriazole, or the like Of the mixture.

Examples of the compound having a pyrazole ring include pyrazole, pyrazoline, pyrazolone, pyrazolidine, pyrazolidone, 3,5-dimethylpyrazole, 3-methyl-5-hydroxypyrazole, 4-aminopyrazole, and the like, or a mixture thereof.
Examples of the compound having a thiazole ring include thiazole, thiazoline, thiazolone, thiazolidine, thiazolidone, isothiazole, benzothiazole, 2-N, N-diethylthiobenzothiazole, p-dimethylaminobenzallodanine, 2-mercaptobenzothiazole and the like. Or a mixture thereof.

  Examples of the compound having an imidazole ring include imidazole, histidine, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methyl. Imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2-phenyl-4-methyl-5-hydromethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 4-formylimidazole, 2-methyl-4-formylimidazole, 2-phenyl-4- Fo Milimidazole, 4-methyl-5-formylimidazole, 2-ethyl-4-methyl-5-formylimidazole, 2-phenyl-4-methyl-4-formylimidazole, 2-mercaptobenzimidazole, etc., or these Of the mixture.

Examples of the substance having an indazole ring include 4-chloroindazole, 4-nitroindazole, 5-nitroindazole, 4-chloro-5-nitroindazole, and a mixture thereof.
Examples of the copper chelate compounds include acetylacetone copper, ethylenediamine copper, phthalocyanine copper, ethylenediaminetetraacetate copper, hydroxyquinoline copper, and a mixture thereof.
Examples of thioureas include thiourea, guanylthiourea, and the like, or a mixture thereof.

As a product having a mercapto group, if the above-mentioned materials are added, mercaptoacetic acid, thiophenol, 1,2-ethanediol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto -1,2,4-triazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane, and the like, or a mixture thereof.
Examples of naphthalene compounds include thionalide.

<(D) Resin coating layer>
The mirror film of the present invention is provided with a (D) resin coating layer on the incident light side for the purpose of preventing light resistance deterioration due to sunlight or ultraviolet rays and preventing silver-containing metal layer deterioration due to oxygen or moisture.
When forming the resin coating layer, a film for forming a resin coating layer in which an ultraviolet absorber is dispersed in various conventionally known resins is pasted, and the surface of the silver-containing metal layer and the silver-containing metal layer of the support are not formed. A method of closely adhering to the peripheral portion, a UV curable resin in which an ultraviolet absorber is dispersed or a thermosetting resin in which an ultraviolet absorber is dispersed is applied to a support surface having a silver-containing metal layer and cured, For example, the surface of the silver-containing metal layer and the peripheral portion where the silver-containing metal layer of the support is not formed can be used.
The resin used for the resin coating layer is not only strong, durable, adhesion to adjacent layers, air and moisture barrier properties, but also transparent, especially for light of the wavelength required by mirror films What can form a film or a layer excellent in the thickness is preferable.

  First, a method for forming a resin coating layer without using a resin film will be described. In this method, a resin material for forming a resin coating layer shown below is dissolved in a solvent, and a laminated body in which a reflective layer containing silver is formed in a region excluding the peripheral portion of the support obtained in the previous step. It is uniformly applied to the surface, that is, the reflection layer and the peripheral surface of the support, and dried to form a layer made of the resin material for forming the resin coating layer, and then the formed resin material for forming the resin coating layer. It is a method of curing the layer.

  Examples of the resin that forms the resin coating layer include cellulose ester resins, polyester resins, polycarbonate resins, polyarylate resins, polysulfone (including polyethersulfone) resins, polyesters such as polyethylene terephthalate and polyethylene naphthalate. Resins, olefin resins such as polyethylene and polypropylene, cellulose diacetate resin, cellulose triacetate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, norbornene resin, polymethylpentene resin And acrylic resins such as polyamide resin, fluorine resin, and polymethyl methacrylate. Of these, polycarbonate resins, polyester resins, norbornene resins, acrylic resins, fluorine resins, olefin resins, and the like are preferable. More specifically, polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PMMA) are preferable. PMMA is more preferable.

The solvent used for dissolving the resin material for forming the resin coating layer may be appropriately selected from those suitable for the resin. For example, acetone, ethyl acetate, butyl acetate, methyl ethyl ketone (MEK), N, N-dimethylformamide (DMF) ), Cyclohexane, cyclohexanol, cyclohexanone, ethylbenzene and the like. Only 1 type may be used for a solvent and it may combine 2 or more types. Further, from the viewpoint of uniformly forming a resin coating layer having excellent adhesion, the solid content concentration of the coating solution is preferably in the range of 1% by mass to 30% by mass.
The method of curing after applying the resin material for forming the resin coating layer is not particularly limited, and a method according to the resin material used for forming the resin coating layer, such as heating or UV irradiation, can be appropriately selected. That's fine.
Moreover, the method etc. which form the said resin material using methods, such as a vacuum evaporation, can also be taken.
The film thickness of the resin coating layer when the resin coating layer is formed using a coating method or a vacuum deposition method is not particularly limited as long as the influence of moisture and oxygen on the silver-containing reflective layer can be suppressed, but the protective effect and durability Considering the properties, it is preferably in the range of 10 μm to 150 μm.
When forming a resin coating layer using a coating method or a vacuum deposition method, the resin material for forming the resin coating layer is directly contacted on the silver-containing metal layer and the support without using an adhesive layer. A coating layer can be formed.

Next, a method for forming a resin coating layer using a resin film will be described.
When the resin coating layer is formed using a resin film, the resin film for forming the resin coating layer is bonded to a support provided with a silver-containing metal layer by a method such as thermal lamination, and pasted through an adhesive. What is necessary is just to adhere | attach a resin film and a support body peripheral part by the method to do. The resin film used here will be described in detail below.
When the resin film is bonded via an adhesive, the resin film may be subjected to corona discharge treatment, heat treatment, and UV surface treatment to improve adhesion.

  Examples of the resin film forming the resin coating layer include cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate, and the like. Polyester film, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic Polystyrene film, polycarbonate film, norvo Nene resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. Among these, polycarbonate resin films, polyester resin films, norbornene resin films, acrylic resin films, fluorine resin films, olefin resin films, and the like are preferable. More specifically, polyvinylidene fluoride (PVDF) films, poly A methyl methacrylate (PMMA) film is preferable, and a PMMA film is more preferable.

  Moreover, you may use the surface protection film etc. which provided the polyolefin-type film marketed as surface protection films, such as building materials, a polyvinyl chloride type film, and the adhesion layer. For commercial products, various materials such as polyethylene, polypropylene monolayer or laminated film, and polymer alloys containing raw materials derived from vegetable oils and fats are used. For example, SPV series [Nitto Denko Corporation], protection tape [Sekisui Chemical Co., Ltd.] Ltd.], Hitarex [Hitachi Chemical Industry Co., Ltd.], Sumilon E. V. Examples include commercial products such as A [Sumilon Co., Ltd.] and Sanitect [San-A Chemical Co., Ltd.]. Among these commercial products, those having high transparency to visible light are used for forming the resin coating layer. That's fine. Among these protective films, those with an adhesive layer can be used as they are for forming a resin coating layer.

Among these resin materials, an acrylic resin is more preferable from the viewpoint of light transmittance, and it is particularly preferable to use a resin material or a resin film mainly composed of polymethyl methacrylate.
In order to effectively suppress the penetration of oxygen and moisture, the resin material constituting the resin coating layer has an oxygen permeability of 1.0 × 10 ⁻⁹ cc when the film is formed to a thickness of 100 μm. It is preferable to include a resin composition of / cm ² · s · 10 mmHg or less. Here, the value measured by MOCON oxygen permeability measuring device OX-TRAN2 / 61 series [trade name, manufactured by Hitachi High-Technologies Corporation] is adopted as the oxygen permeability.
When using a resin film, there is no restriction | limiting in the shaping | molding method, Even if it is the film manufactured by melt casting film forming, the film manufactured by solution casting film forming may be sufficient.
The film thickness of the resin film is selected in accordance with the characteristics of the resin material as long as the necessary protective functions and durability can be achieved. Generally, the thickness of the resin coating layer formed by application of the resin material Similarly, it is preferably in the range of 10 μm to 200 μm.

Moreover, it is preferable that the film used for the resin coating layer contains an ultraviolet absorber, and the aforementioned one can be used as the ultraviolet absorber.
Content of the ultraviolet absorber in a resin protective layer is 0.1-20 mass% with respect to the resin protective layer total mass, Preferably it is 1-15 mass%, More preferably, it is 3-10 mass%. When it is more than 20% by mass, the adhesion is deteriorated, and when it is less than 0.1% by mass, the effect of improving weather resistance is small.

(D) The resin coating layer is preferably bonded onto the (C) silver-containing metal layer via an adhesive layer. The adhesive layer is required to have adhesion for bringing the silver-containing metal layer and the resin coating layer into close contact, weather resistance, smoothness for drawing out high reflection performance, and no light absorption in the reflected light region.
A resin is used for the adhesive layer, and the resin to be used is not particularly limited as long as the above conditions such as adhesion, weather resistance, heat resistance, and smoothness are satisfied. Polyurethane resin, polyester Resin, acrylic resin, melamine resin, epoxy resin, polyamide resin, vinyl chloride resin, vinyl chloride / vinyl acetate copolymer resin, etc. can be used alone or in combination, and from the point of weather resistance A polyurethane-based resin, a mixed resin of a polyester-based resin and a melamine-based resin are preferable, and it is more preferable to mix a curing agent such as isocyanate to obtain a thermosetting type. The adhesive layer may contain the aforementioned ultraviolet absorber, a plasticizer for maintaining flexibility, an antioxidant for preventing deterioration of the film itself, a radical scavenger and the like.

The thickness of the adhesive layer is preferably from 0.01 to 15 μm, more preferably from 0.1 to 5 μm. If the thickness is less than 0.01 μm, the adhesion is poor and there is no effect of forming an adhesive layer, and it becomes difficult to cover and smooth the fine irregularities on the surface of the film substrate, resulting in poor smoothness. This is not preferable. Even if the thickness is thicker than 5 μm, improvement in adhesion cannot be expected, and on the contrary, unevenness in coating may result in poor smoothness or insufficient curing of the adhesive layer, which is not preferable.
As a method for forming the adhesive layer, conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.

  As described above, in the case of forming the resin coating layer (D) by application of a resin material for forming a resin coating layer preferably containing an ultraviolet absorber, oxygen or oxygen can be controlled by controlling the casting conditions and application conditions. Since adhesiveness that can block moisture permeation can be secured, it is not always necessary to open the adhesive layer.

The mirror film of the present invention has the above-described configuration. In the mirror film of the present invention, the reflectance of light having a wavelength of 600 nm is preferably 90% or more, and more preferably 94% or more.
The reflectance was measured with a spectrophotometer UV-3100PC (trade name, manufactured by Shimadzu Corporation), and a value at a wavelength of 600 nm was used.

  In condensing sunlight, the mirror film may be bonded to a rigid housing. The rigid housing refers to a metal such as SUS, Al, and an Al alloy, a resin such as vinyl chloride, polycarbonate, and acrylic, and a composite material such as CRP and FRP. A mirror film can be bonded to the casing with the following adhesive layer on the casing having the shape to be condensed.

The adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, a heat sealing agent, a hot melt agent, and the like is used. For example, polyester resin, urethane resin, polyvinyl acetate resin, acrylic resin, nitrile rubber, silicone resin and the like are used. The laminating method is not particularly limited, and for example, it is preferable to carry out continuously by a roll method from the viewpoint of economy and productivity. The thickness of the adhesive layer is usually selected from a range of about 1 to 50 μm. When the thickness is less than 1 μm, a sufficient adhesive effect cannot be obtained. On the other hand, when the thickness exceeds 50 μm, the pressure-sensitive adhesive layer is too thick and the drying speed is slow, which is inefficient. In addition, the original adhesive strength cannot be obtained, and adverse effects such as residual solvent occur, which is not preferable.
Moreover, you may use resin described by the above-mentioned contact bonding layer for the adhesion layer.
The thickness of the entire mirror film according to the present invention is preferably 75 to 250 μm, more preferably 90 to 230 μm, and still more preferably 100 to 220 μm. When the thickness is 75 μm or less, the mirror film is bent when the mirror film is attached to a metal case or the like, so that sufficient reflectivity cannot be obtained. Therefore, it is not preferable.

  The resin coating layer, which is the outermost layer of the mirror film thus obtained, preferably has a surface roughness of 20 nm or less, more preferably 10 nm or less. It can be a film.

<Manufacturing method of mirror film>
Next, each process is demonstrated one by one about the manufacturing method of the mirror film of this invention. The method described below is one embodiment of the present invention, and the present invention is not limited thereto.
The method for producing a mirror film of the present invention includes a step of forming a plating undercoat polymer layer containing reduced metal particles on a support (referred to as “step 1”), and a metal layer containing silver by electroplating. And a step of forming a resin coating layer (referred to as “Step 3”).

[Step of forming a plating undercoat polymer layer containing reduced metal particles on a support]
The step of forming a plating undercoat polymer layer containing reduced metal particles on a support includes a step of forming a polymer layer containing a metal precursor (referred to as “step 1-1”), and the metal precursor. It is preferable to consist of a process of reducing (referred to as "process 1-2").
In addition, “Step 1-1” is a step of forming a polymer layer by providing a layer on a support and applying energy to the polymer layer forming composition containing a plating undercoat polymer by a method such as coating (“Step It is preferable to include “1-1-1” and a step of imparting a metal precursor to the polymer layer (“step 1-1-2”).
The “composition for forming a polymer layer containing a plating undercoat polymer” means a composition containing a plating undercoat polymer and other components such as a solvent without containing a metal precursor. In addition, the “polymer layer” means a layer formed on a support that does not include a metal precursor and includes a plating undercoat polymer and other components.

(Step 1-1-1)
In Step 1-1-1, by applying energy to the substrate having the polymer layer, the polymerizable group contained in the plating undercoat polymer and the functional group on the surface of the support are activated, so Crosslinking, chemical bonds, etc. are formed between the support and the polymer layer. As a result, the polymer layer and the support are firmly adhered.

The method of providing the polymer layer on the support is not particularly limited, and a method of immersing the support in a composition for forming a polymer layer containing a plating undercoat polymer (for example, a dip coater) or for forming a polymer layer containing a plating undercoat polymer Examples thereof include a method of applying the composition on a support. From the viewpoint of easily controlling the thickness of the resulting polymer layer, a method of applying a polymer layer forming composition containing a plating undercoat polymer on a support is preferred.
The coating method is not particularly limited, and specific methods include a double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coating, blade coater, doctor coater, squeeze coater, reverse roll coater, transfer. Known methods such as a roll coater, an extrusion coater, a curtain coater, a die coater, a gravure roll coating method, an extrusion coating method, and a roll coating method can be used.

The coating amount of the polymer layer forming composition containing the plating undercoat polymer to the support is 0.05 g / m ^{2 to} 10 g / in terms of solid content from the viewpoint of sufficient interaction with the metal precursor described later. m ² are preferred, especially 0.3 g ^/ m 2 to 5 g / ^{m 2} is preferred.
In Step 1-1-1, when the polymer layer is formed, the polymer layer may be exposed in a state where the solvent remains, or may be exposed after drying to remove the residual solvent. From the viewpoint of the surface smoothness of the layer, it is preferable to expose after drying. As drying conditions, the polymer layer is preferably dried at 20 ° C. to 60 ° C. for 1 second to 2 hours, and then dried at a temperature exceeding 60 ° C. for 1 second to 2 hours, and at 20 ° C. to 60 ° C. for 1 second to 20 hours. It is more preferable to dry for 1 second to 20 minutes at a temperature exceeding 60 ° C. after the partial drying.

As an energy providing method in Step 1-1-1, for example, heating or exposure can be used.
Examples of the light source for exposure include a mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.
Plasma irradiation by arc discharge or glow discharge can also be used as a method for imparting energy.

When heating is performed, for example, a general heat heat roller, laminator, hot stamp, electric heating plate, thermal head, laser, blower dryer, oven, hot plate, infrared dryer, heating drum, or the like can be used.
The time required for energy application varies depending on the light source, but is usually between 0.5 seconds and 5 hours.
Moreover, you may combine these energy provision methods. For example, exposure and heating may be combined.
In addition, when energy is applied by exposure, the exposure power makes the surface after removal of the unreacted polymer, which will be described later, smoother in order to facilitate the polymerization and to suppress the decomposition of the polymer. Therefore, it is preferably in the range of 10~8000mJ / cm ^2, and more preferably in the range of 100~3000mJ / cm ^2.
In addition, when energy is imparted by heating, the temperature is preferably in the range of 20 ° C. to 200 ° C. in order to facilitate the polymerization and to suppress thermal denaturation of the support, and is in the range of 40 ° C. to 120 ° C. More preferably, it is in the range of ° C.

Further, the exposure may be performed in an atmosphere in which substitution with an inert gas such as nitrogen, helium, carbon dioxide or the like is performed and the oxygen concentration is suppressed to 600 ppm or less, preferably 400 ppm or less. Furthermore, energy may be applied in a pattern as necessary.
Furthermore, after the energy application, the unreacted plating undercoat polymer may be appropriately removed from the polymer layer after the energy application. Examples of the removal method include a method of using a solvent. For example, when the solvent for dissolving the plating undercoat polymer or the plating undercoat polymer is alkali-soluble, an alkaline developer (sodium carbonate, sodium hydrogen carbonate, aqueous ammonia) is used. , Sodium hydroxide aqueous solution) and the like.

The thickness of the resulting polymer layer is not particularly limited, but is preferably 0.05 to 10 μm, more preferably 0.3 to 5 μm, from the viewpoint of adhesion of the silver-containing metal layer to the support.
Also preferably 0.05 to 10 g / ^{m 2} by dry weight, in particular 0.3 to 5 g / ^{m 2} is preferred.
Furthermore, the surface roughness (Ra) of the polymer layer is preferably 20 nm or less, more preferably 10 nm or less, from the viewpoint of reflection performance.
In addition, it is preferable that content of the polymer in a polymer layer is 2 mass%-100 mass% with respect to the polymer layer whole quantity, More preferably, it is the range of 10 mass%-100 mass%.

(Step 1-1-2)
The method for applying the metal precursor to the polymer layer obtained in Step 1-1-1 is not particularly limited.
For example, a dispersion in which a metal precursor is dispersed in an appropriate dispersion medium, or a solution containing a dissociated metal ion by dissolving a metal salt in an appropriate solvent, and preparing the dispersion or solution (metal precursor liquid) Examples thereof include a method of coating on the polymer layer, and a method of immersing the substrate on which the polymer layer is formed in the dispersion or solution.
The contact time between the polymer layer and the metal precursor-containing liquid (dispersion liquid, solution) is preferably about 30 seconds to 24 hours, and more preferably about 1 minute to 1 hour.
The temperature of the metal precursor-containing liquid at the time of contact is preferably about 5 to 80 ° C, more preferably about 15 to 60 ° C.

By bringing the metal precursor-containing liquid into contact with each other as described above, the interaction group in the plating undercoat polymer is caused to interact by intermolecular force such as van der Waals force, or by coordinate bond by a lone electron pair. The metal precursor can be adsorbed using the interaction.
From the viewpoint of sufficiently performing such adsorption, the metal precursor concentration or the metal ion concentration in the metal precursor-containing liquid is preferably in the range of 0.001 to 50% by mass, A range of 30% by mass is more preferable.

(Step 1-2: Step of reducing metal precursor)
Metal ions, which are metal precursors applied to the polymer layer, are reduced with a metal activation liquid (reducing liquid). The metal activation liquid is composed of a reducing agent capable of reducing a metal precursor (mainly metal ions) to a zero-valent metal and a pH adjusting agent for activating the reducing agent.
It is preferable that the density | concentration of the reducing agent with respect to the whole metal activation liquid is 0.05-50 mass%, and it is more preferable that it is 0.1-30 mass%.
As the reducing agent, it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, or a reducing agent such as formaldehyde or hypophosphorous acid.
In particular, reduction with an aqueous alkaline solution containing formaldehyde is preferred.

As a density | concentration of the pH adjuster with respect to the whole metal activation liquid, it is preferable that it is the range of 0.05-10 mass%, and it is more preferable that it is the range of 0.1-5 mass%.
As the pH adjuster, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen carbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide and the like can be used.
Moreover, as temperature at the time of reduction | restoration, 10 to 100 degreeC is preferable and 20 to 70 degreeC is still more preferable.
These concentrations and temperature ranges are preferably within this range from the viewpoint of the particle diameter of the metal precursor, the surface roughness of the polymer layer, the conductivity (surface resistance value), and the deterioration of the reducing solution during reduction.

In the next step of forming the silver-containing metal layer, the surface resistance value of the plating undercoat polymer layer containing the reduced metal particles is preferably 0.001Ω / □ or more and 100Ω / □ or less, and It is more preferable that it is 03Ω / □ or more and 50Ω / □ or less. Within this range, the plated surface is formed uniformly and smoothly and the reflectance is good.
As a measuring method of surface resistance, it measured with the surface resistance meter (the Mitsubishi Chemical make, Lorestar GP MCP-T600).
Further, from the viewpoint of reflection performance, Ra on the surface of the plating undercoat polymer layer containing reduced metal particles is preferably 20 nm or less, and more preferably 10 nm or less. Similarly, from the viewpoint of reflection performance, the particle size of the reduced metal particles is preferably 1 nm to 200 nm, more preferably 1 nm to 100 nm, and still more preferably 1 nm to 60 nm.

(Step 2: Step of forming a reflective layer containing silver)
The reflective layer containing silver (silver-containing metal layer) is formed on the plating undercoat polymer layer containing the reduced metal particles by electroplating or the like. As a method of electroplating, a conventionally known method can be used.
In the present invention, when the plating undercoat polymer layer containing the reduced metal particles has a function as an electrode, by performing electroplating on the plating undercoat polymer layer containing the reduced metal particles, the silver-containing metal Layers can be formed.
Silver compounds used for plating include silver nitrate, silver acetate, silver sulfate, silver carbonate, silver methanesulfonate, silver ammonia, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, Examples include silver salicylate, silver diethyldithiocarbamate, silver diethyldithiocarbamate, and silver p-toluenesulfonate. Of these, silver methanesulfonate is preferred from the viewpoint of environmental impact and smoothness.

(Step 3: Step of forming a resin coating layer)
A resin coating layer is provided on the silver-containing metal layer. As one aspect thereof, the silver-containing metal layer is bonded to a coating film that forms a resin coating layer.
As a bonding method, there is a method in which the above-mentioned adhesive is applied to a coating film or a silver-containing metal surface and bonded.
Also, a method of fusing the coated film by a method such as thermal lamination, a method of melting the protective film forming material and forming it on the silver-containing metal layer by casting, and after applying the coated film-forming material on the silver-containing metal layer The resin coating layer may be formed by a method of forming a resin coating film by some kind of reaction, a method of forming using a method such as vacuum deposition, or the like. When these methods are used, the resin coating layer can be formed directly on the silver-containing metal layer without using an adhesive layer.

The mirror film thus obtained is bonded to a rigid housing or the like with the above-mentioned adhesive or the like, and used as a material for collecting or collecting solar light. It is built into the equipment for the use.
Since the mirror film of the present invention has the above-described configuration, it is produced by a simple method, has good adhesion between the metal reflective layer and the support, is lightweight, and has excellent light reflection efficiency.

[Comparative Example 1]
(1. Formation of silver-containing metal layer)
As a base material, a PET film substrate (manufactured by TOYOBO, Cosmo Shine A4300) was used. Next, after the chamber was evacuated until the ultimate vacuum reached 0.5 × 10 ⁻⁴ torr (6.7 × 10 ⁻³ Pa), silver (purity 99.9%) was obtained until the film thickness reached 100 nm. Vacuum deposition was performed. During vacuum processing, no gas was generated, and a silver deposited metal film deposited on the entire surface of the substrate was obtained. The appearance was specular.
(2. Formation of resin coating layer)
As an adhesive, LIS-825 (manufactured by Toyo Ink): 41.8% by mass and LCR-901 (manufactured by Toyo Ink): 3% by mass were dissolved in ethyl acetate: 55.2% by mass to obtain an adhesive solution. Was prepared.
The obtained adhesive solution was applied to the silver vapor-deposited surface obtained in the above step by a bar coating method so as to have a thickness of about 10 μm, and dried at room temperature for 2 minutes and at 80 ° C. for 10 minutes.
A UV absorber-containing PMMA film (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G) was laminated as a resin coating layer with a laminator (lamination speed 0.1 m / min, laminating pressure 0.5 MPa). Thereafter, the adhesive was cured by heating at 60 ° C. for 12 hours.

[Comparative Example 2]
(1. Formation of silver-containing metal layer)
After placing a mask with a 3 cm square hollow at the center of a 4 cm square on one side of a 4 cm square PET film substrate (Cosmo Shine A4300, manufactured by TOYOBO), use silver with a purity of 99.9%. A sample of Comparative Example 2 was prepared by forming a silver vapor deposition film with a thickness of 100 nm by the same method as Example 1 and masking a metal having a width of 0.5 cm from the end.
(2. Formation of resin coating layer and sealing of peripheral edge)
As an adhesive, LIS-825 (manufactured by Toyo Ink): 41.8% by mass and LCR-901 (manufactured by Toyo Ink): 3% by mass were dissolved in ethyl acetate: 55.2% by mass to obtain an adhesive solution. Was prepared.
The obtained adhesive solution was applied to the silver vapor-deposited surface obtained in the above step by a bar coating method so as to have a thickness of about 10 μm, and dried at room temperature for 2 minutes and at 80 ° C. for 10 minutes.
As a coating layer, a UV absorber-containing PMMA film (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G) was laminated with a laminator (lamination speed 0.1 m / min, laminating pressure 0.5 MPa). Thereafter, the adhesive was cured by heating at 60 ° C. for 12 hours.

[Comparative Example 3]
(1. Formation of plating undercoat polymer layer containing reduced metal particles)
Anionic surfactant Perex OT-P (manufactured by Kao Corporation) 0.42 mmol, polyoxyethylene alkyl ether nonionic surfactant Emulgen 409P (manufactured by Kao Corporation) 2.1 mmol, toluene 50 ml and ion-exchanged water 100 ml were added. The mixture was stirred until emulsification while maintaining at 20 ° C. To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 1 hour, and then 6 mmol of ammonium persulfate was added to conduct a polymerization reaction for 2 hours. After completion of the reaction, the organic phase was recovered and washed several times with ion-exchanged water to obtain conductive polypyrrole fine particles having reduction performance dispersed in toluene.
The solid content of the conductive polypyrrole fine particles in the toluene dispersion obtained above was about 1.3%. Here, Superbecamine J-820 (manufactured by DIC Corporation) was used as the binder as the binder. 1 part by mass of polypyrrole fine particles was added to obtain a reducing fine particle paint.
The prepared paint containing conductive polypyrrole fine particles was applied to a PET film substrate (manufactured by TOYOBO, Cosmo Shine A4300) with a coating thickness of 100 nm using a micro gravure coater.
After coating, it was heated in an oven at 180 ° C. for 30 minutes to thermally cure the coated film.

(2. Application of metal precursor to plating undercoat polymer layer)
The coated film was immersed in a 0.02% palladium chloride-0.01% hydrochloric acid aqueous solution (pH 3) adjusted to 35 ° C. for 1 minute, and then washed with pure water.
(3. Electroless plating)
Electroless plating was performed at 30 ° C. for 30 minutes using an electroless plating bath having the following composition. The thickness of the obtained electroless copper plating film was 1 μm.
(Composition of electroless plating bath)
・ 774g of distilled water
・ ATS Ad Copper IW-A (Okuno Pharmaceutical Co., Ltd.) 45mL
・ ATS Ad Copper IW-M (Okuno Pharmaceutical Co., Ltd.) 72mL
・ ATS Ad Copper IW-C (Okuno Pharmaceutical Co., Ltd.) 9mL
・ NaOH 1.98 g
・ 2,2'-bipyridyl 1.8mg
The formed Cu plating metal layer was immersed in 30 ° C. S-Dia AG-40 (Sasaki Chemical Co., Ltd.) for 5 minutes for electroless plating.

[Comparative Example 4]
A gas barrier layer (UV blocking layer) covering a laminate of a polypyrrole coating layer, a metal thin film layer and a light reflecting layer on a PET support and an end of the PET support described in Example 7 of the international publication WO2010 / 150570 pamphlet. A mirror film having a layer) was prepared.

[Example 1]
(1. Formation of plating undercoat polymer layer containing reduced metal particles)
[Preparation of Composition A for Forming Plating Undercoat Polymer Layer]
Acrylic polymer (A) having the following structure: In a solution obtained by dissolving 7% by mass in a mixed solvent of 74% by mass of 1-methoxy-2propanol and 19% by mass of water, a photopolymerization initiator (Esacure KTO-46, run Beldy Co.): 0.35% by mass was added and stirred to prepare a plating undercoat polymer solution having the following structure and a weight average molecular weight of 40000.

The obtained plating undercoat polymer solution was applied to a PET film substrate (manufactured by TOYOBO, Cosmo Shine A4300) by a bar coating method so as to have a thickness of about 0.55 μm, at room temperature for 10 minutes, and at 80 ° C. for 5 minutes. After drying for 4 minutes, it was cut into 4 cm square. A mask with a 3 cm square cutout is placed on the center part cut into a 4 cm square so that the film end and the mask end coincide with each other, and the UV irradiation device (GS Yuasa Co., Ltd., UV lamp: metal halide lamp) is used. UV exposure was performed at an exposure dose of 1000 mJ / cm ^{2 at} the wavelength.
The obtained PET film substrate coated with the plating undercoat polymer was immersed in a 1% by mass aqueous sodium hydrogen carbonate solution for 5 minutes and then washed by pouring with pure water for 1 minute to remove unreacted polymer.

(2. Application of metal precursor)
As a solution containing a plating metal precursor, a 1% by mass aqueous solution of silver nitrate was prepared. The PET film substrate coated with the plating undercoat polymer obtained in the above step was immersed in the metal precursor solution for 5 minutes and then rinsed with pure water for 1 minute to give the metal precursor.
(3. Reduction of metal precursor)
As a reducing solution, a mixed aqueous solution of 0.25% by mass of formaldehyde and 0.14% by mass of sodium hydroxide was prepared. The PET film substrate to which the metal precursor obtained in the above step was applied was immersed in the reducing solution for 1 minute and then washed by pouring with pure water for 1 minute to reduce the metal precursor.

(4. Electroplating)
As a pretreatment for electroplating, the PET film substrate having the reduced metal obtained in the above step on the surface is immersed in a 10% by mass aqueous solution of Dyne Cleaner AC100 (manufactured by Daiwa Kasei Co., Ltd.) for 30 seconds and then rinsed with pure water for 1 minute. Washed with Continued electroplating pretreatment likewise, after 10 seconds immersion in 10 wt% aqueous solution of Dyne silver ACC (manufactured by Daiwa Kasei Co., Ltd.) and washed with 1 minute seat flushed with pure water.
As an electroplating solution, Dyne Silver Bright PL50 (manufactured by Daiwa Kasei Co., Ltd.) was used, and the pH was adjusted to 9.0 with 8M potassium hydroxide. The PET film substrate having the pretreated reduced metal on the surface was immersed in an electroplating solution, plated at 0.5 A / dm ² for 20 seconds, and washed by pouring with pure water for 1 minute.
As an electroplating post-treatment, the plated PET film substrate was immersed in a 10% by mass aqueous solution of Dyne Silver ACC (manufactured by Daiwa Kasei Co., Ltd.) for 90 seconds, and then washed by pouring with pure water for 1 minute.
Thus, a laminate having a silver-containing reflective layer in a region excluding the peripheral portion of the support was obtained.

(5. Formation of resin coating layer)
As an adhesive, LIS-825 (manufactured by Toyo Ink Co., Ltd.): 41.8% by mass and LCR-901 (manufactured by Toyo Ink Co., Ltd.): 3% by mass were dissolved in ethyl acetate: 55.2% by mass to obtain an adhesive solution. Was prepared.
The obtained adhesive solution was used for the surface of the laminate having the silver-containing reflective layer formed in the region excluding the peripheral portion of the support obtained in the above step and the peripheral portion of the support (the silver-containing reflective layer was formed). The adhesive layer was formed by applying a bar coating method so as to have a thickness of about 10 μm and drying at room temperature for 2 minutes and at 80 ° C. for 10 minutes.
A UV absorber-containing PMMA film (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G) was laminated as a resin coating layer with a laminator. The laminating speed was 0.1 m / min, and the laminating pressure was 0.5 MPa. Thereafter, the adhesive is cured by heating at 60 ° C. for 12 hours to form a resin coating layer covering the surface of the laminate and the peripheral edge of the support via the adhesive, and the mirror film of Example 1 Got.

(Synthesis Example 1: Synthesis of acrylic polymer (B))
In a 2000 mL three-necked flask, 216 g of 1-methoxy-2-propanol was added and heated to 90 ° C. under a nitrogen stream, and then 319 g of acrylic acid, 11 g of acrylamide, and 11 g of V-601 (manufactured by Wako Pure Chemical Industries) 11-methoxy- A solution of 366 g of 2-propanol was added dropwise over 4 hours. After reacting for 2 hours, a solution of 5 g of V-601 in 36 g of 1-methoxy-2-propanol was added dropwise over 1 hour and further reacted for 2 hours.
Subsequently, 1.3 g of 2,6-di-trol-butyl-4-toluol, and 1.3 g of tetrabutylammonium bromide and 74 g of glycidyl methacrylate were added as a catalyst and reacted at 100 ° C. After completion of the reaction, 33 g of 1-methoxy-2-propanol was added for dilution to prepare a 1-methoxy-2-propanol solution having an acrylic polymer (B) represented by the following structural formula having a solid mass of 40%. The obtained acrylic polymer (B) had a mass average molecular weight of 38,000 and an acid value of 10.2 meq / g.

(Synthesis Example 2: Synthesis of acrylic polymer (C))
In a 2000 mL three-necked flask, 143 g of 1-methoxy-2-propanol was added and heated to 70 ° C. under a nitrogen stream, and then 149 g of acrylic acid, 7.2 g of acrylonitrile, 14.2 g of styrene, 68.2 g of ethyl acrylate, and V -501 (manufactured by Wako Pure Chemical Industries, Ltd.) 7.2 g of a 1-methoxy-2-propanol 219 g solution was added dropwise over 4 hours, followed by further reaction for 4 hours.
Next, 1 g of 2,6-ditertiarybutyl-4-toluol, 1 g of tetrabutylammonium bromide and 49 g of glycidyl methacrylate were added as a catalyst and reacted at 100 ° C. After the reaction, 22 g of 1-methoxy-2-propanol was added to dilute to prepare a 1-methoxy-2-propanol solution having a solid content mass of 40% of the acrylic polymer (C) having the following structure represented by the following structural formula. . The obtained acrylic polymer (C) had a mass average molecular weight of 20,000 and an acid value of 6.1 meq / g.

(Synthesis Example 3: Synthesis of acrylic polymer (D))
In a 1000 mL three-necked flask, 126 g of 1-methoxy-2-propanol was added and heated to 100 ° C. under a nitrogen stream, and then 136 g of methacrylic acid, 73 g of benzyl methacrylate, and 6.8 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) A 1-methoxy-2-propanol 201 g solution was added dropwise over 3 hours. After reacting for 2 hours, a solution of 3 g of V-601 in 42 g of 1-methoxy-2-propanol was added dropwise over 1 hour, and the mixture was further reacted for 2 hours.
Next, 0.8 g of 2,6-ditertiarybutyl-4-toluol, and 0.8 g of tetrabutylammonium bromide and 52.2 g of glycidyl methacrylate were added as a catalyst and reacted at 100 ° C. After the completion of the reaction, 24 g of 1-methoxy-2-propanol was added for dilution to prepare a 1-methoxy-2-propanol solution having an acrylic polymer (D) represented by the following structural formula and having a solid content mass of 40%. The obtained acrylic polymer (D) had a mass average molecular weight of 37,000 and an acid value of 4.9 meq / g.

(Synthesis Example 4: Synthesis of acrylic polymer (E))
In a 2000 mL three-necked flask, 256 g of 1-methoxy-2-propanol was added and heated to 100 ° C. in a nitrogen stream, and then 296 g of acrylic acid, 160 g of butyl acrylate, and 10 g of V-601 (manufactured by Wako Pure Chemical Industries) 10- A solution of 151 g of methoxy-2-propanol was added dropwise over 7 hours. After reacting for 2 hours, a solution of 3 g of V-601 in 49 g of 1-methoxy-2-propanol was added dropwise over 1 hour and further reacted for 2 hours.
Next, 1 g of 2,6-ditertiarybutyl-4-toluol, 2 g of tetrabutylammonium bromide and 114 g of allyl glycidyl ether as a catalyst were added and reacted at 100 ° C. After completion of the reaction, 271 g of 1-methoxy-2-propanol was added for dilution to prepare a 1-methoxy-2-propanol solution having an acrylic polymer (E) represented by the following structural formula having a solid content mass of 40%. The obtained acrylic polymer (E) had a mass average molecular weight of 29,000 and an acid value of 5.0 meq / g.

(Synthesis Example 5: Synthesis of acrylic polymer (F))
In a 2000 mL three-necked flask, 350 g of 1-methoxy-2-propanol was added and heated to 70 ° C. in a nitrogen stream, and then 252 g of acrylic acid, 75 g of ethyl acrylate, 40 g of acrylonitrile, and 12 g of V-501 (manufactured by Wako Pure Chemical Industries, Ltd.) 156 g of 1-methoxy-2-propanol was added dropwise over 7 hours. After reacting for 2 hours, a solution of 3 g of V-501 in 45 g of 1-methoxy-2-propanol was added dropwise over 1 hour, and the mixture was further reacted for 2 hours.
Next, 1 g of 2,6-ditertiarybutyl-4-toluol, 2 g of tetrabutylammonium bromide and 190 g of vinylbenzyl glycidyl ether as a catalyst were added and reacted at 100 ° C. After completion of the reaction, 285 g of 1-methoxy-2-propanol was added for dilution to prepare a 1-methoxy-2-propanol solution having an acrylic polymer (F) represented by the following structural formula having a solid mass of 40%. The obtained acrylic polymer (F) had a mass average molecular weight of 21,000 and an acid value of 4.6 meq / g.

(Synthesis Example 6: Synthesis of acrylic polymer (G))
In a 2000 mL three-necked flask, 400 g of 1-methoxy-2-propanol was added and heated to 100 ° C. under a nitrogen stream, and then 198 g of acrylic acid, 117 g of hexyl acrylate, 255 g of 3-ethyl-3-oxetanylmethyl methacrylate, and V- 601 (manufactured by Wako Pure Chemical Industries, Ltd.) 13 g of 1-methoxy-2-propanol 306 g solution was added dropwise over 7 hours. After reacting for 2 hours, 50 g of 1-methoxy-2-propanol in 3 g of V-501 was added dropwise over 1 hour, and the reaction was further continued for 2 hours. After the reaction, 100 g of 1-methoxy-2-propanol was added to prepare a 1-methoxy-2-propanol solution having a solid content mass of 40% of the acrylic polymer (G) represented by the following structural formula. The obtained acrylic polymer (G) had a mass average molecular weight of 18,000 and an acid value of 4.9 meq / g.

In the synthesis examples, the remaining amount of catalyst, reaction time, acid value, mass average molecular weight, and color number were measured as follows.
<Reaction time>
The time when the residual amount of glycidyl methacrylate was 1% or less was determined by the gas chromatography.
<< Measurement conditions >>
Column: DB-5 (l: 30 m, Φ: 0.53 mm, d: 1.5 μm)
Injection temperature: 250 ° C
Detection temperature: 250 ° C
Column temperature: After holding at 100 ° C. for 5 minutes, 10 ° C./min. After heating up to 280 ° C. at a heating rate of 10 minutes, hold for 10 minutes Sample injection amount: 4 μL
<Acid value>
It measured by the titration using sodium hydroxide aqueous solution, and calculated | required the value with respect to the solid content of a high molecular compound.
<Mass average molecular weight>
It was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[Examples 2 to 7]
In Example 1, instead of the acrylic polymer (A) used in the formation of the plating undercoat polymer layer containing reduced metal particles, the acrylic polymers (B), (C), (D ), (E), (F) and (G) were used in the same manner as in Example 1 to obtain mirror films of Examples 2 to 7, respectively.

[Examples 8 to 14]
(1. Formation of silver-containing metal layer)
Before performing electrosilver plating in Examples 1 to 7, a copper plating bath having the following composition was subjected to electroplating treatment of 3 A / dm ² for 45 seconds, and a copper-containing layer and a silver-containing reflection were applied on the plating undercoat polymer layer. The laminated body for Examples 8-14 which has a layer was produced.
(Composition of electrolytic copper plating bath)
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Copper Greeme PCM (Meltex Co., Ltd.) 3mL
・ Water 500g
(5. Formation of resin coating layer)
As an adhesive, LIS-825 (manufactured by Toyo Ink): 41.8% by mass and LCR-901 (manufactured by Toyo Ink): 3% by mass were dissolved in ethyl acetate: 55.2% by mass to obtain an adhesive solution. Was prepared.
The obtained adhesive solution is applied to the surface of the “laminated body having a silver-containing reflective layer”, which is a region excluding the peripheral portion of the support obtained in the above step, so that the thickness is about 10 μm. And dried at room temperature for 2 minutes and at 80 ° C. for 10 minutes.
A UV absorber-containing PMMA film (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G) was laminated as a resin coating layer with a laminator. The laminating speed was 0.1 m / min, and the laminating pressure was 0.5 MPa. Thereafter, the adhesive was cured by post-heating at 60 ° C. for 12 hours, and a resin coating layer covering the surface of the laminate and the peripheral portion was formed via the adhesive, and the mirror films of Examples 8 to 14 Got.

[Examples 15 to 21]
(1. Formation of silver-containing metal layer)
Between the copper electroplating and the silver electroplating in Examples 8 to 14, 4 A / dm ² , 72 seconds of electroplating treatment was added in a nickel plating bath having the following composition, and a copper-containing layer on the plating undercoat polymer layer The laminated body for Examples 15-21 which has a nickel containing layer and a silver containing reflection layer was produced.
(Composition of electro nickel plating bath 1L)
・ Nickel sulfate 100g
・ Nickel chloride 15g
・ Boric acid 45g
-BR220 makeup (Rohm and Haas Electric Materials Co., Ltd.) 10mL
-BR220 carrier (Rohm and Haas Electric Materials Co., Ltd.) 35mL
・ BR220 Replenisher (Rohm and Haas Electric Materials Co., Ltd.) 2mL
・ NAW-A (Rohm and Haas Electric Materials Co., Ltd.) 3mL
・ Water balance

(2. Formation of resin coating layer)
As an adhesive, LIS-825 (manufactured by Toyo Ink Co., Ltd.): 41.8% by mass and LCR-901 (manufactured by Toyo Ink Co., Ltd.): 3% by mass were dissolved in ethyl acetate: 55.2% by mass to obtain an adhesive solution. Was prepared.
The obtained adhesive solution is applied to the surface of the “laminated body having a silver-containing reflective layer”, which is a region excluding the peripheral portion of the support obtained in the above step, so that the thickness is about 10 μm. To form a resin layer (step of forming a layer made of a resin material for forming a resin coating layer), and the resin layer was cured by drying at room temperature for 2 minutes and at 80 ° C. for 10 minutes (curing the resin layer) Process).
Thus, the mirror film of Examples 15-21 which coat | covered the said laminated body with the resin coating layer formed by the apply | coating method was obtained.

[Example 22]
The laminated body which has a silver containing reflection layer in the area | region except the peripheral part of a support body like Example 1 was obtained.
(5. Formation of resin coating layer)
As a coating layer, a UV absorber-containing PMMA film (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G) is directly laminated on the surface and peripheral edge of the laminate, and lamination is performed by thermocompression bonding at a temperature of 120 ° C. and a load of 0.5 Pa. A resin coating layer was formed to obtain a mirror film of Example 22.

Example 23
The laminated body which has a silver containing reflection layer in the area | region except the peripheral part of a support body like Example 1 was obtained.
(5. Formation of resin coating layer)
As a coating layer, a coating solution for forming a resin coating layer obtained by dissolving 10 wt% of UV absorber-containing PMMA film (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G) in acetone is used so that the dry film thickness becomes 75 μm. It apply | coated to the laminated body surface and the peripheral part, and the coating liquid layer for resin coating layer formation was formed. The formed coating liquid layer was dried at a temperature of 80 ° C. for 1 hour to be cured, and a resin coating layer was formed on the surface of the laminate and the peripheral edge portion to obtain a mirror film of Example 23.
In these mirror films of Examples 1 to 23, a resin coating layer in close contact with the surface of the silver-containing reflective layer formed in the central portion and the support surface of the peripheral portion is formed, and the entire film surface including the peripheral portion is sealed. The structure was stopped.

(6. Lamination of mirror film to rigid housing)
The mirror films obtained in Examples 1 to 23 and Comparative Example 2 were each bonded to a casing.
First, an adhesive similar to that used in the resin coating layer forming step was applied to a SUS304 plate having a size of 4 cm × 4 cm using a spin coater at 600 rpm for 20 seconds, then at room temperature for 2 minutes and at 80 ° C. for 10 minutes. Then, the mirror film was bonded to the surface of the casing by drying the substrate for a minute and then bonding the surface of the support of each mirror film that does not have the silver-containing reflective layer to the adhesive surface with a roller.
The mirror films of Comparative Examples 1, 3 and 4 were also applied to the casing in the same manner as the mirror films obtained in Examples 1 to 23 and Comparative Example 2 except that a 3 cm × 3 cm SUS304 plate was used. Combined.

(Performance evaluation)
1. Salt spray test The salt spray test is carried out according to JIS Z 2371, using the obtained mirror film itself, neutral salt spray: 480 hours, and visually observing the plated surface after the test to corrode the Ag layer, Dissolution was determined according to the following criteria. The results are shown in the table below.
A: Ag corrosion and no dissolution B: Ag corrosion and dissolution

2. Adhesion test In the adhesion test, the obtained mirror film was cut into 2 mm square grids with a cutter in accordance with JIS H8504 tape test method to form 100 grids, and then pulled with tape. A peel test was performed and evaluated according to the following criteria. The results are shown in Tables 3 to 4 below. Evaluations 3 and 4 are at a level where there is no practical problem based on the following criteria.
1: About 75% or more peeled 2: Exceeded about 25% and less than about 50% peeled 3: Within about 25% peeling 4: No peeling

  From the results of Tables 3 to 4, it is provided with a plating undercoat polymer layer using a photocurable acrylic polymer resin, and is provided with a silver-containing reflective layer only in a region excluding the support periphery by patterning, and the support periphery It has been clarified that the mirror films of Examples 1 to 23 according to the present invention having a structure in which the resin coating layer is in close contact have high adhesion, corrosion resistance, and dissolution resistance.

10, 20 Mirror film 12 Support 14 Plating undercoat polymer layer 15 Undercoat resin layer 16 Reflective layer containing silver (silver-containing metal layer)
17 Metal layer 18 Resin coating layer 19 Polypyrrole coating layer 20 Light reflection layer 22 Adhesive layer 24 Protective tape

Claims (19)

  A plating undercoat polymer layer comprising a support, a plating undercoat polymer layer containing reduced metal particles, a reflective layer containing silver, and a resin coating layer in this order, and containing the reduced metal particles And the reflective layer containing the said silver is provided in the area | region except the peripheral part of the said support body, The mirror film with which the peripheral part of the said support body and the said resin coating layer are closely_contact | adhered.   The mirror film according to claim 1, wherein the plating undercoat polymer layer contains a polymer having at least a carbonyl group.   The plating undercoat polymer layer includes an acrylic polymer having an acidic group and a polymerizable group in a side chain, and the acrylic polymer is imparted with energy in the plating undercoat polymer layer, or the polymerizable groups or the polymerizable groups. The mirror film according to claim 1 or 2, wherein a cross-linked structure or a chemical bond is formed between a group and the support.   The mirror film according to claim 3, wherein the energy application includes UV exposure.   The mirror film according to any one of claims 1 to 4, wherein the reflective layer containing silver is a layer including a metal multilayer film having at least a metal film containing silver on the resin coating layer forming side.   The mirror film according to any one of claims 1 to 5, wherein the support is a polyester film or a polyimide film.   The said resin coating layer contains the resin composition containing 1 or more types of resin selected from the group which consists of polycarbonate-type resin, polyester-type resin, norbornene-type resin, urethane resin, an acrylic resin, and an olefin resin. The mirror film according to claim 6.   The mirror film according to any one of claims 1 to 7, wherein a peripheral edge portion of the support and the resin coating layer are in close contact with each other via an adhesive layer.   The mirror film according to claim 8, wherein the resin coating layer and the reflective layer containing silver are in close contact via an adhesive layer.   The mirror film according to any one of claims 1 to 7, wherein a peripheral edge portion of the support and the resin coating layer are in direct contact with each other and are in close contact with each other.   A reflecting mirror comprising the mirror film according to any one of claims 1 to 10 on a rigid housing. Forming a plating undercoat polymer layer in a region excluding the peripheral edge on the support;
Applying a metal precursor to the plating undercoat polymer layer;
Reducing the applied metal precursor;
Forming a reflective layer containing silver by electroplating in a region excluding the peripheral edge on the support; and
The manufacturing method of the mirror film of any one of Claims 1-10 including the process of forming a resin coating layer so that the reflection layer containing the said silver and the peripheral part of the said support body may be covered. .   A step of forming a plating undercoat polymer layer in a region excluding a peripheral portion on the support, a step of contacting a composition for forming a plating undercoat polymer layer containing a plating undercoat polymer on the support; and the support. The manufacturing method of the mirror film of Claim 12 including the process of providing energy only to the area | region except an upper peripheral part, and fixing a plating undercoat polymer layer on the said support body.   The step of forming a plating undercoat polymer layer in a region excluding the peripheral portion on the support includes the step of forming a plating undercoat polymer layer on the entire surface of the support, and the plating undercoat polymer at the peripheral portion of the support. The method for producing a mirror film according to claim 12 or 13, comprising a step of removing the layer.   The method for producing a mirror film according to claim 13, wherein the energy application includes UV exposure. The plating undercoat polymer is represented by the following formula (C) and an interactive group-containing unit comprising a polymerizable group-containing unit represented by the following formula (A) and a non-dissociable functional group represented by the following formula (B). A copolymer containing an interactive group-containing unit composed of an ionic polar group, a copolymer containing a unit represented by the following formula (A) and a unit represented by the following formula (B), or The manufacturing method of the mirror film of any one of Claim 13 to 15 containing the copolymer containing the unit represented by the following formula (A), and the unit represented by the following formula (C).

In the above formulas (A) to (C), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and X, Y, Z, and U independently represents a single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ , L ² , and L ³ each independently represent Represents a single bond or a substituted or unsubstituted divalent organic group, W represents a non-dissociative functional group that interacts with the plating catalyst or a precursor thereof, and V interacts with the plating catalyst or a precursor thereof. It represents an ionic polar group that forms an action.   The step of forming a plating undercoat polymer layer in a region excluding the peripheral edge on the support includes a step of applying a polymer layer forming composition containing a material that generates active species to the support. The manufacturing method of the mirror film of any one of Claim 16.   The step of forming the resin coating layer so as to cover the reflective layer containing silver and the peripheral portion of the support is a resin for forming a resin coating layer on the support on which the reflective layer containing silver is formed. A step of dissolving the material in a solvent, applying and drying to form a layer made of the resin material for forming the resin coating layer, and a step of curing the layer made of the resin material for forming the resin coating layer The manufacturing method of the mirror film of any one of Claims 12-17.   The step of forming the resin coating layer so as to cover the reflective layer containing silver and the peripheral edge of the support is a support in which the reflective layer containing silver is formed on the resin film via the adhesive layer. The manufacturing method of the mirror film of any one of Claims 12-17 including the process closely_contact | adhered on a body.