JP2012096392A - Pattern forming film, and method of forming metal thin film pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming film that is useful as a decorative film for insert formation, wrapping film, or film for making transparent electrodes, and can decorate metal color patterns.SOLUTION: A pattern forming film has at least a metal thin film layer or pattern printing layer on a base material. The pattern printing layer is in contact with a metal thin film layer. Resin comprising the pattern printing layer is at least one kind selected from a group comprising vinyl chloride resin, vinyl acetate resin, and polyvinyl chloride/acetate copolymer resin, wherein an average acid value of the resin is ≥7 mgKOH/g.

Description

  The present invention relates to a pattern forming film, and more particularly to a pattern forming film that imparts a metal pattern or a metal color pattern, and a method for forming a metal thin film pattern.

Conventionally, a metal thin film layer has been formed on a plastic film by a vacuum deposition method, a sputtering method, or the like for the purpose of imparting a metallic luster or a gas barrier property. These materials are used for packaging films and decorative sheets.
Moreover, in the packaging film, the transparent barrier film which transparentized the metal thin film layer is proposed for the purpose of providing the visibility of the contents, etc. (refer patent document 1), and in a decorative sheet, metallic luster, A partially vapor-deposited decorative sheet for the purpose of imparting aesthetics and various durability has been proposed (see Patent Document 2).

In the above-mentioned Patent Document 1, a method of making a metal vapor-deposited film transparent by supplying oxygen gas under specific conditions at the time of vacuum vapor deposition is taken. With this technique, a uniform transparent metal vapor-deposited film is obtained. However, a partially transparent metal vapor deposition film cannot be obtained.
On the other hand, in Patent Document 2, a method for obtaining a patterned metal vapor deposition film by forming a desired resist pattern layer on a metal vapor deposition film formed on a film and etching the metal vapor deposition film by an etching method. Has been proposed.

JP-A-10-330915 Japanese Patent Laid-Open No. 5-39583

As described above, the etching method is effective as a method for patterning a metal vapor-deposited film, but requires a number of steps such as a resist layer forming step, an etching step, and a resist layer removing step performed as necessary. As a result, the process is complicated and the cost is increased due to an increase in the number of processes.
Therefore, the present invention can be used for a wide range of applications such as packaging films having metal thin films, decorative sheets such as decorative films for insert molding, and films for producing transparent electrodes, and can be produced by a simple method. An object of the present invention is to provide a pattern forming film of a metal thin film layer that is possible.

As a result of intensive studies to achieve the above-mentioned problems, the inventors of the present invention are a pattern forming film having a metal thin film layer and a pattern printing layer, and using a resin having a specific acid value for the pattern printing layer. Thus, it has been found that the above problems can be solved.
That is, the present invention is a pattern forming film having at least a metal thin film layer and a pattern printing layer on a substrate, the pattern printing layer being in contact with the metal thin film layer and constituting the pattern printing layer. Is at least one selected from the group consisting of a vinyl chloride resin, a vinyl acetate resin, and a vinyl chloride / vinyl acetate copolymer resin, wherein the average acid value of the resin is 7 mg KOH / g or more. A film for forming a pattern and a method for forming a metal thin film pattern using the film for forming a pattern are provided.

  According to the present invention, a pattern forming film and a metal thin film pattern useful as a decorative film for insert molding capable of decorating a metal color pattern, a film for packaging, a film for producing a transparent electrode, and the like are effectively used. And the method of forming simply can be provided.

It is sectional drawing which shows one aspect of the film for pattern formation of this invention. It is sectional drawing which shows the other aspect of the film for pattern formation of this invention. It is sectional drawing which shows the three-dimensional shaping | molding decoration film using the film for pattern formation of this invention. It is sectional drawing which shows the three-dimensional shaping | molding decoration film using the film for pattern formation of this invention. It is sectional drawing which shows the three-dimensional shaping | molding decoration film using the film for pattern formation of this invention. It is sectional drawing which shows the three-dimensional shaping | molding decoration film using the film for pattern formation of this invention.

The pattern forming film of the present invention has at least a metal thin film layer and a pattern printed layer on a substrate, and is characterized in that the pattern printed layer and the metal thin film layer are in contact with each other.
As one of the embodiments, as shown in FIG. 1, a pattern forming film 10 is formed by laminating a metal thin film layer 12 and a pattern printing layer 13 in this order on a base material 11. Moreover, as another aspect, as shown in FIG. 2, it is the film 10 for pattern formation formed by laminating | stacking the pattern printing layer 13 and the metal thin film layer 12 on the base material 11 in this order.

Moreover, FIGS. 3-6 is the example used for the three-dimensional shaping | molding decoration film which is a preferable aspect of the film for pattern formation of this invention, and FIG.3 and FIG.4 is a laminate type three-dimensional shaping decoration film 20 FIG. 5 and 6 show a transfer-type three-dimensional molded decorative film 30. FIG.
In the three-dimensional decorative film (laminate type) shown in FIG. 3, the metal thin film layer 12 and the pattern print layer 13 are provided on the base material 11 in this order, and a solid print layer 14 may be provided if desired. Further, the substrate 11 has a primer layer 15 and a surface protective layer 16 on the side opposite to the metal thin film layer 12 (hereinafter sometimes referred to as “the back side of the substrate”).
Next, the three-dimensional molded decorative film (laminate type) shown in FIG. 4 has the pattern printing layer 13 and the metal thin film layer 12 in this order on the substrate 11, and may be provided with a solid printing layer 14 if desired. . In addition, a primer layer 15 and a surface protective layer 16 are provided on the back surface side of the substrate in the substrate 11.
On the other hand, in the three-dimensional decorative film (transfer type) shown in FIG. 5, the surface protective layer 16 and the primer layer 15 are laminated on the base material 11, and then the metal thin film layer 12 is laminated by a vapor deposition method or the like. A pattern printing layer 13 and, if necessary, a solid printing layer 14 are provided thereon by gravure printing or the like. In the three-dimensional decorative film (transfer type) shown in FIG. 6, the surface protective layer 16, the primer layer 15, and the pattern printing layer 13 are laminated on the substrate 11, and then the metal thin film layer 12 is deposited by a vapor deposition method or the like. Is laminated. A solid print layer 14 is provided thereon by gravure printing or the like as necessary.
Hereinafter, the film for pattern formation of the present invention will be described with reference to the drawings.

(Base material)
There is no restriction | limiting in particular as the base material 11 used for the film for pattern formation of this invention, A plastic film, a glass substrate, etc. are used according to a use. Suitable plastic films for decorative films and packaging films include, for example, acrylic resins; polyethylene resins, polypropylene resins, polybutene resins, ethylene-propylene copolymer resins, ethylene-propylene-butene copolymers. Polyolefin resins such as polymer resins and olefin thermoplastic elastomers; Polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); Polycarbonate resins; Acrylic modified urethane resins, Polyester modified urethane resins, Chlorinated Polyurethane resins such as vinyl-vinyl acetate copolymer-modified urethane resins; polystyrene resins; vinyl chloride resins; vinyl acetate resins; vinyl chloride-vinyl acetate copolymer resins, etc. It can be used in combination one or more of these.
Of these, polyester resins are preferable in terms of adhesion and cost, and polyethylene terephthalate (PET) subjected to easy adhesion treatment is particularly preferable.
In addition, a coloring agent, a lubricant, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, an antistatic agent, an antibacterial agent, a flame retardant, and the like are added to the base material as necessary. Also good.

  Although the thickness of a base material is suitably selected from viewpoints, such as cost, a moldability, and designability, it is 10-250 micrometers normally, and 25-100 micrometers is more preferable. In addition, the substrate to be used may be subjected to so-called easy-adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, and an easy-adhesion layer such as an anchor layer is provided on the surface of the substrate. It may be what was made.

[Metal thin film layer]
The metal thin film layer 12 concerning this invention is a layer provided in the base material 11, and gives the same high glossiness as a metal surface in a decorating film, a packaging film, etc., and provides designability. Moreover, in the film for transparent electrode preparation, it is for forming an electrode.
In the present invention, the pattern printing layer 13 and the metal thin film layer 12 are in contact with each other. The pattern forming film of the present invention is, for example, a decorative film, which is heated in a film processing process such as vacuum forming and laminated or transferred in contact with an injection resin, and other backer layers described later. In these heating processes, the contact portion of the metal thin film layer 12 with the pattern printing layer 13 is oxidized, and the metal color changes or becomes transparent (hereinafter referred to as “transparent”). In this case, a unique design is imparted to the pattern forming film or a resin molded product using the pattern forming film.
Further, in the packaging film, the above-mentioned transparency is progressed by heat treatment in a step of directly heat-treating the film, a heat-sealing step in packaging with the film, or a lamination step with a film layer to be described later. To do. The heat treatment temperature is not particularly limited as long as the effect of the present invention is achieved, but is usually 100 ° C. or higher, preferably 100 to 250 ° C.

The metal that can be used in the present invention is not particularly limited as long as the effects of the present invention are achieved, and examples thereof include aluminum, nickel, copper, silver, gold, platinum, tin, brass, indium, chromium, and zinc. A metal can also be used in combination of 2 or more types.
Of these metals, tin and indium are preferable from the viewpoint of transparency and high extensibility. In addition, a material having good extensibility has an advantage that, for example, in a case where it is used as a decorative film, cracks do not occur even if the material is stretched when three-dimensionally formed.

There are various methods for forming the metal thin film layer of the present invention, but using any of the above metals, it is possible to process any material by using a vapor deposition method such as vacuum vapor deposition, sputtering, or ion plating. It is preferable from the point that a film excellent in decorativeness can be applied.
In the present invention, the vacuum deposition method is particularly preferable in terms of low cost and less damage to the substrate, and the deposition conditions are appropriately set according to the melting temperature or evaporation temperature of the metal to be used. The conditions are such that the degree is 10 ⁻³ to 10 ⁻⁴ Pa and the temperature is 1000 to 1100 ° C.

As the thickness of the metal thin film layer, an optical density of O.D. The D value is preferably about 0.5 to 3, more preferably about 0.8 to 1.5.
In addition, when forming a metal thin film on the base material 11 by vacuum deposition or the like, the base material is subjected to a so-called easy-adhesion treatment such as corona discharge treatment, plasma treatment, or ozone treatment as described above in order to enhance adhesion. It is also a preferable aspect that a metal thin film is formed later.

[Pattern printing layer]
The pattern printing layer 13 in the present invention is in contact with the metal thin film layer 12 and oxidizes the metal at the contact portion to make the metal thin film layer transparent in a pattern. Therefore, as a design, it is possible to develop a unique design that looks like a pattern is lost with respect to glitter solid printing.
In addition, if a colored layer is provided between the metal thin film layer 12 and the pattern printing layer 13 or on the pattern printing layer 13 (not shown), a design in which the color of the colored layer appears on the glossy solid printing can be obtained. can get.
The resin constituting the pattern printing layer is a vinyl chloride resin, a vinyl acetate resin, or a vinyl chloride / vinyl acetate copolymer resin (hereinafter, these may be collectively referred to as “vinyl resin”). It is essential that the average acid value of the resin is 7 mgKOH / g or more.
As described above, the resin constituting the pattern print layer is a vinyl resin having an average acid value of 7 mgKOH / g or more, and there is no particular upper limit on the average acid value. The average acid value is preferably 10.5 mgKOH / g or less.
The number average molecular weight of the resin is preferably 10,000 to 100,000, and the glass transition temperature (Tg) is preferably 70 to 90 ° C.

The film for pattern formation of the present invention has the above-mentioned base material, metal thin film layer, and pattern printing layer as essential constituent requirements. When this is used as a three-dimensional decorative film, various other constituent elements are used. It is preferable to have.
First, when the film for pattern formation of the present invention is used as a film for simultaneous injection molding, the film consisting of the above essential constituents can be used as it is, and the pattern printing layer is in contact with the injection resin. Thus, a resin molded product can be obtained.
On the other hand, when the film for pattern formation of the present invention is used for insert molding, an insert molding sheet can be obtained by thermally laminating a backer layer on the pattern printing layer side, or a solid printing layer 14 described later. And can be dry laminated on the backer layer.

[Solid printing layer]
In the embodiment shown in FIG. 1, a uniform and uniform solid print layer 14 is provided on the pattern print layer 13. Here, the solid printing layer 14 enhances the adhesion between the metal thin film layer provided on the substrate and the injection molding resin, the backer layer, and the like, and also functions as an adhesive layer that stabilizes the metal thin film layer. Is. As the resin constituting the solid printing layer, a resin having an average acid value of 7 mgKOH / g or more and not a vinyl chloride resin, a vinyl acetate resin, or a vinyl chloride / vinyl acetate copolymer resin is selected. This is because these vinyl resins make the metal thin film layer transparent and cancel the effect of the pattern printing layer.

Specific examples of the resin constituting the solid printing layer include acrylic resin, polyester resin, cellulose resin, and the like. If the vinyl resin is used, the average acid value of the resin is 1 to 6 mgKOH / g. There are some (hereinafter sometimes referred to as “low acid value vinyl resins”). These may be used alone or in combination of two or more. Among these resins, the low acid value vinyl resin and acrylic resin are particularly preferable because sufficient adhesiveness is obtained, transparency is high, and handling is easy.
For the vinyl resin, the average acid value is 1 to 6 mgKOH / g. It is preferable that the average acid value of the vinyl resin is 1 mgKOH / g or more because sufficient adhesion between the metal thin film layer and other resins such as an injection molding resin and a backer layer can be obtained. On the other hand, when it is 6 mgKOH / g or less, the metal thin film layer is not transparent, and the effect of the pattern printing layer is not canceled. From the above viewpoint, the average acid value of the vinyl resin is more preferably 2 to 5 mgKOH / g.
The average acid value of the vinyl resin can be controlled by preparing a mixture of a plurality of vinyl resins having a known average acid value.
Further, the acid value of the resin constituting the solid print layer can be directly measured, or when the resin is a mixture of a plurality of resins, it can be obtained from the acid value of the constituent resin by the following formula. .
Acid value = acid value of resin 1 × weight of resin 1 + acid value of resin 2 × weight of resin 2+.. ./Weight of all resins

Further, regarding the acrylic resin, the polyester resin, and the cellulose resin, the metal thin film layer is not made transparent without depending on the acid value.
Of the resins constituting the solid print layer, vinyl chloride / vinyl acetate copolymer resin is most preferable from the viewpoint of adhesiveness.
Moreover, it is preferable that the number average molecular weights of resin which comprises a solid printing layer are 10,000-100,000, and it is preferable that a glass transition temperature (Tg) is 70-90 degreeC.

The solid printing layer is prepared by adding a solvent to the resin as described above or a mixture of two or more kinds, if necessary, and preparing a varnish on the metal thin film layer and / or pattern printing layer. It can be formed by coating with a known coating method such as coating or kiss coating, and drying with hot air usually at 40 to 60 ° C. for about 1 to 2 minutes.
Moreover, as a film thickness of a solid printing layer, it is about 1-2 micrometers normally.

[Surface protective layer]
3 and 4, the surface protective layer 16 is provided on the back surface side of the substrate 11. The surface protective layer has a function of protecting the surface of the substrate and imparting abrasion resistance, scratch resistance, chemical resistance, and the like.
The surface protective layer is formed by applying a resin composition containing a curable resin to the back surface of the base material directly or via another layer and crosslinking and curing the resin composition. By having a surface protective layer made of a curable resin that has been crosslinked and cured, the surface characteristics of the film for pattern formation can be improved.

As the curable resin used here, a thermosetting resin such as an ionizing radiation curable resin or a two-component curable resin is used, and a plurality of these are used, for example, an ionizing radiation curable resin and a thermosetting resin are used in combination. The so-called hybrid type may be used.
Of these, ionizing radiation curable resins are preferred from the viewpoint of increasing the crosslink density of the resin forming the surface protective layer and improving the surface wear resistance and scratch resistance, and are coated without solvent. In view of easy handling and handling, an electron beam curable resin is more preferable.

(Ionizing radiation curable resin)
The ionizing radiation curable resin refers to a resin having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.
Typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable as the polymerizable monomer, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate The system etc. are mentioned.
Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  In the present invention, a monofunctional (meth) acrylate can be appropriately used in combination with the polyfunctional (meth) acrylate and the like within a range that does not impair the object of the present invention, for the purpose of reducing the viscosity. . These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  In addition, when using an ultraviolet curable resin composition as an ionizing radiation curable resin composition, about 0.1-5 mass parts of initiators for photopolymerization may be added with respect to 100 mass parts of resin compositions. desirable. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.

(Thermosetting resin)
Thermosetting resins include epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, carboxyl functional acrylic resin, amide functional copolymer Examples include coalescence and urethane resin.
Among thermosetting resins, two-component curable resins are preferable, and two-component curable resins of polyol and isocyanate are preferable. As the two-component curable resin, the same resin as described later in detail in the primer layer can be used.

(Additive)
The resin composition constituting the surface protective layer of the pattern forming film of the present invention may contain various additives other than those described above as long as the performance is not impaired. Examples of various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.

The surface protective layer may contain a weather resistance improver for enhancing weather resistance, an abrasion resistance improver for enhancing wear resistance, and other additives.
As such a weather resistance improving agent, an ultraviolet absorber or a light stabilizer described in detail later can be used. In addition, examples of the wear resistance improver include spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is preferably about 30 to 200% of the normal film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.

(Method for forming surface protective layer)
The formation of the surface protective layer can be obtained by preparing a coating liquid containing the above-mentioned resin composition for forming the surface protective layer, applying it, and crosslinking and curing it. In addition, the viscosity of a coating liquid should just be a viscosity which can form a non-hardened resin layer on the surface of a base material by the below-mentioned coating system, and there is no restriction | limiting in particular.
In the present invention, the prepared coating liquid is applied to the surface of the substrate or the surface of the primer layer described later, such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. The coating is preferably performed by gravure coating to form an uncured resin layer.
Next, the uncured resin layer formed as described above is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
The irradiation dose is preferably such that the crosslinking density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 100 kGy (1 to 10 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  The surface protective layer may have a recess. There is no restriction | limiting in particular about the method of giving a recessed part to a surface protective layer, For example, it gives by embossing. The embossing may be performed by a normal method using a known single-wafer or rotary embossing machine.

[Primer layer]
Moreover, when providing a surface protective layer, it is preferable to provide the primer layer 15 between a base material and a surface protective layer. The primer layer is a layer that has a function of improving adhesiveness, and further exhibits an effect of improving moldability and weather resistance adhesion. That is, it functions also as a stress relaxation layer for the surface protective layer, and has an effect of making it difficult for fine cracks and whitening to occur in the stretched portion of the surface protective layer.

As the resin constituting the primer layer, (meth) acrylic resin, urethane resin, (meth) acrylic / urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorinated A one-component resin such as polyethylene or a two-component resin as shown below is used, and among these, a two-component resin is preferable in terms of adhesion.
The two-component resin is preferably formed using, for example, a polycarbonate urethane acrylate, a polyester urethane acrylate, or a resin composed of a polycarbonate urethane acrylate and an acrylic polyol, and more preferably a polycarbonate urethane acrylate resin. preferable. By forming a primer layer using these resins, a film for pattern formation with good adhesion between the substrate and the surface protective layer can be obtained.

  The mass ratio of the acrylic component and the urethane component of the polycarbonate urethane acrylate is not particularly limited, but the mass ratio of the urethane component: acrylic component is in the range of 80:20 to 20:80 in terms of weather resistance and adhesion. It is preferable that the range is 70:30 to 30:70.

  The mass ratio of the polycarbonate urethane acrylate and the acrylic polyol is preferably in the range of 100: 0 to 10:90 of the polycarbonate urethane acrylate alone, more preferably in the range of 100: 0 to 30:70.

In order to improve the weather resistance, the primer layer 15 includes a weather resistance improver such as an ultraviolet absorber (UVA) and a light stabilizer (HALS), a colorant for giving a colored appearance, and other additives. It can be included.
The ultraviolet absorber may be either inorganic or organic, and as the inorganic ultraviolet absorber, titanium oxide, cerium oxide, zinc oxide or the like having an average particle size of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type, a salicylate type, an acrylonitrile type etc. can be mentioned preferably, for example. Of these, triazines are preferred because they have a high ability to absorb ultraviolet rays and do not easily deteriorate even with high energy such as ultraviolet rays.

  Preferred examples of the light stabilizer include hindered amine light stabilizers. Moreover, the ultraviolet absorber and light stabilizer which have a reactive group in a molecule | numerator can also be used as a ultraviolet absorber or a light stabilizer.

  Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue are used.

The thickness of the primer layer 15 is not particularly limited as long as the effects of the present invention can be obtained. However, from the viewpoint of obtaining sufficient adhesion and stress relaxation properties, a range of 0.5 to 4 μm is preferable, and 1 A range of ˜2 μm is preferred.
In addition, the primer layer 15 is formed by applying the resin composition as it is or in a state in which the resin composition is dissolved or dispersed in a solvent to the substrate by applying a known printing method, coating method, or the like, and then drying and curing. Can be done. Alternatively, the primer layer may be left in a state where it is not completely cured, and then the surface protective layer may be applied to cure both.
Moreover, when forming this primer layer on a base material, easy adhesion processes, such as a corona discharge process and a plasma process, can be given with respect to a base material, and it can also make it adhesiveness with a base material improved.

[Film layer]
The film for pattern formation of this invention may provide a film layer further as needed on the solid printing layer 14 provided as needed.
Here, the film layer is referred to by various names depending on the use of the pattern forming film of the present invention. For example, if the pattern forming film of the present invention is used as a decorative film for insert molding, This is a so-called backer layer. Moreover, when using as a packaging film, it becomes a film layer which can contact contents, such as a foodstuff, for example.
As materials that can be used as the film layer, the same materials as those used for the substrate, particularly plastic films, are preferably used. Moreover, the thickness is also set suitably according to a use.

When the pattern forming film of the present invention is used for insert molding, it is preferable that a backer layer is laminated on the solid printing layer 14 and integrated (not shown). This backer layer has a function of improving adhesion to the decorative molded body. The resin used for the backer layer is selected according to the resin to be molded, but generally, an ABS resin (acrylonitrile-butadiene-styrene copolymer resin), a polyolefin resin, a styrene resin, an acrylic resin, Preferred examples include vinyl chloride resins and polycarbonate resins, and one or more of these can be used in combination. As the polyolefin resin, polypropylene resin is preferable.
Among these resins, the resin used for the backer layer particularly preferably includes an ABS resin and a polypropylene resin, and most preferably includes an ABS resin.
The thickness is preferably about 100 to 500 μm, and more preferably about 250 to 400 μm.

  Moreover, when using the film for pattern formation of this invention as a film for packaging, what is necessary is just to select a suitable material for a film layer suitably according to the content etc. with which it is filled. The thickness is about 20 to 200 μm.

[Another aspect of the pattern forming film of the present invention as a decorative film]
5 and 6 are aspects of the film for forming a pattern of the present invention other than those shown in FIGS. 3 and 4 and show a transfer type decorative film (film for forming a pattern) as described above. . By adopting such a transfer type, since the base material 11 is peeled off, a low-cost material or a thin material can be used as the base material, and a non-moldable material can be used. This is advantageous in that it can be used.

[Method of manufacturing decorative molded product]
The film for pattern formation of the present invention can be used for the injection molding simultaneous decorating method that does not require a backer layer, but is suitable for insert molding that requires a backer layer, and is a vacuum forming step, a trimming step, and a resin. It is suitably used for an insert molding method comprising an injection process.
In the insert molding method, in the vacuum forming process, the pattern forming film of the present invention is vacuum formed into a molded product surface shape in advance (off-line pre-molding) with a vacuum forming die, and then trimmed as necessary to form. Get a film. This molded film is inserted into an injection mold, the injection mold is clamped, a resin in a fluid state is injected into the mold and solidified, and a pattern-forming film is placed on the outer surface of the resin molding simultaneously with the injection molding. Integrate and manufacture decorative molded products.
Further, in the simultaneous injection molding decoration method, as described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, etc., a decorative film is placed between both male and female molds of injection molding, The resin in a state is injected and filled into a mold, and a decorative film is laminated on the surface simultaneously with the molding of the resin molded product, thereby decorating the resin molded product to produce a decorated molded product.

As the injection resin, a resin corresponding to the application is used, and a thermoplastic resin such as a polyolefin resin such as polyethylene or polypropylene, an ABS resin, a styrene resin, a polycarbonate resin, an acrylic resin, or a vinyl chloride resin is representative. In addition, thermosetting resins such as urethane resins and epoxy resins can be used depending on applications.
The decorative molded body produced as described above has a surface protective layer, and in particular, the surface protective layer is not cracked during the molding process, and the surface has high wear resistance and scratch resistance. Have.

[Other Embodiments of Pattern-Forming Film of the Present Invention]
As described above, the film for pattern formation of the present invention is useful as a decorative film, but is also useful as a film for packaging, a film for producing a transparent electrode, and the like.
For example, if it is a film for packaging, it can be set as the film which has a gas barrier, providing the visibility of the contents by partially making a metal thin film layer transparent. In addition, since a metallic pattern can be drawn freely, a novel design can be provided. Therefore, the film for pattern formation of the present invention is a film for packaging confectionery such as snack confectionery, semi-fresh confectionery, high-class confectionery, gas-filled confectionery with a long product life, and oxygen scavenger packaging; coffee beans, instant coffee, tea, green tea Film for packaging of luxury goods such as; Boiled / retort food, pickles, boiled fish, ham, liquid sauce, cup lid material, microwave oven food film, etc .; freeze-dried food, sprinkles, spices and other dry food Suitable for packaging film.

  Moreover, the film for pattern formation of this invention can use suitably indium, tin, and zinc as a metal which comprises a transparent metal thin film layer. ITO, which is a composite oxide of indium and tin, is used as a transparent electrode, and zinc oxide is also a material expected to be used as a transparent electrode. In the present invention, a high acid value vinyl resin is printed in a pattern on these metals and brought into contact with each other to oxidize these metals and form a patterned oxide film. In other words, various shapes of transparent electrodes can be freely designed by a printing technique.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Evaluation methods)
(1) Adhesiveness Adhesiveness was evaluated by a cross-cut adhesion test for the solid print layer of the pattern forming film obtained in each of the examples and comparative examples. A solid print layer is cut into 100 squares to create a grid, and an adhesive tape (“Cello Tape (registered trademark)” manufactured by Nichiban Co., Ltd.) is applied to the grid and peeled in the direction of 90 degrees. The number was evaluated. The evaluation criteria were as follows.
○: All 100 squares were not peeled off.
Δ: 95 to 99 squares out of 100 squares were not peeled off.
X: 5 or more squares out of 100 squares were peeled off.
(2) Appearance The backer layer was heat-sealed using an embossing machine (100t press machine, manufactured by Toho Machinery Co., Ltd.) on the solid print layer of the pattern forming film obtained in each Example and Comparative Example. The fusing temperature was 140 ° C., the pressure was 2000 kPa, and pressing was performed for 2 hours. Thus, the decorative film with a backer layer was obtained, and it heated up at the speed | rate about 40 to 45 second until this film temperature became 170 degreeC, it heated, and the external appearance was evaluated visually. The evaluation criteria are as follows.
○: A part of the metal color became transparent, the pattern of the pattern printing layer appeared, and high designability was obtained.
X: The pattern of the pattern printing layer did not appear.

Example 1
A PET film having a thickness of 25 μm was plasma-treated to provide an easy-adhesion layer, and tin was deposited thereon by a vacuum deposition method. The conditions for vacuum deposition were a degree of vacuum of 10 ⁻³ Pa and a temperature of 1000 ° C. The metal thin film layer 12 thus obtained had an optical density OD value of 0.7 to 1.4.
Next, a vinyl chloride / vinyl acetate copolymer resin having an average acid value of 7.0 was applied on the metal thin film layer 12 by gravure printing to form a pattern printing layer 13. Next, a vinyl chloride / vinyl acetate copolymer resin having an average acid value of 4.2 was applied by gravure printing to provide a uniform solid print layer 14 to obtain a decorative film for pattern formation. The thickness of the solid print layer after drying at 50 ° C. was set to 2 μm.
The results of evaluating the film for pattern formation by the above method are shown in Table 1.
The vinyl chloride / vinyl acetate copolymer resin having an acid value of 7.0 constituting the pattern printing layer has an average acid value of 7, a number average molecular weight of 70,000 and a vinyl chloride / vinyl acetate copolymer having a Tg of 78 ° C. shown in Table 2. The vinyl chloride / vinyl acetate copolymer resin having an acid value of 4.2 constituting the solid printing layer using the polymer resin A as it is has an average acid value of 7, a number average molecular weight of 70,000 and a Tg of 78 ° C. shown in Table 2. This is a mixture of vinyl chloride / vinyl acetate copolymer resin A and vinyl chloride / vinyl acetate copolymer resin B having an average acid value of 0, a number average molecular weight of 50000, and a Tg of 75 ° C. in a ratio of 6: 4 (mass ratio). is there.

Example 2
In Example 1, a decorative film for pattern formation was produced in the same manner as in Example 1 except that the formation order of the metal thin film layer 12 and the pattern printing layer 13 was changed. The results evaluated in the same manner as in Example 1 are shown in Table 1.

Comparative Example 1
In Example 1, a pattern forming film was obtained in the same manner as in Example 1 except that a vinyl chloride / vinyl acetate copolymer resin having an average acid value of 5.6 was used as the resin constituting the pattern printing layer. It was. The vinyl acid / vinyl acetate copolymer resin having an average acid value of 5.6 is a mixture of the copolymer resin A and the copolymer resin B shown in Table 2 at a ratio of 2: 8 (mass ratio). It is. The results evaluated in the same manner as in Example 1 are shown in Table 1.

  ADVANTAGE OF THE INVENTION According to this invention, the film for pattern formation useful as a decorative film for insert molding which can decorate a metal color pattern, a film for packaging, a film for transparent electrode production, etc. can be provided. In particular, when used as a decorative film for three-dimensional molding, it has an unprecedented design feeling, follows three-dimensional processing, and can be used as a decorative film for insert molding that can give the appearance of excellent luster. A particularly useful pattern forming film can be provided. Such a decorative film can be suitably used for in-mold molding, insert molding, and the like, and is particularly useful for insert molding.

DESCRIPTION OF SYMBOLS 10 Pattern forming film 11 Base material 12 Metal thin film layer 13 Pattern printing layer 14 Solid printing layer 15 Primer layer 16 Surface protective layer 20 Pattern forming film (laminate type)
30 Film for pattern formation (transfer type)

Claims (9)

  A film for forming a pattern having at least a metal thin film layer and a pattern printing layer on a substrate, the pattern printing layer being in contact with the metal thin film layer, and a resin constituting the pattern printing layer being a vinyl chloride resin, A film for pattern formation, which is at least one selected from the group consisting of vinyl acetate resins and vinyl chloride / vinyl acetate copolymer resins, and has an average acid value of 7 mgKOH / g or more.   The film for pattern formation of Claim 1 formed by laminating | stacking a metal thin film layer and a pattern printing layer in this order on a base material.   The film for pattern formation of Claim 1 formed by laminating | stacking a pattern printing layer and a metal thin film layer in this order on a base material.   The number average molecular weights of resin which comprises the said pattern printing layer are 10,000-100,000, and the glass transition temperature is 70-90 degreeC, The film for pattern formation of any one of Claims 1-3.   The pattern forming film according to any one of claims 1 to 4, wherein a metal constituting the metal thin film layer is tin or indium.   The film for pattern formation according to claim 1, wherein the metal thin film layer is formed by a vapor deposition method.   Furthermore, the resin having a solid print layer and the resin constituting the solid print layer is neither a vinyl chloride resin, a vinyl acetate resin or a vinyl chloride / vinyl acetate copolymer resin having an average acid value of 7 mgKOH / g or more. The film for pattern formation of any one of Claims 1-6 characterized by these.   A method for forming a metal thin film pattern using a pattern forming film in which at least a metal thin film layer and a pattern printed layer are laminated in this order on a substrate, the pattern printed layer being in contact with the metal thin film layer and The resin constituting the layer is at least one selected from the group consisting of vinyl chloride resin, vinyl acetate resin, and vinyl chloride / vinyl acetate copolymer resin, and the average acid value of the resin is 7 mgKOH / g or more The method for forming a metal thin film pattern, comprising heat-treating the film for pattern formation at 100 ° C. or higher.   A method of forming a metal thin film pattern using a pattern forming film in which at least a pattern printing layer and a metal thin film layer are laminated in this order on a substrate, the pattern printing layer being in contact with the metal thin film layer, and The resin constituting the layer is at least one selected from the group consisting of vinyl chloride resin, vinyl acetate resin, and vinyl chloride / vinyl acetate copolymer resin, and the average acid value of the resin is 7 mgKOH / g or more The method for forming a metal thin film pattern, comprising heat-treating the film for pattern formation at 100 ° C. or higher.

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