JP2017185762A - Transfer film, decorative material, touch panel and manufacturing method of decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer film for forming a decorative layer on a surface of a touch panel or the like, capable of forming a black resin cured layer high in optical concentration and having suppressed glare of the decorative layer by undesired reflection, a decorative material, a touch panel with the decorative material and a manufacturing method of the decorative material.SOLUTION: There is provided a transfer film having: a temporary supporter; and a black resin layer that is provided on the temporary supporter and contains (A) a black pigment, (B) a dye, (C) an alkali-soluble resin, (D) an ethylenic unsaturated group-containing compound and (E) a photoinitiator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transfer film, a decorative material, a touch panel provided with a decorative material, and a method for manufacturing the decorative material.

Various image display devices such as cathode ray tube display devices, plasma displays, electroluminescence displays, fluorescent display devices, field emission displays and liquid crystal display devices (LCDs), or smartphones or tablet terminals equipped with touch panels. In the display, a decorative material having a decorative layer on the substrate is provided on the surface of the display for the purpose of applying various designs such as concealing the wiring arranged in the main body. For example, a decorative material provided with a decorative layer, which is a black resin cured layer containing a black pigment, is widely used on the periphery of the surface of an image display device for the purpose of concealing wiring.
Small terminals equipped with touch panels are used not only in rooms equipped with fluorescent lamps and LED (light emitting diode) lighting, but also under natural light, such as outdoors. Sometimes.

A black light-shielding film having a high light-shielding property can be formed. A photosensitive resin composition has been proposed (see, for example, Patent Document 1).
The black resin film contains a black pigment, an alkali-soluble polymer compound, an ethylenically unsaturated bond-containing compound and a photopolymerization initiator. After heating at 240 ° C. for 80 minutes, further heating at 300 ° C. for 30 minutes. A black resin film having a bulk strength of 100 N / 1.6 mmφ (φ is a diameter) or more has been proposed (for example, see Patent Document 2).
In Patent Document 2, as a method for producing a black resin film, a process of applying a photosensitive resin composition containing a black pigment, an alkali-soluble polymer compound, an ethylenically unsaturated bond-containing compound, and a photopolymerization initiator on a substrate. And a step of exposing the photosensitive resin composition on the substrate, a step of developing the exposed photosensitive resin composition, and a step of performing post-exposure after the development step, the following conditions (A) or A method for producing a black resin film that satisfies the condition (B) is described.
Condition (A): The photopolymerization initiator is an α-aminoalkylphenone compound or an α-hydroxyalkylphenone compound.
Condition (B): Post-exposure after the development step is performed from both the surface direction on the side in contact with the substrate of the photosensitive resin composition and the surface direction on the side not in contact with the transparent substrate.

JP, 2015-180932, A JP2013-228695A

According to the study by the present inventors, when directly viewing the screen displayed on the display, depending on the wavelength in the environment of use, it is inherently absorbed in a wide wavelength range and has high concealability, and is added to be visually recognized as black. It turned out that reflection, scattering, etc. of the light which are not desired generate | occur | produce in a decoration layer, a decoration layer may look glaring, and there exists a concern that an external appearance falls.
The black tourism resin composition described in Patent Document 1 mainly focuses on the black color, by combining an organic pigment or dye having a chromaticity of the same color as the light shielding material with a black pigment that is a light shielding material, The object is to form a black matrix of a color filter having black color characteristics as reflected light. However, it is not exposure from the back side such as a color filter, but about undesired light reflection and light scattering when light hits from the viewing side in a black resin cured layer formed in a large area such as a decorative layer of a touch panel No consideration has been given.
According to the studies by the present inventors, the technique described in Patent Document 1 has not led to suppression of glare in the case where light hits from the viewing side, and in particular, improves the uniformity of the decorative layer. For this purpose, it has been found that when the black resin layer is formed using a transfer method, the glare of the decorative layer is more noticeable.

  Patent Document 2 describes that a black resin film for a decoration layer is formed on the front plate side of the touch panel by heating at 240 ° C. for 80 minutes. However, for example, when a resin substrate is used as a base material and a black resin hardened layer is formed on the resin base material, heating is performed under the conditions described in Patent Document 2 because only low temperature heating of about 130 ° C. to 170 ° C. is possible. It was difficult to apply this method to the production of a decorative film using a resin base material. Moreover, the light-shielding film formed by the technique described in Patent Document 2 still has room for improvement in terms of suppressing glare of the decorative layer due to reflection as viewed from the viewing side.

A problem to be solved by an embodiment of the present invention is a transfer film for forming a black resin cured layer provided as a decorative layer on the surface of a touch panel or the like, which has a high optical density and glare due to undesired reflection. It is providing the transfer film which can form the black resin hardened layer by which sticking was suppressed.
Problems to be solved by another embodiment of the present invention include a decorative material having a black resin cured layer with high optical density and suppressed glare caused by reflection, a touch panel including the decorative material, and a decorative material It is in providing the manufacturing method of.

The present invention includes the following embodiments.
[1] A temporary support, provided on the temporary support, (A) a black pigment, (B) a dye, (C) an alkali-soluble resin, (D) an ethylenically unsaturated group-containing compound, and (E) light And a black resin layer containing a polymerization initiator.
[2] (A) The transfer film according to [1], wherein the black pigment is carbon black.
[3] The transfer film according to [2], wherein the carbon black is carbon black whose surface is coated with a resin.

[4] The transfer film according to any one of [1] to [3], wherein the (B) dye is a blue dye.
[5] The transfer film according to any one of [1] to [4], wherein the (B) dye is an anthraquinone dye.
[6] The transfer film according to any one of [1] to [5], which has a thermoplastic resin layer between the temporary support and the black resin layer.
[7] The transfer film according to [6], which has an intermediate layer between the black resin layer and the thermoplastic resin layer.

[8] A patterned black resin formed by a black resin layer in the transfer film according to any one of [1] to [7] on a substrate selected from the group consisting of a glass substrate and a resin substrate. A decorative material having a hardened layer.
[9] A touch panel comprising the decorative material according to [8].

[10] A step of transferring the black resin layer of the transfer film according to any one of [1] to [7] onto a substrate selected from the group consisting of a glass substrate and a resin substrate; Patterning the black resin layer by a photolithography method to form a patterned black resin layer, applying energy to the formed patterned black resin layer to form a patterned black resin cured layer, The manufacturing method of the decorating material containing.

According to one embodiment of the present invention, a transfer film for forming a decorative layer on the surface of a touch panel or the like, which forms a black resin cured layer with high optical density and suppressed glare caused by unwanted reflection Can be provided.
According to another embodiment of the present invention, a decorative material having a black resin cured layer with high optical density and suppressed glare of the decorative layer due to undesired reflection, a touch panel including the decorative material, and decorative A method for manufacturing the material can be provided.

It is a schematic sectional drawing which shows an example of a structure of the transfer film of this embodiment. It is a schematic plan view which shows an example of a touchscreen provided with the decorating material in which the patterned black resin cured layer was formed.

Hereinafter, the transfer film of the present invention, a decorative material obtained using the transfer film, a method for producing the decorative material, and a touch panel including the decorative material will be described.
The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples.

In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. To do.
In this specification, the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.

[Transfer film]
The transfer film of this embodiment is provided on a temporary support and a temporary support, and (A) a black pigment, (B) a dye, (C) an alkali-soluble resin, (D) an ethylenically unsaturated group-containing compound, And (E) a black resin layer containing a photopolymerization initiator.
The transfer film may have a layer other than the temporary support and the black resin layer, and examples of the other layer include an intermediate layer, a thermoplastic resin layer, and a protective release layer.
The transfer film of this embodiment can be used for forming a decorative layer on at least one surface of an image display device such as a touch panel.
The decorative layer, which is a patterned black resin cured layer formed by the transfer film of the present embodiment, has a high optical density, suppresses glare due to undesired light reflection, and has good light shielding properties and appearance.
Hereinafter, the structure of the transfer film of this embodiment is demonstrated.

<Configuration>
FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the transfer film of the present embodiment.
The transfer film 10 shown in FIG. 1 has a temporary support 12, a black resin layer 14, and a protective release layer (hereinafter sometimes referred to as a protective film) 16 in this order. FIG. 1 shows a mode in which the temporary support 12, the black resin layer 14, and the protective film 16 are laminated adjacent to each other, but this embodiment is not limited to this, and as will be described later, the temporary support 12 and Further, a thermoplastic resin layer (not shown) may be further provided between the black resin layer 14 and an intermediate layer is further provided between the black resin layer 18 and the optionally provided thermoplastic resin layer. An embodiment having (not shown) can be taken.
The transfer film 10 of this embodiment can be used as a transfer film for forming a decorative layer, that is, a patterned black resin cured layer, on one surface of an image display device such as a touch panel.
A method for producing a decorative material by transferring the black resin layer 14 onto the substrate using the transfer film 10 of the present embodiment will be described later.

The operational effects of the present embodiment are not clear, but are considered as follows.
The black pigment dispersed in a resin matrix containing an alkali-soluble resin, an ethylenically unsaturated group-containing compound, etc. can block the light from the backlight that is the light source of the image display device, but the incident light from the viewing side is In addition, undesired reflection or scattering of light may occur on the pigment surface, the resin layer surface, etc., and glare may be felt when viewing the black resin layer.
In this embodiment, (A) black pigment and (B) dye coexist in the resin matrix in the black resin layer, so that (B) dye is on the surface of (A) black pigment in the black resin layer. Since the light reflected or scattered is absorbed, and part of the incident light to the black resin layer is also absorbed, transmission of unwanted reflected light, scattered light, etc. to the black resin layer surface is suppressed, It is estimated that the glare felt visually is suppressed and the black resin layer has a high jet black feeling.
When the black resin layer is formed by a coating method, the surface of the layer on which the low molecular weight component of the black resin layer forming composition such as a surfactant added to improve the film thickness uniformity is formed. It is unevenly distributed and transmission and scattering at the time of light incidence are suppressed to some extent. In the black resin layer formed by the transfer method using the transfer film, the low molecular weight component at the time of coating is unevenly distributed on the temporary support side, that is, the side opposite to the side to be observed, and formed by the coating method. Compared to the black resin layer, the effect of suppressing transmission and scattering at the time of incident light cannot be sufficiently obtained, and thus the glare is felt more strongly. For this reason, it is thought that the effect of this embodiment is remarkable in the black resin layer formed of the transfer film.
In addition, this embodiment is not restrict | limited to the said estimation mechanism at all.

<Black resin layer>
The transfer film of the present embodiment comprises (A) a black pigment, (B) a dye, (C) an alkali-soluble resin, (D) an ethylenically unsaturated group-containing compound, and (E) a photopolymerization initiator. Have

(A) Black pigment There is no restriction | limiting in particular in the black pigment which can be used for the black resin layer in this embodiment, as long as the light-shielding property required in the black resin cured layer formed can be expressed.
As the black pigment, a known black pigment, for example, a black pigment selected from organic pigments and inorganic pigments can be suitably used. Inorganic pigments include pigments containing metal compounds such as metal pigments and metal oxide pigments.
From the viewpoint that the optical density of the formed black resin layer is good, examples of the black pigment include titanium oxide pigments such as carbon black, titanium carbon, iron oxide, and titanium black, and graphite. Black is preferred.
Carbon black is also available as a commercial product, and examples thereof include black pigment dispersion FDK-911 [trade name: FDK-911] manufactured by Tokyo Ink Co., Ltd.
The carbon black that can be used for the transfer film of the present embodiment is carbon black whose surface is coated with a resin (hereinafter sometimes referred to as resin-coated carbon black). Is preferable in that it becomes better. In addition, the coating of carbon black with a resin may be performed as long as at least a part of the surface of carbon black is coated, and the entire surface may be coated.
The resin-coated carbon black can be produced, for example, by the method described in paragraph Nos. [0036] to [0042] of Japanese Patent No. 5320652. Moreover, it is also available as a commercial item, for example, SF Black GB4051 by Sanyo Dye Co., Ltd. is mentioned.

The particle diameter of the black pigment is preferably 0.001 μm to 0.3 μm, more preferably 0.01 μm to 0.2 μm in terms of number average particle diameter, from the viewpoint of dispersion stability. The “particle size” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle size” refers to the particle size of any 100 particles. The average value of the particle diameters is obtained.
In addition, the number average particle diameter of the pigment used for the transfer film of this embodiment is a viewing angle using the photograph which image | photographed 300,000 times the black resin layer containing a black pigment with the transmission electron microscope (JEOL). The particle diameter can be measured for any 100 particles contained in, and the average value of the measured values can be calculated.

The content of the black pigment in the black resin layer, that is, the content of the black pigment with respect to the total solid content in the composition for forming the black resin layer is preferably 10% by mass to 70% by mass, and 20% by mass to 60%. More preferably, it is more preferably 30% by mass to 55% by mass.
When the content of the black pigment is 10% by mass or more, the optical density of the black resin cured layer can be increased while keeping the film thickness thin. When the content of the black pigment is 70% by mass or less, the curing sensitivity when patterning the black resin layer is improved.
The total solid content in the composition for forming a black resin layer means the total mass of nonvolatile components excluding the solvent contained in the composition.

The black pigment is desirably used in the composition for forming a black resin layer as a dispersion. The dispersion can be prepared by adding and dispersing a composition obtained by previously mixing a black pigment and a pigment dispersant in an organic solvent or a vehicle described later. A vehicle refers to a portion of a medium in which a pigment is dispersed when the composition for forming a black resin layer is in a liquid state, and is a liquid component that forms a black resin layer by combining with a black pigment (for example, a binder). And a medium such as an organic solvent for dissolving and diluting it.
The disperser used for dispersing the black pigment is not particularly limited. For example, a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, page 438, Known dispersing machines such as a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, the black pigment as the dispersoid may be finely pulverized using frictional force by mechanical grinding described on page 310 of the document.
In addition, what is necessary is just to select a pigment dispersant according to the pigment and solvent which are contained in the composition for black resin layer formation, for example, a commercially available dispersing agent can be used.

(B) Dye There is no restriction | limiting in particular in the dye which can be used for the black resin layer in this embodiment. Known dyes, for example, known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970), or dyes available as commercial products are appropriately selected and used. Can do.
Specific examples of the dye include azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolates. And dyes such as complexes.

Hereinafter, dyes that can be used in the present embodiment are listed, but the present embodiment is not limited thereto.
Examples of yellow dyes include C.I. I. Direct Yellow 1, C.I. I. Direct Yellow 11, C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 28, C.I. I. Acid Yellow 1, C.I. I. Acid Yellow 3, C.I. I. Acid Yellow 11, C.I. I. Acid Yellow 17, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 38, C.I. I. Acid Yellow 40, C.I. I. Acid Yellow 42, C.I. I. Acid Yellow 76, C.I. I. Acid Yellow 98, C.I. I. Basic Yellow 1, C.I. I. Disperse Yellow 3, C.I. I. Disperse Yellow 4, C.I. I. Disperse Yellow 7, C.I. I. Disperse Yellow 31, C.I. I. Disperse Yellow 61, C.I. I. Solvent Yellow 2, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 16, C.I. I. Solvent Yellow 21, C.I. I. Solvent Yellow 33, C.I. I. Solvent yellow 56 etc. are mentioned.

  Examples of the orange dye include C.I. I. Acid Orange 1, C.I. I. Acid Orange 7, C.I. I. Acid Orange 8, C.I. I. Acid Orange 10, C.I. I. Acid Orange 20, C.I. I. Acid Orange 24, C.I. I. Acid Orange 28, C.I. I. Acid Orange 33, C.I. I. Acid Orange 56, C.I. I. Acid Orange 74, C.I. I. Direct Orange 1, C.I. I. Disperse Orange 5, C.I. I. Solvent Orange 1, C.I. I. Solvent Orange 2, C.I. I. Solvent Orange 5, C.I. I. Solvent Orange 6, C.I. I. Solvent orange 45 etc. are mentioned.

  Examples of red dyes include C.I. I. Direct Red 20, C.I. I. Direct Red 37, C.I. I. Direct Red 39, C.I. I. Direct Red 44, C.I. I. Acid Red 6, C.I. I. Acid Red 8, C.I. I. Acid Red 9, C.I. I. Acid Red 13, C.I. I. Acid Red 14, C.I. I. Acid Red 18, C.I. I. Acid Red 26, C.I. I. Acid Red 27, C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 88, C.I. I. Acid Red 89, C.I. I. Acid Red 92, C.I. I. Acid Red 94, C.I. I. Acid Red 97, C.I. I. Acid Red 111, C.I. I. Acid Red 114, C.I. I. Acid Red 115, C.I. I. Acid Red 134, C.I. I. Acid Red 145, C.I. I. Acid Red 154, C.I. I. Acid Red 180, C.I. I. Acid Red 183, C.I. I. Acid Red 184, C.I. I. Acid Red 186, C.I. I. Acid Red 198, C.I. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Disper thread 5, C.I. I. Disper thread 7, C.I. I. Disperse thread 13, C.I. I. Disperse thread 17, C.I. I. Disperse thread 58, C.I. I. Solvent Red 1, C.I. I. Solvent Red 3, C.I. I. Solvent Red 8, C.I. I. Solvent Red 23, C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27, C.I. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 100 etc. are mentioned.

Examples of purple dyes include C.I. I. Direct violet 22, C.I. I. Acid Violet 49, C.I. I. Basic Violet 2, C.I. I. Basic Violet 7, C.I. I. Basic Violet 10, C.I. I. Disper violet 24 etc. are mentioned.
Examples of blue dyes include C.I. I. Direct Blue 25, C.I. I. Direct Blue 86, C.I. I. Direct Blue 90, C.I. I. Direct Blue 108, C.I. I. Acid Blue 1, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Acid Blue 103, C.I. I. Acid Blue 104, C.I. I. Acid Blue 158, C.I. I. Acid Blue 161, C.I. I. Basic Blue 1, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9, C.I. I. Basic Blue 25, C.I. I. Solvent Blue 5, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 67, C.I. I. Solvent Blue 70 etc. are mentioned.

Examples of the green dye include C.I. I. Acid Green 3, C.I. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Basic Green 1, C.I. I. Basic green 4 etc. are mentioned.
Examples of brown dyes include C.I. I. Direct Brown 6, C.I. I. Direct Brown 58, C.I. I. Direct Brown 95, C.I. I. Direct Brown 101, C.I. I. Direct Brown 173, C.I. I. Acid brown 14 etc. are mentioned.

Of these, blue dyes are preferable from the viewpoint of the effect of suppressing glare due to reflection of the patterned black resin cured layer to be formed.
More specifically, a blue dye having a maximum absorption wavelength at a wavelength of 500 nm to 700 nm is preferable. Among the blue dyes, anthraquinone dyes are preferable from the viewpoint that the hue is closer to black.

  The content of the dye in the black resin layer is preferably 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the black pigment from the viewpoint of more effectively expressing the antireflection ability. It is more preferable that it is 20 parts by mass. When the content of the dye is within the above range, the antireflection effect in the formed black resin cured layer, that is, the effect of suppressing glare by visual observation becomes better.

(C) Alkali-soluble resin The black resin layer contains an alkali-soluble resin (hereinafter sometimes referred to as a binder). The alkali-soluble resin is not particularly limited as long as it is a resin that can be at least partially dissolved by contact with an alkaline solvent, and can be appropriately selected from known resins.
As the alkali-soluble resin, for example, resins described in paragraph No. [0025] of JP 2011-95716 A and paragraphs [0033] to [0052] of JP 2010-237589 A can be used.
It is preferable that the black resin layer in the transfer film of this embodiment contains the binder which has a carboxyl group from a viewpoint that pattern formation property is more favorable. By containing a binder having a carboxyl group, the linearity of the formed pattern end portion becomes better, and so-called edge roughness tends to be improved.
The acid value of the binder is preferably 50 mgKOH / g or more from the viewpoint of improving the alkali solubility in the unexposed area during pattern formation and improving the edge roughness described above. The acid value of the binder is more preferably 60 mgKOH / g or more, and further preferably 65 mgKOH / g or more.

The acid value of the binder can be measured, for example, by the following method.
(1) A resin solution (y (g)) having a solid content concentration (x (%)) is diluted with propylene glycol monomethyl ether acetate to prepare a sample solution having a solid content concentration of 1 mass% to 10 mass%.
(2) A 0.1 mol / L potassium hydroxide / ethanol solution (titer a) was applied to the sample solution using a potentiometer (Hiranuma Sangyo Co., Ltd., apparatus name “Hiranuma Automatic Titrator COM-550”). ) And measure the amount of potassium hydroxide / ethanol solution (b (mL)) required by the end of titration.
(3) Further, titration is performed on water by the same method as in (2), and the amount of potassium hydroxide / ethanol solution (c (mL)) necessary until the end of titration is measured.
(4) The solid content acid value of the resin emulsion is determined by calculating with the following formula.
Solid content acid value (mgKOH / g) = {5.611 × (bc) × a} / {(x / 100) × y}

More specifically, as the binder used in the black resin layer in the present embodiment, a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid, a random copolymer of benzyl (meth) acrylate / acrylic acid , Cyclohexyl (meth) acrylate (a) / methyl (meth) acrylate (b) / (meth) acrylic acid copolymer (c) glycidyl (meth) acrylate adduct, allyl (meth) acrylate / (meth) acrylic acid A copolymer of benzyl (meth) acrylate / (meth) acrylic acid / hydroxyethyl (meth) acrylate can be used.
In this specification, (meth) acrylate means one or both of acrylate and methacrylate, and (meth) acrylic acid means one or both of acrylic acid and methacrylic acid, respectively. .

  The content of the alkali-soluble resin contained in the black resin layer is preferably in the range of 1% by mass to 70% by mass with respect to the total solid content in the black resin layer, and is in the range of 5% by mass to 60% by mass. It is more preferable that the range is 10% by mass to 50% by mass.

(D) Ethylenically unsaturated group-containing compound The black resin layer contains an ethylenically unsaturated group-containing compound (hereinafter sometimes referred to as a polymerizable compound). As the polymerizable compound used in the present embodiment, a photopolymerizable compound is preferable.
The photopolymerizable compound has an ethylenically unsaturated group as a photopolymerizable group.
More preferably, the ethylenically unsaturated group-containing compound includes a compound having a (meth) acryloyl group. In addition, the (meth) acryloyl group in this specification is used in the meaning which shows one or both of an acryloyl group and a methacryloyl group.
Examples of the ethylenically unsaturated group-containing compound that can be suitably used in this embodiment include a polymerizable compound described in paragraph Nos. [0023] to [0024] of Patent No. 4098550, and tricyclodecanediol dimethanol diacrylate. And bifunctional polymerizable compounds such as ethoxylated bisphenol A diacrylate.
Examples of the polymerizable compound include not only the monofunctional or bifunctional compounds described above, but also, for example, dipentaerythritol hexaacrylate (hereinafter sometimes referred to as DPHA), dipentaerythritol (penta / hexa) acrylate, A polymerizable compound having at least five ethylenically unsaturated groups such as pentaerythritol octaacrylate can also be preferably used depending on the purpose.
In addition, urethane monomers such as urethane (meth) acrylate compounds can also be preferably used.

When the black resin layer contains a polymerizable compound having at least five ethylenically unsaturated groups, it is preferable from the viewpoint that the sensitivity during pattern formation and the strength of the formed patterned black resin cured layer are further improved.
A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, it is preferable from a viewpoint that the sensitivity at the time of pattern formation improves using it in combination of 2 or more types of polymeric compounds.
When using 2 or more types of polymeric compounds for a black resin layer, it is preferable to use combining the polymeric compound which has at least 5 ethylenically unsaturated group, and a bifunctional polymeric compound. The bifunctional polymerizable compound is preferably used in the range of 10% by mass to 90% by mass, and in the range of 20% by mass to 85% by mass with respect to the total content of all polymerizable compounds contained in the black resin layer. It is more preferable to use in the range of 30% by mass to 80% by mass. The polymerizable compound having at least 5 ethylenically unsaturated groups is preferably used in the range of 10% by mass to 90% by mass with respect to the total content of all polymerizable compounds, and is 15% by mass to 80% by mass. It is more preferable to use in the range, and it is more preferable to use in the range of 20% by mass to 70% by mass.
The average molecular weight of the polymerizable compound is preferably 200 to 3000, more preferably 250 to 2600, and particularly preferably 280 to 2200.

  In the black resin layer, the content ratio of (D) polymerizable compound to (C) binder ((D) polymerizable compound content / (C) binder content) is 0.1 to 2 times in terms of mass ratio. Is preferably 0.2 times to 1.5 times, more preferably 0.3 times to 1 time.

  The content of the polymerizable compound contained in the black resin layer is preferably in the range of 5% by mass to 50% by mass with respect to the total solid content in the black resin layer, and is in the range of 10% by mass to 40% by mass. It is more preferable that the range is 10% by mass to 30% by mass.

(E) Photopolymerization initiator The black resin layer in this embodiment contains a photopolymerization initiator.
As the photopolymerization initiator used for forming the black resin layer, polymerization initiators described in paragraph numbers [0031] to [0042] of JP 2011-95716 A, paragraph numbers of JP 2015-014783 A [ Oxime polymerization initiators described in [0064] to [0081].
A commercial item can be used for a photoinitiator. Examples of commercially available products include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethane-1-one. , [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) Trade name: IRGACURE OXE-02, manufactured by BASF), 2- (dimethylamino) 2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1 (trade name: IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: IRGACURE 1173, manufactured by BASF), 1-hydroxy -Cyclohexyl-phenyl-ketone (trade name: IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF), trade name of oxime ester series : Lunar 6 (manufactured by DKSH Japan), 2,4-di Chi Lucio xanthone (manufactured by Nippon Kayaku Co., Ltd., "Kayacure DETX-S"), DFI-091 fluorene oxime polymerization initiator, DFI-020 (both manufactured by Daitokemikkusu Ltd.) and the like preferably.

Of these, it is preferable to use an initiator other than a halogen-containing polymerization initiator such as a trichloromethyltriazine compound used for a color filter material or the like from the viewpoint of increasing sensitivity, and an α-aminoalkylphenone compound, α-hydroxy Oxime polymerization initiators such as alkylphenone compounds and oxime ester compounds are more preferable, and it is particularly preferable to include the oxime polymerization initiator described above from the viewpoint of further improving the sensitivity during pattern formation.
The content of the (E) photopolymerization initiator in the black resin layer is the mass ratio of the (D) ethylenically unsaturated group-containing compound described above [(E) photopolymerization initiator / (D) ethylenically unsaturated group. Containing compound] is 0.05 to 0.50, the taper angle of the formed patterned black resin cured layer becomes closer to a rectangle, and precipitation of the (E) photopolymerization initiator from the black resin layer occurs. From the viewpoint of being more effectively suppressed, it is more preferably 0.07 to 0.30.

(F) Other components contained in the black resin layer In addition to the components (A) to (E) described above, the black resin layer in the transfer film of the present embodiment has a range that does not impair the effects of the present embodiment. Depending on the purpose, various compounds other than the components (A) to (E) described above (hereinafter may be referred to as other components) may be included.
Examples of other components include (A) particles other than black pigment, thiol compounds, solvents, and the like, but are not limited thereto.

(F-1) Thiol Compound The black resin layer in the present embodiment preferably contains a thiol compound from the viewpoint of further increasing the sensitivity during pattern formation.
As a thiol compound, the functional number which is the number of thiol groups (also referred to as mercapto groups) may be monofunctional or bifunctional or more.
When the black resin layer contains a thiol compound, the thiol compound is preferably a bifunctional or higher functional compound, more preferably a bifunctional to tetrafunctional compound, more preferably a bifunctional to trifunctional compound. It is particularly preferred that
Examples of the monofunctional thiol compound that can be included in the black resin layer include N-phenylmercaptobenzimidazole.
Examples of the bifunctional or higher functional thiol compound that can be contained in the black resin layer include 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1, Showa Denko), 1,3,5-tris (3- Mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenz MT NR1 manufactured by Showa Denko), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz) MT PE1 manufactured by Showa Denko), pentaerythritol tetrakis (3-mercaptopropionate) (“PEMP” manufactured by Sakai Chemical Industry Co., Ltd.), and the like.

(F-2) Additive The black resin layer may contain an additive. Examples of the additives include surfactants described in paragraph No. [0017] of Japanese Patent No. 4502784, paragraph Nos. [0060] to [0071] of JP-A-2009-237362, and Japanese Patent No. 4502784. Thermal polymerization inhibitor (also referred to as polymerization inhibitor, preferably phenothiazine) described in paragraph [0018], and other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706 Is mentioned.
As the surfactant, it is preferable to use a fluorine-containing surfactant, for example, Megafac (registered trademark) F-780 manufactured by DIC Corporation, from the viewpoint of improving the film property at the time of forming the black resin layer.

(F-3) Solvent The black resin layer preferably further contains a solvent.
Examples of the solvent that may be contained when the black resin layer is produced by coating include the following solvents.
As the solvent, a commonly used solvent can be used without particular limitation. Specific examples of the solvent include esters, ethers, ketones, and aromatic hydrocarbons.
In addition, as in Solvent described in paragraph numbers [0054] and [0055] of US2005 / 282073A1, the methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PEGMEA), cyclohexanone, Cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate and the like can be suitably used for the black resin layer.
Among the aforementioned solvents, 1-methoxy-2-propyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone Cyclohexanone, diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate, and methyl ethyl ketone are preferably used as the solvent.
When a black resin layer contains a solvent, a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
As the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 ° C. to 250 ° C. can be used as necessary.

(Film thickness)
The black resin layer in the transfer film of this embodiment can be formed using the black resin layer forming composition containing each component described above.
The film thickness of the obtained black resin layer is preferably 0.5 μm to 10.0 μm from the viewpoint of design when used as a decorating material, and more preferably 1.0 μm to 8.0 μm. Preferably, it is 1.5 micrometers-5.0 micrometers.

<Temporary support>
The transfer film of this embodiment has a temporary support.

A flexible material can be used for forming the temporary support.
Examples of the temporary support that can be used for the transfer film of the present embodiment include a cycloolefin copolymer film, a polyethylene terephthalate (hereinafter sometimes referred to as “PET”) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a PET film is particularly preferable from the viewpoint of handling.
The temporary support may be transparent, or may be colored by containing dyed silicon, alumina sol, chromium salt, zirconium salt or the like.
The temporary support can be provided with conductivity by the method described in JP-A-2005-221726, and the temporary support provided with conductivity is also suitably used for the transfer film of this embodiment. .

<Other layers>
The transfer film of this embodiment may have a thermoplastic resin layer described in paragraph No. [0026] of Japanese Patent No. 4502784 between the temporary support and the black resin layer described above.
Further, an intermediate layer may be further provided between the black resin layer described above and the thermoplastic resin layer.
As an intermediate | middle layer, the intermediate | middle layer as described in the paragraph number [0027] of the patent 4502784 is mentioned, for example.
In the transfer film of this embodiment, it is preferable to further provide a protective film or the like on the surface of the black resin layer described above. As the protective film, protective films described in paragraph numbers [0083] to [0087] and [0093] of JP-A-2006-259138 can be appropriately used.

In addition, the transfer film of this embodiment as described above can be produced according to the method for producing a curable transfer material described in paragraph numbers [0094] to [0098] of JP-A-2006-259138.
That is, the transfer film manufacturing method includes a step of forming a black resin layer on the temporary support. Furthermore, it is preferable to further include a step of forming a thermoplastic resin layer before forming the aforementioned black resin layer on the temporary support.

It is preferable that the manufacturing method of a transfer film includes the process of forming an intermediate | middle layer between a thermoplastic resin layer and a coloring composition layer after the process of forming the thermoplastic resin layer as stated above.
In the case of forming a transfer film having an intermediate layer, a solution (thermoplastic resin layer coating solution) in which a thermoplastic organic polymer and an additive used in combination are dissolved on a temporary support is dissolved. After coating and drying to provide a thermoplastic resin layer, an intermediate layer coating solution prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer is applied on the provided thermoplastic resin layer. Then, the intermediate layer is laminated by drying, and further, a black resin layer forming composition prepared using a solvent that does not dissolve the intermediate layer is applied onto the laminated intermediate layer and dried to form a black resin layer. By doing so, it can be suitably manufactured.
In addition, it is preferable that the component contained in the composition for black resin layer formation is a coating liquid composition containing each component contained in the above-mentioned black resin layer, and a solvent.

<Decoration materials>
The decorative material of the present embodiment is a patterned black resin cured layer formed by the black resin layer in the transfer film of the present embodiment described above on a substrate selected from the group consisting of a glass substrate and a resin substrate. Have The obtained patterned black resin cured layer corresponds to the decorative layer in the decorative material.

  Moreover, it is preferable that the decorating material of this embodiment produced using the transfer film of this embodiment is manufactured with the manufacturing method of the following decorating materials.

<Method for producing decorative material>
The method for producing a decorative material of the present embodiment includes a step of transferring the black resin layer of the transfer film of the present embodiment described above onto a substrate selected from the group consisting of a glass substrate and a resin substrate, Patterning the formed black resin layer by a photolithography method to form a patterned black resin layer; and applying energy to the formed patterned black resin layer to form a patterned black resin cured layer; ,including.

(Base material)
As the base material in the decorative material, it is preferable to use a material which is optically free and has high transparency.
From such a viewpoint, a glass substrate and a resin substrate that are highly transparent are preferable.
Among these, a resin base material is preferable from the viewpoint of being lightweight and difficult to break. Specific examples of the resin base material include base materials made of resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate (PC), triacetyl cellulose (TAC), and cycloolefin polymer (COP). it can.

The base material preferably has a refractive index of 1.6 to 1.78 and a film thickness of 50 μm to 200 μm from the viewpoint of further improving the visibility of the display image.
The substrate may have a single layer structure or a laminated structure of two or more layers. When the substrate has a laminated structure of two or more layers, the refractive index means the refractive index of the entire layer of the substrate.
As long as the refractive index range is satisfied, the material forming the substrate is not particularly limited.
In addition, the thickness of a base material means the total thickness of all the layers, when it is a laminated structure of two or more layers.

The black resin layer in the aforementioned transfer film is transferred to the surface of the substrate, and an exposure process for pattern exposure and a development process for developing unexposed areas are performed.
As an example of the exposure step, the development step, and other steps of the black resin layer transferred onto the substrate, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 is described in the present invention. Can also be suitably used.

An exposure process is a process of exposing the black resin layer transcribe | transferred on the base material.
Specifically, a mask on which a predetermined pattern is formed is disposed above the black resin layer transferred onto the substrate, that is, between the black resin layer and the exposure light source, and then the mask, the temporary support, And a method of exposing the black resin layer from above the mask through the mask.
The exposure light source can be appropriately selected and used as long as it can irradiate light in a wavelength region that can cure the black resin layer (eg, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure amount is usually about 5 J / cm ^{2 to} 200 mJ / cm ² , and preferably about 10 J / cm ^{2 to} 100 mJ / cm ² .

The pattern exposure may be performed after the temporary support is peeled off, or may be exposed before the temporary support is peeled off, and then the temporary support may be peeled off. The pattern exposure may be exposure through a patterned mask or scanning exposure (digital exposure) using a laser or the like.
A decorative material in which a decorative layer that is a patterned black resin cured layer is formed on a base material is manufactured through the above-described steps.
FIG. 2 is a schematic plan view illustrating an example of the touch panel 18 including a decorative material on which a patterned black resin cured layer (decorative layer) 20 is formed. In FIG. 2, the area | region displayed in black shows the formation area of the decoration layer 20. In FIG. Since the decorative material includes the decorative layer 20 having a shape as shown in FIG. 2, the wiring arranged on the main body of the touch panel 18 can be concealed.

The development step is a step of developing the exposed black resin layer.
In this invention, it is a development process of the narrow meaning in which the unexposed part in the black resin layer by which pattern exposure was carried out is developed and removed with a developing solution, and a patterned black resin layer is formed.
Development can be performed using a developer. There is no restriction | limiting in particular as a developing solution, A well-known developing solution like the developing solution described in Unexamined-Japanese-Patent No. 5-72724 can be used. The developer is preferably a developer capable of dissolving the unexposed black resin layer. For example, a developer containing a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable.
A small amount of an organic solvent miscible with water may be added to the developer. Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

  As the development method described above, any of paddle development, shower development, shower development + spin development, dip development, and the like may be used. Here, shower development will be described. A patterned black resin layer can be formed by removing uncured portions by spraying a developer onto the black resin layer after exposure by showering. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

<Heat treatment>
It is preferable that the manufacturing method of a decorating material includes the process (post-baking process) heat-processed at 130 to 170 degreeC after the process of transferring a black resin cured layer. A method for producing a decorative material, in which a decorative layer is formed after other members such as an electrode pattern, a lead-out wiring, a light-shielding conductive film, and an overcoat layer are previously formed on the substrate by heat treatment at such a temperature. However, heat treatment can be performed without adversely affecting other members.
As for the temperature of the process to heat-process, it is more preferable that it is 140 to 160 degreeC, and it is especially preferable that it is 140 to 150 degreeC.
The time for the heat treatment step is preferably 1 minute to 60 minutes, more preferably 10 minutes to 60 minutes, and further preferably 20 minutes to 50 minutes.

  The manufacturing method of a decorating material may have the process of providing energy to a pattern-like black resin layer, further promoting hardening, and forming a pattern-like black resin cured layer. By applying energy, the crosslink density of the patterned black resin layer is improved, and the strength of the produced patterned black resin cured layer is further improved. The energy application can be appropriately selected from heating, irradiation with actinic rays, for example, entire exposure with ultraviolet rays. From the viewpoint of the effect and the simplicity of the process, the energy application is preferably heating.

[Touch panel]
The touch panel according to the present embodiment includes the decorative material according to the present embodiment. The decorative material is arranged on the outermost surface of the touch panel.

There is no restriction | limiting in particular in the touchscreen which can apply the decorating material which concerns on this embodiment, According to the objective, it can select suitably. For example, a surface capacitive touch panel, a projected capacitive touch panel, a resistive touch panel, and the like can be given. Details will be described later as a resistive touch panel according to the present embodiment and a capacitive touch panel according to the present embodiment.
The touch panel includes so-called touch sensors and touch pads. The layer structure of the touch panel sensor electrode part in the touch panel is a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper or through-hole method, or a single-area layer method. Either is acceptable. In addition, the projected capacitive touch panel is preferably AC (alternating current) driving rather than DC (direct current) driving, and more preferably a driving method in which the voltage application time to the electrodes is short.

(Resistive touch panel)
The resistive film type touch panel according to the present embodiment is a resistive film type touch panel including the decorative material according to the present embodiment.
The resistive touch panel has a basic configuration in which conductive films of a pair of upper and lower substrates having a conductive film are disposed via a spacer at a position where the conductive films face each other. The configuration of the resistive film type touch panel is well known, and any known technique can be applied without any limitation in the present embodiment.

(Capacitive touch panel)
The capacitive touch panel according to the present embodiment is a capacitive touch panel including the decorative material according to the present embodiment.
Examples of the capacitive touch panel system include a surface capacitive type and a projected capacitive type. The projected capacitive touch panel has a basic arrangement in which an X-axis electrode (hereinafter also referred to as an X electrode) and a Y-axis electrode (hereinafter also referred to as a Y electrode) orthogonal to the X electrode are disposed via an insulator. Consists of configuration. As a specific aspect, an aspect in which the X electrode and the Y electrode are formed on separate surfaces on one substrate, an aspect in which the X electrode, the insulator layer, and the Y electrode are formed in this order on the single substrate. Examples include an embodiment in which an X electrode is formed on one substrate and a Y electrode is formed on another substrate (in this embodiment, a configuration in which two substrates are bonded together is the above basic configuration). The configuration of the capacitive touch panel is known, and any known technique can be applied without any limitation in the present embodiment.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Examples 1 to 5, Comparative Example 1]
<Preparation of composition for forming black resin layer>
A black resin layer forming composition was prepared by thoroughly stirring and mixing these components in accordance with the formulation described in Table 1 below.
Details of the compounds described in Table 1 are as follows. In Table 1, the abbreviations shown in [] are used.

(A) SF Black GB4051 (trade name: Resin-coated carbon black dispersion) [SF Black GB4051] manufactured by Sanyo Dye Co., Ltd.
・ Black pigment dispersion FDK-911 [trade name: FDK-911] manufactured by Tokyo Ink Co., Ltd.
・ K pigment dispersion 1
Carbon black, a dispersant, a polymer and a solvent were mixed so that the composition of the following K pigment dispersion 1 was obtained, and a K pigment dispersion 1 was obtained using a three roll and bead mill.
(K pigment dispersion 1)
-Resin-coated carbon black produced according to the description in paragraph Nos. [0036] to [0042] of Japanese Patent No. 5320652 13.1% by mass
-Dispersant 1 [the following structure] 0.65 mass%
・ Polymer 6.72% by mass
(Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000)
Propylene glycol monomethyl ether acetate 79.53% by mass

(B) Dye / Dye (A-1) The following structure / Dye (B-1) The following structure / Dye Oil Blue 613 (made by Orient Corporation of America) [Table 1 shows Oil Blue 613]
・ Dye Balifast Blue 2606 (Orient Corporation of America) [Valifast Blue 2606]

(C) Alkali-soluble resin / benzyl methacrylate / methacrylic acid copolymer [mass-based copolymerization ratio: 82/18]
(D) Ethylenically unsaturated group-containing compound, Shin-Nakamura Chemical Co., Ltd. A-NOD-N (trade name) [A-NOD-N]
-Shin-Nakamura Chemical Co., Ltd. A-DCP (trade name) [A-DCP]
・ A-BPE-10 (trade name) [A-BPE-10] manufactured by Shin-Nakamura Chemical Co., Ltd.
-Shin-Nakamura Chemical Co., Ltd. UA-32P (trade name) [UA-32P]
-Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) DPHA (75% by mass PGMEA solution of dipentaerythritol hexaacrylate) (PGMEA solution of KAYARAD DPHA)
-Taisei Fine Chemicals, 8UX-015A (trade name) [8UX-015A]

(E) Photopolymerization initiator, BASF Corporation Irgacure (registered trademark) OXE02 [Irgacure OXE02]
・ Irgacure 907 [Irgacure 907] manufactured by BASF
・ DFI-020 [DFI-020] manufactured by Daito Chemix
(Surfactant)
-DIC Corporation Mega Fuck (registered trademark) F-780 [Mega Fuck F-780F]

<Production of transfer film>
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the above-mentioned composition for forming a black resin layer was applied and dried. By the above-described method, a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a black resin layer having a dry film thickness of 2.0 μm are formed on the temporary support. Finally, a protective film (12 μm thick polypropylene film) was pressure-bonded. Thus, transfer films of Examples 1 to 5 and Comparative Example 1 having a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), a black resin layer, and a protective film were produced.

(Coating solution for thermoplastic resin layer: Formulation H1)
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.36 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) ) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio)) = 63 / 37,
Weight average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts by mass. 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts by mass・ Fluoropolymer 0.54 parts by mass (40 parts of C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ and H (OCH (CH ₃ ) CH ₂ ) ₇ 55 parts of OCOCH═CH ₂ and H (OCH ₂ CH ₂ ) ₇ Copolymer with 5 parts of OCOCH = CH ₂ , weight average molecular weight 30,000, 30% by weight methyl ethyl ketone solution, manufactured by DIC, trade name: Megafak F780F)

(Coating liquid for intermediate layer: prescription P1)
PVA205 32.2 parts by mass (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
・ 14.9 parts by mass of polyvinylpyrrolidone (APS Japan, K-30)
-524 parts by mass of distilled water-429 parts by mass of methanol

<Measurement of reflectance>
The protective film was removed from the obtained transfer films of Examples 1 to 5 and Comparative Example 1, and the surface of the black resin layer exposed after the removal and the glass substrate (Corning Corp. Eagle XG) were transparent. The decorative material was formed by bonding with an adhesive tape (manufactured by 3M, OCA tape 8171CL: trade name).
About the obtained decorating material, the reflectance in wavelength 550nm was measured using the integrating sphere reflectometer (JASCO Corporation V570) from the side in which the black resin layer was formed. The results are shown in Table 1. When the reflectance is less than 5.0%, it is evaluated that suppression of visual glare can be confirmed.

<Sensory evaluation by visual observation of black resin layer (decorative layer)>
In the room where the three-wavelength fluorescent lamp was lit, the observation was made while changing the angle with respect to the illumination, and the blackness of the decorative layer was evaluated according to the following criteria.
Five people evaluated and adopted the most numerous evaluation results.
A: The jet-black feeling of the decoration layer is high, and turbidity is not confirmed.
B: The jet black feeling of the decoration layer was low, and a slight turbidity was felt.
C: The blackness of the decorative layer is very low and turbid.

  From the results in Table 1, the black resin layer formed by the transfer film of each example has a lower reflectance than the black resin layer formed by the transfer film of Comparative Example 1, and is not desired due to the black pigment. It can be seen that reflection is suppressed. Moreover, also in the sensory evaluation by visual observation, the glare caused by light reflection was suppressed, and the black resin layer had a high jet black feeling and a good appearance. On the other hand, the black resin layer formed of the transfer film of Comparative Example 1 had a very low jet black feeling due to undesired glare caused by reflection, a turbidity, and an inferior appearance.

10 Transfer Film 12 Temporary Support 14 Black Resin Layer 16 Protective Release Layer (Protective Film)
18 Touch panel 20 Patterned black resin cured layer (decorative layer)

Claims (10)

  A temporary support, provided on the temporary support, (A) a black pigment, (B) a dye, (C) an alkali-soluble resin, (D) an ethylenically unsaturated group-containing compound, and (E) initiation of photopolymerization And a black resin layer containing an agent.   The transfer film according to claim 1, wherein the (A) black pigment is carbon black.   The transfer film according to claim 2, wherein the carbon black is carbon black whose surface is coated with a resin.   The transfer film according to any one of claims 1 to 3, wherein the (B) dye is a blue dye.   The transfer film according to claim 1, wherein the (B) dye is an anthraquinone dye.   The transfer film according to any one of claims 1 to 5, further comprising a thermoplastic resin layer between the temporary support and the black resin layer.   The transfer film according to claim 6, further comprising an intermediate layer between the black resin layer and the thermoplastic resin layer.   The patterned black resin cured layer formed by the said black resin layer in the transfer film as described in any one of Claims 1-7 on the base material chosen from the group which consists of a glass base material and a resin base material. Decorating material having.   A touch panel comprising the decorative material according to claim 8. A step of transferring the black resin layer of the transfer film according to any one of claims 1 to 7, on a substrate selected from the group consisting of a glass substrate and a resin substrate;
Patterning the transferred black resin layer by a photolithography method to form a patterned black resin layer;
Applying energy to the formed patterned black resin layer to form a patterned black resin cured layer;
The manufacturing method of the decorating material containing.