JP6703104B2 - Transfer film - Google Patents

Description

The present disclosure relates to the transfer fill-time.

An image display device such as a cathode ray tube display device, a plasma display, an electroluminescence display, a fluorescent display, a field emission display and a liquid crystal display device (Liquid Crystal Display; LCD), or a variety of smartphones or tablet terminals equipped with a touch panel. In a display, a decorating material having a decorating layer on a substrate is provided on the surface of the display for the purpose of giving various designs such as hiding the wiring arranged in the main body. For example, on the surface of an image display device, for the purpose of hiding the wiring, a decorative material having a decorative layer which is a black resin cured layer containing a black pigment on its peripheral portion is widely used.
The decorative layer used for applications such as a touch panel may be formed using a transfer film having a photosensitive resin layer. When the decorative layer is formed using a transfer film, for example, the step of transferring the photosensitive resin layer of the transfer film to a substrate, the step of exposing the photosensitive resin layer with a desired pattern, and the step of developing the photosensitive resin layer Process, a process of heat-treating (baking) the photosensitive resin layer to form a tapered shape. By heat-treating the photosensitive resin layer to soften it and to make the pattern into a tapered shape, it is possible to prevent the pattern of the decorative layer from being chipped after a lapse of time, and to improve the hiding property of the wiring, which is the purpose of the decorative layer. be able to.

Although not intended for use as a touch panel or the like as described above, as a composition capable of forming a stable black resin cured layer, for example, at least one of metal particles and particles having a metal, and a high-boiling point solvent having a boiling point of 120° C. or higher. A photosensitive resin composition containing at least one kind and at least one kind of a resin and a precursor thereof and having a content ratio of the high boiling point solvent of 70% or more with respect to the total amount of the solvent has been proposed (for example, Japanese Patent Application Laid-Open Publication No. 2004-242242). (See Japanese Patent Publication No. 2008-256735).

Further, a photosensitive resin composition containing a resin having a glass transition temperature of 70° C. or lower, metal particles, a polymerizable monomer, and a polymerization initiator, and a light-shielding film for a display device using the photosensitive resin composition Has been proposed (see, for example, Japanese Patent Laid-Open No. 2008-249868).

The photosensitive resin composition described in JP-A-2008-256735 and the photosensitive resin composition described in JP-A-2008-249868 are both compositions for forming a black resin cured layer for color resist applications. Therefore, in order to form a hard light-shielding layer such as a black matrix having high strength and excellent durability for a color resist, a baking process at a high temperature of 200° C. or higher is required after pattern formation.
Further, at the high temperature of the photosensitive resin composition described in JP 2008-256735 A and JP 2008-249868 A, the high temperature baking step is performed for the purpose of forming a hard film excellent in light shielding property. No consideration is given to softening the pattern and forming a tapered shape by the baking process.
Further, in applications such as touch panels, for example, a resin base material may be used as the base material, and when forming a decorative layer on the resin base material, the heating temperature is 140° C. in the step of baking to form a tapered shape. It is required to carry out a low temperature baking step of baking at a relatively low temperature of about 150° C. to 150° C., and to soften by the low temperature baking step. In this case, the photosensitive resin compositions described in JP 2008-256735 A and JP 2008-249868 A cannot form a tapered shape by the low temperature baking process, and for example, decoration on a touch panel. It cannot be used for applications such as pattern formation.
On the other hand, in order to be able to form a tapered shape by the low temperature baking process, the photosensitive resin layer before being subjected to the baking process becomes soft to some extent, and the problem that the protective film becomes difficult to peel off may occur. It became clear by the study of the inventors.
In order to enhance the releasability between the protective film and the photosensitive resin layer, it may be possible to perform a releasing treatment on the surface of the protective film which is in contact with the photosensitive resin layer. However, for example, when the protective film is roughened as a release treatment, it may affect the surface of the obtained photosensitive resin layer. This is because the surface of the photosensitive resin layer formed on the surface of the base material at the time of transfer reflects the unevenness of the roughened protective film, and the smoothness decreases, and the unevenness formed is sufficient even after the heat treatment. It is considered that the appearance of the obtained decorative layer deteriorates. Therefore, there has been a demand for a technique capable of achieving both the taper formability of the photosensitive resin layer and the peelability of the protective film.

An object of one embodiment of the present invention is to form a taper shape by a low temperature baking step, preferably a low temperature baking step at a heating temperature of about 140°C to 150°C, and transfer the protective film with good peelability. Ru der to provide a film.

Means for solving the problems include the following embodiments.
<1> A temporary support, a photosensitive resin layer provided on the temporary support and containing a binder, a polymerizable monomer, and a pigment, and a protective film provided in contact with the photosensitive resin layer. The ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.32 to 0.50 on a mass basis, and the surface roughness Rz of the surface of the protective film on the side in contact with the photosensitive resin layer. Of less than 0.12 μm.

<2> The transfer film according to <1>, wherein the protective film is a polyester film.
<3> The transfer film according to <1> or <2>, wherein the pigment is a black pigment.

<4> The transfer film according to any one of <1> to <3>, in which the polymerizable monomer contains a bifunctional polymerizable monomer.
<5> The transfer film according to any one of <1> to <4>, in which the polymerizable monomer contains a polymerizable monomer having a molecular weight of 500 or less.
<6> The transfer film according to any one of <1> to <5>, in which the binder contains a binder having a weight average molecular weight of 5,000 to 10,000.

<7> The transfer film according to any one of <1> to <6>, further including a functional layer between the temporary support and the photosensitive resin layer.
<8> The transfer film according to any one of <1> to <7>, which has a surface roughness Rz of 0.01 μm or more and less than 0.12 μm.
<9> The ratio of the content of the polymerizable monomer to the content of the binder is transferred fill beam according to any one of less than 0.35 or more 0.40 by weight <1> to <8>.

According to one embodiment of the present invention, a taper shape can be formed by a low temperature baking process, preferably a low temperature baking process at a heating temperature of about 140° C. to 150° C., and transfer with good peeling property of a protective film. film Ru is provided.

It is a schematic sectional drawing which shows an example of a structure of the transfer film of one Embodiment of this invention. It is a schematic plan view which shows an example of the touch panel provided with a decoration pattern. It is a pattern sectional view for explaining an angle in an end of a decoration pattern in evaluation of a taper angle of an example.

Hereinafter, the transfer film, the decorative pattern, and the touch panel of the present disclosure will be described in detail.
The description of the constituents described below may be made based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples.

In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
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 plurality of substances corresponding to each component in the composition, unless otherwise specified. ..

In the present specification, the term “process” is included in this term as long as the intended purpose of the process is achieved, not only as an independent process but also when it cannot be clearly distinguished from other processes.
In addition, in the present specification, “(meth)acrylic acid” is a concept that includes both acrylic acid and methacrylic acid, and “(meth)acrylate” is a concept that includes both acrylate and methacrylate, The "(meth)acryloyl group" is a concept including both an acryloyl group and a methacryloyl group.
In the present specification, the “total solid content” means the total mass of the non-volatile components excluding the solvent contained in the composition.

<Transfer film>
The transfer film of the present disclosure, a temporary support, a photosensitive resin layer provided on the temporary support, containing a binder, a polymerizable monomer, and a pigment, a protective film provided in contact with the photosensitive resin layer, And the ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.32 to 0.50 on a mass basis, and the surface of the protective film on the side in contact with the photosensitive resin layer. Is a transfer film having a surface roughness Rz of less than 0.12 μm.

The details of the mechanism of action of the transfer film according to one embodiment of the present invention are unknown, but it is presumed as follows.
The photosensitive resin layer included in the transfer film of the present disclosure includes a binder and a polymerizable monomer, and the ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.32 or more on a mass basis. Therefore, the thermal sag property when baking the patterned photosensitive resin layer formed after the developing step of the photosensitive resin layer formed by the transfer film becomes good, and the low temperature baking step, preferably the heating temperature The patterned hardened material formed by the low temperature baking process of about 140° C. to 150° C. easily forms a tapered shape. That is, even if the pattern-shaped cured product has an inverse taper shape or a rectangular shape, so-called heat sagging, which easily deforms the cured product into a tapered shape by a low temperature baking process, easily occurs.
Further, the ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.50 or less on a mass basis, so that the photosensitive resin layer exists adjacent to the photosensitive resin layer. Good peelability from the protective film.
By setting the content ratio of the binder and the polymerizable monomer in the photosensitive resin layer in the transfer film of the present disclosure to the above-mentioned appropriate range, the balance between the taper formability due to low temperature baking and the peelability of the protective film becomes good. Further, even when using a protective film excellent in smoothness such that the surface roughness Rz of the surface of the protective film in contact with the photosensitive resin layer is less than 0.12 μm, the photosensitive resin layer can be easily removed from the protective film. It can be peeled off.
Furthermore, the photosensitive resin layer surface formed by peeling has excellent smoothness by reflecting the smooth surface of the protective film, and the decorative pattern formed by the transfer film of the present disclosure has an additional effect of excellent appearance. It is thought to play.

[Photosensitive resin layer]
The photosensitive resin layer in the transfer film of the present disclosure contains a binder, a polymerizable monomer, and a pigment. Hereinafter, each component contained in the photosensitive resin layer will be described.

〔binder〕
The photosensitive resin layer contains a binder.
The binder is preferably a resin that can be at least partially dissolved by contact with an alkaline solvent, and can be used by appropriately selecting from known resins.
The binder can be appropriately selected and used from the resins described in paragraphs [0025] of JP2011-95716A and paragraphs [0033] to [0052] of JP2010-237589A, for example.

From the viewpoint of improving the pattern formability of the photosensitive resin layer, it is preferable to contain a binder having a carboxy group as the binder. By containing the binder having a carboxy group, the linearity of the end portion of the formed pattern becomes better, and so-called edge roughness tends to be improved.

Specific examples of the binder include a random copolymer of benzyl (meth)acrylate/(meth)acrylic acid, a random copolymer of styrene/(meth)acrylic acid, cyclohexyl (meth)acrylate/(meth)acrylic acid. /Methyl (meth)acrylate copolymer, cyclohexyl (meth)acrylate/methyl (meth)acrylate/(meth)acrylic acid copolymer glycidyl (meth)acrylate adduct, benzyl (meth)acrylate /(meth) Glycidyl (meth)acrylate adduct of acrylic acid copolymer, allyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/hydroxyethyl (meth)acrylate Examples thereof include copolymers.
Among them, a benzyl (meth)acrylate/(meth)acrylic acid random copolymer is preferable from the viewpoint of developability.

A commercially available product may be used as the binder. Hereinafter, examples of commercially available products that can be used in one embodiment of the present invention will be given, and the weight average molecular weight (Mw) will be described together. Examples of commercially available products include Acrybase (registered trademark) FFS-6058 (Mw: 5000) and FF187 (Mw: 30000) manufactured by Fujikura Kasei Co., Ltd., and ACRYT (registered trademark) 8KB-001 (Mw: manufactured by Taisei Fine Chemical Co., Ltd.). 8KB series such as 13000).

As the binder in one embodiment of the present invention, a binder having a weight average molecular weight (Mw) of 4,000 to 30,000 can be used. The Mw of the binder is preferably in the range of 4000 to 25000, and more preferably in the range of 5000 to 10000. When the Mw of the binder used in one embodiment of the present invention is 4000 or more (preferably 5000 or more), the linearity of the formed pattern becomes good and the tack of the formed pattern is suppressed, so the protective film. The peelability of is further improved. When the Mw of the binder is 30,000 or less (preferably 10,000 or less), the heat dripping property is improved, the taper formability by low temperature baking is further improved, and the generation of development residues during pattern formation is suppressed. .. From the above points, the photosensitive resin layer in one embodiment of the present invention more preferably contains a binder having an Mw in the range of 5,000 to 10,000, from the viewpoint that the taper formability is further improved.
In addition, from the viewpoint that the peelability of the protective film is further improved, the photosensitive resin layer preferably has a small content of the binder having an Mw of 21,000 or more, and the Mw is 21,000 based on the total solid content of the photosensitive resin layer. The content of the above binder is preferably 12% by mass or less, more preferably 9% by mass or less, and further preferably 0% by mass (that is, not containing).

The weight average molecular weight of the binder can be measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve is "standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A". -2500", "A-1000", and "n-propylbenzene".
<Condition>
-GPC: HLC (registered trademark)-8020GPC (manufactured by Tosoh Corporation)
-Column: TSKgel (registered trademark), Super Multipore HZ-H (Tosoh Corporation, 4.6 mm ID x 15 cm) three-eluent: THF (tetrahydrofuran)
・Sample concentration: 0.45% by mass
・Flow rate: 0.35 ml/min
・Sample injection volume: 10 μl
・Measuring temperature: 40℃
・Detector: Differential refractometer (RI)

The acid value of the binder is preferably 50 mgKOH/g or more from the viewpoint of improving the alkali solubility of the unexposed portion during pattern formation and improving the linearity of the pattern. The acid value of the binder is more preferably 70 mgKOH/g or more, further preferably 100 mgKOH/g or more.

The acid value of the binder can be measured, for example, by the following method.
(1) Propylene glycol monomethyl ether acetate is added to a resin solution (y(g)) having a solid content concentration (x(%)) to dilute it to prepare a sample solution having a solid content concentration of 1% by mass to 10% by mass. ..
(2) Using the potentiometer (manufactured by Hiranuma Sangyo Co., Ltd., device name "Hiranuma automatic titrator COM-550"), a 0.1 mol/L potassium hydroxide/ethanol solution (titer a ) And measure the amount of potassium hydroxide/ethanol solution (b (mL)) required by the end of the titration.
(3) Further, titration is performed on water in the same manner as in (2), and the amount of potassium hydroxide/ethanol solution (c (mL)) required by the end point of titration is measured.
(4) The solid content acid value of the resin is determined by calculating with the following formula.
Solid acid value (mgKOH/g)={5.611×(bc)×a}/{(x/100)×y}

The content of the binder in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass based on the total solids contained in the photosensitive resin layer. Mass% is more preferable.

[Polymerizable monomer]
The photosensitive resin layer contains at least one kind of polymerizable monomer. When the photosensitive resin layer contains the polymerizable monomer, the linearity of the formed pattern becomes good. The polymerizable monomer is a monomer having at least one polymerizable group in the molecule, and the polymerizable group is not particularly limited.
Examples of the polymerizable group include an ethylenically unsaturated group and an epoxy group. An ethylenically unsaturated group is preferable, and a (meth)acryloyl group is more preferable.

The polymerizable monomer in the photosensitive resin layer preferably contains a so-called polyfunctional polymerizable monomer having two or more polymerizable groups, and more preferably contains a bifunctional polymerizable monomer.
By using a polyfunctional polymerizable monomer, it is possible to suppress the generation of a development residue when developing the photosensitive resin composition.
By using a bifunctional polymerizable monomer, generation of a development residue can be suppressed even in development in a weak alkaline developing solution (for example, an aqueous sodium carbonate solution).

Examples of the polymerizable monomer include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and phenoxyethyl(meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol. Di(meth)acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, di Pentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, tri(acryloyloxyethyl) ) Cyanurate, glycerin tri(meth)acrylate; polyfunctional (meth)acrylates such as polymerizable monomers obtained by adding propylene oxide to ethylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin, and (meth)acrylated. it can.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183 and JP-B-49-43191. Polyester acrylates described in JP-B-52-30490 and JP-B-52-30490; and polyfunctional (meth)acrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth)acrylic acid.
Above all, it is preferable to include a polyfunctional acrylate as the polymerizable monomer.

A commercially available commercial product may be used as the polymerizable monomer. Examples of commercially available products include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 304), tricyclodecane dimenanol dimethacrylate (DCP, Shin-Nakamura chemical ( Co., Ltd., bifunctional, molecular weight 332), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 268), 1,6-hexanediol diacrylate (A -HD-N, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 226), 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (A-BPEF, Shin-Nakamura Chemical Co., Ltd.) Bifunctional, molecular weight 546), urethane acrylate (UA-160TM, Shin Nakamura Chemical Co., Ltd., bifunctional, molecular weight 1600), 1,6-hexanediol diacrylate (V#230, Osaka Organic Chemistry, bifunctional, Molecular weight 22), trimethylolpropane triacrylate A-TMPT, Shin-Nakamura Chemical Co., Ltd., trifunctional, molecular weight 296), trimethylolpropane ethylene oxide (EO) modified (n≈1) triacrylate (M-350, Toago). Synthesis, trifunctional), pentaerythritol tetraacrylate (A-TMMT, Shin Nakamura Chemical Co., Ltd., tetrafunctional, molecular weight 352), pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (UA-306H, Kyoeisha chemistry, 6 functional) ), pentaerythritol triacrylate toluene diisocyanate urethane prepolymer (UA306T, Kyoeisha chemistry, 6 functional), dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku, 6 functional, molecular weight 579), urethane (meth)acrylate (UA-32P). , Shin-Nakamura Chemical Co., Ltd., 9-functional), urethane (meth)acrylate (8UX-015A, Taisei Fine Chemical Co., Ltd., 15-functional), and the like.

The polymerizable monomer preferably contains a polymerizable monomer having a molecular weight of 500 or less.
When the photosensitive resin layer in one embodiment of the present invention contains a polymerizable monomer having a molecular weight of 500 or less, the formability of a cured product in a tapered shape during low temperature baking is further improved.
In addition, the photosensitive resin layer in one embodiment of the present invention may include a polymerizable monomer having a molecular weight of more than 500. However, from the viewpoint that the taper shape formability becomes better, the content of the polymerizable monomer having a molecular weight of 500 or less is preferably 50% by mass or more, and 60% by weight with respect to all the polymerizable monomers contained in the photosensitive resin layer. It is more preferably at least mass%.

The molecular weight of the polymerizable monomer is determined by mass spectrometry (for example, liquid chromatography (LC/MS) analysis, gas chromatography (GC/MS) analysis, fast atom collision chromatography (FAB/MS analysis), etc.). , Can be obtained from the molecular formula.

The content of the polymerizable monomer contained in the photosensitive resin layer is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photosensitive resin layer, and 10% by mass. % To 30% by mass is more preferable.

The polymerizable monomers may be used alone or in combination of two or more. Above all, it is preferable to use two or more polymerizable monomers in combination, from the viewpoint of further improving the sensitivity in pattern formation.
Further, from the viewpoint of suppressing the residue in carbonic acid development and film strength, it is preferable that the photosensitive resin layer contains a bifunctional polymerizable monomer, and a bifunctional polymerizable monomer and a non-bifunctional polymerizable monomer are contained. It is more preferable to include.

When a bifunctional polymerizable monomer and a non-bifunctional polymerizable monomer are used in combination, the bifunctional polymerizability with respect to the total mass of the polymerizable monomer (the total amount of the bifunctional polymerizable monomer and the non-bifunctional polymerizable monomer) The mass ratio of the monomers (bifunctional polymerizable monomer/total polymerizable monomer mass) is preferably 50% by mass or more.
When the (bifunctional polymerizable monomer/polymerizable monomer total mass) is 50% by mass or more, it is advantageous from the viewpoints of suppressing a development residue by a weak alkaline developing solution (for example, an aqueous solution of sodium carbonate) and film strength.

(Contents of binder and polymerizable monomer)
The content ratio of the above-mentioned polymerizable monomer to the content of the above-mentioned binder in the photosensitive resin layer (hereinafter, may be referred to as M/B ratio) is in the range of 0.32 to 0.50 on a mass basis. And 0.32 to 0.49 is preferable, 0.35 to 0.40 is more preferable, and 0.35 or more and less than 0.40 is further preferable.
As described above, when the M/B ratio is 0.32 or more, the thermal sag of the patterned photosensitive resin layer is good, the tapered shape of the pattern is easily formed by the low temperature baking process, and further the development is performed. Generation of residues is further suppressed.
When the M/B ratio is 0.50 or less, the releasability between the photosensitive resin layer and the protective film existing adjacent to the photosensitive resin layer is good, and the linearity of the formed pattern is more excellent. It will be good.

[Pigment]
The photosensitive resin layer in the transfer film of the present disclosure contains at least one kind of pigment.
The pigment is not particularly limited and can be appropriately selected according to the purpose.
Examples of the pigment include known organic pigments and inorganic pigments. In addition, as the pigment, a commercially available pigment dispersion (for example, water as a dispersion medium, a liquid compound, a pigment dispersion in which a pigment is dispersed in a pigment-insoluble resin or the like), or a surface-treated pigment (for example, a resin or a pigment derivative) is used. It is also possible to use a surface-treated pigment whose surface is treated with a pigment or the like).
Examples of organic pigments and inorganic pigments include black pigments, white pigments, blue pigments, cyan pigments, green pigments, orange pigments, purple pigments, brown pigments, yellow pigments, red pigments, and magenta pigments.
Among them, black pigments, white pigments, blue pigments and the like are preferable, and black pigments are more preferable, from the viewpoint that the decorative layer has good light-shielding properties.

(Black pigment)
The black pigment is not particularly limited as long as it can exhibit the required light-shielding property in the formed photosensitive resin layer.
As the black pigment, a known black pigment, for example, a black pigment selected from organic pigments and inorganic pigments can be preferably 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 photosensitive resin layer is good, examples of the black pigment include carbon black, titanium carbon, iron oxide, titanium oxide pigments such as titanium black, graphite, and aniline black. Of these, carbon black is preferable. The CI number of aniline black is C.I. I. Pigment Black 1 and the CI number of carbon black is C.I. I. Pigment Black 7.
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 is preferably a carbon black whose surface is coated with a resin (hereinafter, also referred to as resin-coated carbon black) from the viewpoint that the uniform dispersibility of the carbon black in the photosensitive resin layer becomes better. The carbon black may be coated with the resin as long as at least a part of the surface of the 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 paragraphs [0036] to [0042] of Japanese Patent No. 5320652. It is also available as a commercial product, and as a commercial product of resin-coated carbon black. For example, SF Black GB4051 manufactured by Sanyo Pigment Co., Ltd. may be mentioned.

From the viewpoint of dispersion stability, the particle size 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 size. The "particle size" referred to here is the diameter when the electron micrograph image of the particle is a circle of the same area, and the "number average particle size" is the particle size for any 100 particles. The average value of this particle size is obtained.
The number average particle diameter of the black pigment contained in the photosensitive resin composition is 300,000 times the photograph of the photosensitive resin layer containing the black pigment with a transmission electron microscope (JEOL). The particle size of any 100 particles included in the viewing angle can be measured and calculated as an average value of the measured values.

Pigment in the photosensitive resin layer (if the photosensitive resin layer contains only a black pigment or a pigment other than black, the content of a black pigment or a pigment other than black; if it contains a black pigment and a pigment other than black, the sum of both. The content of (mass) is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and more preferably 30% by mass to the total solid content of the photosensitive resin layer. It is more preferably 55% by mass, further preferably 20% by mass to 45% by mass.
When the content of the black pigment is 10% by mass or more, the optical density of the photosensitive resin 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 becomes good.

The black pigment is preferably used as a dispersion liquid in the photosensitive resin composition. The dispersion liquid can be prepared by adding a composition obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent or vehicle described later and dispersing the composition. The vehicle is a part of a medium in which the pigment is dispersed when the photosensitive resin composition is in a liquid state, and is a component that is liquid and forms a photosensitive resin layer by binding with a black pigment (for example, a binder). ) And a medium such as an organic solvent for dissolving and diluting the same.
The disperser used when dispersing the black pigment is not particularly limited and includes, for example, Kunizo Asakura, "Encyclopedia of Pigments", First Edition, Asakura Shoten, 2000, kneader described on page 438, Known dispersing machines such as roll mills, attritors, super mills, dissolvers, homomixers, and sand mills can be used. Further, the black pigment, which is a dispersoid, may be finely pulverized by using frictional force by mechanical milling described on page 310 of the same document.
The pigment dispersant may be selected according to the pigment and solvent contained in the photosensitive resin composition, and for example, a commercially available dispersant can be used.

(Pigments other than black)
Organic pigments other than black include, for example, pigments described in JP-A-2008-224982, paragraph numbers [0030] to [0044], which exhibit a hue other than black, and C.I. I. Pigment Green 58, C.I. I. Pigment Blue 79 includes a pigment in which the chlorine (Cl) substituent is changed to a hydroxyl group (OH), and among these pigments, the following pigments can be preferably used. However, the pigment that can be contained in the photosensitive resin layer according to the embodiment of the present invention is not limited to the pigments described below.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185.
C. I. Pigment Orange 36, 38, 62, 64
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255.
C. I. Pigment Violet 19, 23, 29, 32
C. I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66.
C. I. Pigment Green 7, 36, 37, 58

[Other ingredients]
The photosensitive resin layer in one embodiment of the present invention may contain components other than the binder, the polymerizable monomer and the pigment described above.
Other components contained in the photosensitive resin layer include a polymerization initiator, a polymerization inhibitor, a thiol compound, a dye, a solvent, a surfactant, a silane coupling agent, a UV absorber, an antioxidant, a sensitizer, an amine. A compound etc. are mentioned.

(Polymerization initiator)
The photosensitive resin layer may contain at least one kind of polymerization initiator. The content of the polymerization initiator in the photosensitive resin layer is preferably more than 0 mass% and less than 9 mass% with respect to the total solid content contained in the photosensitive resin layer.
When the photosensitive resin layer contains a polymerization initiator, the pattern formability by exposure and development is further improved. When the content of the polymerization initiator is less than 9% by mass in the case of containing the polymerization initiator, thermal sagging easily occurs in the low temperature baking, and the formability of the taper shape of the formed pattern is further improved.

From the same viewpoint as above, the content of the polymerization initiator in the photosensitive resin layer is preferably more than 0% by mass and less than 10% by mass, more preferably 1% by mass or more and 7% by mass or less, based on the total solid content. It is more preferably 2% by mass or more and 6% by mass or less.

Examples of the polymerization initiator include polymerization initiators described in paragraphs [0031] to [0042] of JP2011-95716A, and oxime-based compounds described in paragraphs [0064] to [0081] of JP2015-014783A. A polymerization initiator may be used.
A commercially available commercial product can be used as the polymerization initiator. 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 , 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, BASF). Made), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF), oxime ester-based trade name: Lunar 6 (made by DKSH Japan Co., Ltd.), 2, 4 -Diethylthioxanthone ("Kayakyu DETX-S" manufactured by Nippon Kayaku Co., Ltd.), fluorene oxime-based polymerization initiators DFI-091, DFI-020 (both manufactured by Daito Chemix Co., Ltd.) and the like are preferable.

Among them, it is preferable to use an initiator other than a halogen-containing polymerization initiator such as a trichloromethyltriazine-based compound used for a color filter material or the like from the viewpoint of increasing sensitivity, and α-aminoalkylphenone-based compound, α-hydroxyalkyl Oxime-based polymerization initiators such as phenone-based compounds and oxime ester-based compounds are more preferable, and it is particularly preferable to include the above-mentioned oxime-based polymerization initiators from the viewpoint of further improving the sensitivity during pattern formation.

The content of the polymerization initiator in the photosensitive resin layer is such that the mass ratio (polymerization initiator/polymerizable monomer) to the polymerizable monomer described above is 0.05 to 0.50. The taper angle of the patterned cured product formed by the method is closer to a rectangle, and the precipitation of the polymerization initiator from the photosensitive resin layer is preferably suppressed from the viewpoint of being more effectively, 0.07 to 0.30. Is more preferable.

(Polymerization inhibitor)
The photosensitive resin layer may include at least one kind of polymerization inhibitor.
When the photosensitive resin layer contains the polymerization inhibitor, generation of development residues is further suppressed.
As the polymerization inhibitor, for example, a thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph [0018] of Japanese Patent No. 4502784 can be used. Among them, phenothiazine, phenoxydine, and methoxyphenol can be preferably used.

When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.05% by mass with respect to the total solid content of the photosensitive resin layer. -1 mass% is more preferable, and 0.1 mass%-0.8 mass% is still more preferable.

(Contents of polymerization initiator and polymerization inhibitor)
When the photosensitive resin layer in one embodiment of the present invention contains a polymerization initiator and a polymerization inhibitor, the content ratio of the polymerization inhibitor to the polymerization initiator (polymerization inhibitor/polymerization initiator ratio) is based on the mass basis. And is preferably 0 to 0.1, and more preferably 0.02 to 0.05.
When the polymerization inhibitor/polymerization initiator ratio is 0.02 or more, generation of development residues is further suppressed. On the other hand, when the polymerization inhibitor/polymerization initiator ratio is 0.05 or less, the linearity of the formed pattern becomes better.

The preferable range of the content of the polymerization initiator in the photosensitive resin layer varies depending on the presence or absence of the polymerization inhibitor.
As the combination of the content of the polymerization initiator and the content of the polymerization inhibitor in the photosensitive resin composition, when the polymerization initiator is 1% by mass to 3% by mass, the polymerization inhibitor is 0.06% by mass to 0. 15 mass% is preferable, when the polymerization initiator is 3 mass% to 6 mass%, the polymerization inhibitor is more preferably 0.15 mass% to 0.3 mass%, and the polymerization initiator is 6 mass% to 9 mass%. In this case, the content of the polymerization inhibitor is more preferably 0.3% by mass to 0.45% by mass.

(Thiol compound)
The photosensitive resin layer can contain a thiol compound. By containing the thiol compound, the sensitivity during pattern formation can be further increased.
The thiol compound may be a compound having a thiol group (also referred to as a mercapto group) having a monofunctional function or a bifunctional or higher functional compound.
When the photosensitive resin layer contains a thiol compound, the thiol compound is preferably a bifunctional or higher functional compound from the viewpoint of further increasing the sensitivity, more preferably a bifunctional to tetrafunctional compound, and a bifunctional to trifunctional compound. Particularly preferred is a compound.
Examples of the monofunctional thiol compound that can be contained in the photosensitive resin layer include N-phenylmercaptobenzimidazole.
Examples of the bifunctional or higher functional thiol compound that can be contained in the photosensitive 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 Showa Denko KK), pentaerythritol tetrakis(3-mercaptobutyrate) ( Karenz MT PE1 (Showa Denko), pentaerythritol tetrakis (3-mercaptopropionate) (“PEMP” manufactured by Sakai Chemical Industry Co., Ltd.), and the like.

(dye)
The photosensitive resin layer can contain a dye as a coloring component in addition to the above-mentioned pigment.
The dye that can be used in the photosensitive resin layer is not particularly limited. Known dyes, for example, known dyes described in documents such as "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1970) or commercially available dyes may be appropriately selected and used. You can
Specific examples of the dye include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolates. Examples include dyes such as complexes.

When the photosensitive resin layer contains a dye, the content of the dye is 1 part by mass with respect to 100 parts by mass of the above-mentioned pigment from the viewpoint that the cured product on the pattern to be formed can exhibit antireflection ability. It is preferably from 40 parts by mass to 40 parts by mass, more preferably from 1 part by mass to 20 parts by mass. When the content of the dye is within the above range, the antireflection effect in the formed photosensitive resin layer, that is, the effect of suppressing glare by visual observation becomes better.

(Additive)
The photosensitive resin layer may contain a known additive such as a surfactant. Examples of the additive include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of Japanese Patent Laid-Open No. 2009-237362, and further, Japanese Patent Laid-Open No. 2000-310706. Other additives described in paragraphs [0058] to [0071] of the above.
As the surfactant, a fluorine-containing surfactant, for example, Megafac (registered trademark) F-784-F, F-780 manufactured by DIC Co., Ltd., etc., from the viewpoint of improving film properties at the time of coating and forming the photosensitive resin layer. Is preferably used.

(solvent)
The photosensitive resin layer can include a solvent.
The photosensitive resin layer, when produced by coating using the composition for forming a photosensitive resin layer, the solvent that may be contained in the photosensitive resin layer is not particularly limited, particularly commonly used solvents It can be used without limitation.
Specific examples of the solvent include esters, ethers, ketones, aromatic hydrocarbons and the like.
Further, similar to Solvent described in paragraphs [0054] and [0055] of US2005/282073A1 specification, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PEGMEA), cyclohexanone, cyclo Hexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate and the like can be suitably used for the photosensitive resin layer.
Among the above-mentioned 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 the photosensitive resin layer contains a solvent, the solvent may be used alone or in combination of two or more.
As the solvent, an organic solvent having a boiling point of 180° C. to 250° C. (high-boiling point solvent) can be used as necessary.

The film thickness of the photosensitive resin layer in the transfer film of the present disclosure is preferably 0.5 μm to 10.0 μm from the viewpoint of designability when used as a decorating material, and 1.0 μm to 8.0 μm. It is more preferable that the thickness is 1.5 μm to 5.0 μm.

[Layer structure of transfer film]
The transfer film of the present disclosure has a temporary support, the above-mentioned photosensitive resin layer, and a protective film. The transfer film has a protective film on the side of the photosensitive resin layer opposite to the side on which the temporary support is arranged. In the present disclosure, the protective film is provided in contact with the photosensitive resin layer.
The transfer film may have a layer other than the temporary support, the photosensitive resin layer, and the protective film. Examples of the other layer include a functional layer and a thermoplastic resin layer.
The transfer film can be used for forming a decorative pattern on at least one surface of an image display device such as a touch panel, and has a photosensitive resin layer capable of forming a tapered shape in low temperature baking.
The decorative pattern, which is a patterned hardened layer formed of the transfer film, has a tapered shape and is excellent in the linearity of the pattern.

FIG. 1 is a schematic sectional view showing an example of the structure of a transfer film according to an embodiment of the present invention.
The transfer film 10 shown in FIG. 1 has a temporary support 12, a photosensitive resin layer 14, and a protective film 16 in this order. FIG. 1 shows an embodiment in which the temporary support 12, the photosensitive resin layer 14, and the protective film 16 are laminated adjacent to each other, but the present invention 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 photosensitive resin layer 14 and the photosensitive resin layer 14, and a further thermoplastic resin layer (not shown) may be provided between the photosensitive resin layer 14 and the thermoplastic resin layer which is optionally provided. An embodiment having a functional layer (not shown) can be taken.
The transfer film 10 can be used as a transfer film for forming a decorative pattern, that is, a patterned hardened layer on one surface of an image display device such as a touch panel.
A method of manufacturing the decorative pattern by transferring the photosensitive resin layer 14 onto the substrate using the transfer film 10 of the present disclosure will be described later.

[Temporary support]
The transfer film of the present disclosure 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 include a cycloolefin copolymer film, a polyethylene terephthalate (hereinafter sometimes referred to as “PET”) film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, and the like. , PET films are 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 and the like.
When the temporary support is transparent, the protective film may be peeled off and transferred, and then the photosensitive resin layer may be pattern-exposed through the temporary support to form a decorative pattern.
Conductivity can be imparted to the temporary support by the method described in JP-A-2005-221726, and the temporary support imparted with conductivity is also suitably used for the transfer film of the present disclosure.

[Protective film]
The transfer film has a protective film on the surface of the above-mentioned photosensitive resin layer. By including the protective film, it is possible to protect the transfer film from being contaminated or damaged by impurities such as dust during storage.
The surface roughness Rz of the surface of the protective film on the side in contact with the above-mentioned photosensitive resin layer is less than 0.12 μm, preferably less than 0.1 μm, and more preferably less than 0.08 μm. .. The lower limit of the surface roughness Rz is not particularly limited and may be 0.01 μm or more.

The surface roughness Rz of the protective film can be measured by the method described below.
First, a surface profile of an optical film is obtained using a three-dimensional optical profiler (New View7300, manufactured by Zygo) under the following conditions. The measurement analysis software used is MicroProbe Application of MetroPro ver 8.3.2. Next, the Surface Map screen is displayed by the above analysis software (MetroPro ver 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen. The difference between the upper limit and the lower limit of the distribution height at the peak position is read from the obtained histogram data, and is set as Rz.
(Measurement condition)
Objective lens: 50 times Zoom: 0.5 times Measurement area: 1.00 mm x 1.00 mm
(Analysis conditions)
Removed: plane
Filter: off
FilterType: average
Remove spikes: on
Spike Height (xRMS): 7.5

As the protective film, one that can be easily peeled from the photosensitive resin layer can be used, and a material that is the same as or similar to the material of the temporary support can be suitably selected. Specifically, for example, the protective film described in paragraphs [0083] to [0087] and [0093] of JP 2006-259138 A can be appropriately used.
The protective film is preferably a flexible film.
Examples of the protective film that can be used as the transfer film include a cycloolefin copolymer film, a polyolefin film (for example, polypropylene film), a polyester film (for example, polyethylene terephthalate (hereinafter sometimes referred to as “PET”) film, and a polyethylene film. Examples thereof include a phthalate (hereinafter sometimes referred to as “PEN”) film), a cellulose triacetate film, a polystyrene film, a polycarbonate film, and the like.
Among them, a polyolefin film or a polyester film is preferable, and a PET film is more preferable, from the viewpoint of handling property and easy formation of a protective film having a smooth surface.

When forming the protective film, polyester such as PET has excellent surface smoothness when formed into a film, and therefore, the above-mentioned surface can be formed by an ordinary film forming method, for example, melt extrusion film forming using a die. A film can be obtained that is within the range of roughness.
Further, a commercially available film suitable for the above surface roughness can be applied as the protective film.

The transfer film has the above-mentioned photosensitive resin layer, and since the surface roughness of the protective film is within the range described above, the taper formability of the decorative pattern by the photosensitive resin layer and the protective film The releasability from the photosensitive resin layer is well balanced and good.

[Other layers]
The transfer film 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, a functional layer may be further provided between the above-mentioned photosensitive resin layer and an optional thermoplastic resin layer, or between the temporary support and the above-mentioned photosensitive resin layer.
Examples of the functional layer include the oxygen barrier film having an oxygen barrier function described in paragraph No. [0027] of Japanese Patent No. 4502784.

The transfer film of the present disclosure described above can be produced according to the method for producing a curable transfer material described in paragraphs [0094] to [0098] of JP 2006-259138 A.
The oxygen barrier film is preferably a film that uses a resin that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution, and the resin used to form the oxygen barrier film is appropriately selected from known resins. be able to. Among them, a combination of polyvinyl alcohol and polyvinylpyrrolidone is preferable.
The dry thickness of the functional layer is generally 0.2 μm to 5 μm, preferably 0.5 μm to 3 μm, more preferably 1 μm to 2.5 μm.

[Thermoplastic resin layer]
The transfer film may further have a thermoplastic resin layer described in paragraph [0026] of Japanese Patent No. 4502784 between the temporary support and the photosensitive resin layer.
As a component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable.
When the transfer film has the thermoplastic resin layer, cushioning properties can be imparted to the transfer film, and the transfer property can be improved regardless of the case where the transfer surface has irregularities.
The dry thickness of the thermoplastic resin layer is generally 2 μm to 30 μm, preferably 5 μm to 20 μm, and particularly preferably 7 μm to 16 μm.

(Method of manufacturing transfer film)
The transfer film can be produced according to the method for producing a curable transfer material described in paragraphs [0094] to [0098] of JP-A 2006-259138.
That is, the method for producing a transfer film includes a step of forming a photosensitive resin layer on a temporary support and a step of providing a protective film on the surface of the photosensitive resin layer.
Furthermore, before forming the above-mentioned photosensitive resin layer on the temporary support, at least one of a step of forming a thermoplastic resin layer and a step of forming a functional layer may be included.

When the transfer film has a thermoplastic resin layer, the method for producing the transfer film comprises a step of forming a functional layer between the thermoplastic resin layer and the photosensitive resin layer after the step of forming the thermoplastic resin layer described above. It is preferable to include.
In the case of forming a transfer film having a functional layer, a solution (thermoplastic resin layer coating solution) in which a thermoplastic organic polymer and an additive optionally used in combination are dissolved is formed on a temporary support. After coating and drying to form a thermoplastic resin layer, a functional layer coating liquid 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 functional layer is laminated by drying, and the photosensitive resin composition prepared by using a solvent that does not dissolve the functional layer is further applied onto the laminated functional layer and dried to form the photosensitive resin layer. It can be preferably prepared by providing a protective film on the surface of the formed photosensitive resin layer.
The components contained in the photosensitive resin layer are as described above.

<Decorative pattern>
The decorative pattern that is one embodiment of the present invention is a patterned cured product of the photosensitive resin layer in the transfer film of the present disclosure described above. The decorative pattern of the present disclosure can be applied as a decorative pattern included in a touch panel or the like.
The decorative pattern is arranged on the surface of a base material selected from the group consisting of a glass base material and a resin base material, and is a pattern formed by patterning a photosensitive resin layer transferred by the transfer film of the present disclosure described above. The patterned cured layer, which is a cured product of a photosensitive resin, corresponds to the decorative pattern according to one embodiment of the present invention.

The decorative pattern produced using the transfer film of the present disclosure is preferably produced by the following decorative pattern producing method.

<Method of manufacturing decorative pattern>
The decorative pattern is manufactured by a step of transferring the photosensitive resin layer of the transfer film of the present disclosure described above onto a base material selected from the group consisting of a glass base material and a resin base material, and the transferred photosensitive resin. Patterning the layer by a photography method, a step of forming a patterned photosensitive resin layer, a step of applying energy to the formed patterned photosensitive resin layer to form a patterned cured layer, Can be suitably performed by a method including.

[Base material]
As the base material, it is preferable to use a material having high optical transparency without optical distortion.
From such a viewpoint, a glass substrate or a resin substrate, which is a highly transparent substrate, is preferable.
Above all, a resin base material is preferable from the viewpoint of being lightweight and less likely to be damaged. 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 displayed image.
The base material may have a single-layer structure or a laminated structure of two or more layers. When the base material has a laminated structure of two or more layers, the refractive index means the refractive index of all the base material layers. The refractive index is a value measured by ellipsometry at a wavelength of 550 nm.
The material forming the base material is not particularly limited as long as it satisfies such a range of refractive index.
The thickness of the substrate means the total thickness of all layers when it has a laminated structure of two or more layers.

An exposure step of transferring the photosensitive resin layer in the above-mentioned transfer film to the surface of the base material and performing pattern exposure, and a developing step of developing the unexposed portion are performed.
As an example of the exposure step, the development step, and other steps of the photosensitive resin layer transferred onto the substrate, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 can be used. It can be preferably used also in one embodiment.

The exposure step is a step of exposing the photosensitive resin layer transferred onto the base material.
Specifically, a mask on which a predetermined pattern is formed is arranged above the photosensitive resin layer transferred onto the substrate, that is, between the photosensitive resin layer and the exposure light source, and then the mask and the temporary support are provided. There is a method of exposing the photosensitive resin layer from above the mask through the body.
The exposure light source can be appropriately selected and used as long as it can irradiate light in a wavelength range capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specific examples include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp. The exposure dose is usually about 5 J/cm ^{2 to} 200 mJ/cm ² , preferably about 10 J/cm ^{2 to} 100 mJ/cm ² .

The pattern exposure may be performed after peeling the temporary support, or may be performed before peeling the temporary support, and then the temporary support may be peeled. The pattern exposure may be exposure through a patterned mask or scanning exposure (digital exposure) using a laser or the like.
Through the steps described above, a decorative pattern that is a patterned hardened layer is formed on the base material.
FIG. 2 is a schematic plan view showing an example of the touch panel 18 including the patterned hardening layer (decorative pattern) 20. Since the touch panel 18 includes the decorative pattern 20 having the shape shown in FIG. 2, the wiring arranged on the main body of the touch panel 18 can be hidden.

The developing step is a step of developing the exposed photosensitive resin layer.
In one embodiment of the present invention, the development is a development process in a narrow sense, in which the unexposed portion of the photosensitive resin layer that has been subjected to pattern exposure is developed and removed by a developing solution to form a patterned cured product.
Development can be performed using a developing solution. The developing solution is not particularly limited, and known developing solutions such as the developing solution described in JP-A-5-72724 can be used. The developer is preferably a developer capable of dissolving the unexposed photosensitive resin layer. For example, a compound having pKa=7 to 13, for example, a compound having pKa=7 to 13 (eg, sodium carbonate, potassium hydroxide, etc.) Is preferable in the concentration of 0.05 mol/L to 5 mol/L. More specifically, an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide and the like can be mentioned. As the developer, an aqueous sodium carbonate solution is preferable from the viewpoint of buffering property.

A small amount of an organic solvent miscible with water may be added to the developer. Examples of the organic solvent 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, 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 further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

The developing method may be any of paddle developing, shower developing, shower developing+spin developing, dip developing, and the like. Here, shower development will be described. By spraying a developing solution onto the exposed photosensitive resin layer by a shower to remove the uncured portion, a patterned cured product can be formed. Further, after development, it is preferable to remove a 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.

[Post-processing: Effect promotion processing]
The method for producing a decorative pattern may include a post-treatment step of applying energy to the formed patterned cured product after the developing step to further accelerate the curing.
By applying energy in the post-treatment step, the cross-linking density of the patterned cured product is improved, and the strength of the decorative pattern that is the produced patterned cured product is further improved.
Examples of the energy applying treatment include heat treatment and actinic ray irradiation treatment.
Irradiation with actinic rays includes, for example, overall exposure with ultraviolet rays.
From the viewpoint of the curing acceleration effect by the post-treatment and the simplicity of the process, the energy application is preferably the heat treatment described in detail below.

[Heat treatment]
The heat treatment in the method for producing a decorative pattern is performed after the developing step, and includes a step of performing heat treatment at 130° C. to 170° C. (post bake step).
Manufacturing of a decorative pattern in which a decorative pattern is formed after other members such as an electrode pattern, a lead wiring, a light-shielding conductive film, and an overcoat layer are previously formed on a base material by heat treatment at such a temperature. Also in the method, the heat treatment can be performed without adversely affecting other members.
The temperature of the heat treatment step is more preferably 140°C to 160°C, further preferably 140°C to 150°C.
In the above-described transfer film of the present disclosure, the effect of the patterned cured product is promoted by heat treatment, and further, the patterned cured product is heated by the low temperature baking at 140° C. to 150° C., and the decorative pattern is tapered. A shape is formed.
The time of 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.

In the transfer film of the present disclosure described above, since the photosensitive resin layer and the protective film are configured as described above, the peelability between the protective film and the photosensitive resin layer is good, and by the low temperature baking step as described above, The patterned cured product quickly forms a tapered shape, and the decorative pattern, which is the formed cured product of the tapered shape, is excellent in the appearance and the concealing property of the wiring and the like when provided in a touch panel or the like.

<Touch panel>
The touch panel has the above-mentioned decoration pattern. The decorative pattern is arranged on the outermost surface of the touch panel.

The touch panel to which the decorative pattern can be applied is not particularly limited, and can be appropriately selected according to the purpose. For example, a surface type electrostatic capacity type touch panel, a projection type electrostatic capacity type touch panel, a resistive film type touch panel, etc. are mentioned. Details will be described later as a resistive film type touch panel and an electrostatic capacitance type touch panel.
The touch panel includes so-called touch sensor and touch pad. The layer structure of the touch panel sensor electrode portion 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 one substrate, a single-sided jumper or through-hole method, or a single-area layer method. Either is fine. In addition, the projection capacitive touch panel is more preferably AC (alternate current) driving 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 resistance film type touch panel is a resistance film type touch panel including the decorative pattern described above.
The resistive film type touch panel has a basic configuration in which conductive films of a pair of upper and lower substrates having conductive films are arranged via a spacer at positions where the conductive films face each other. Note that the configuration of the resistive film type touch panel is known, and known techniques can be applied without any limitation.

[Capacitive touch panel]
The capacitive touch panel is a capacitive touch panel including the above-mentioned decorative pattern.
Examples of the capacitive touch panel system include a surface capacitive type and a projected capacitive type. A projection-type capacitive touch panel is a basic type 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 arranged via an insulator. Consist of the composition. More specifically, the X electrode and the Y electrode are formed on different surfaces of one substrate, and the X electrode, the insulating layer, and the Y electrode are formed in this order on one substrate. A mode in which an X electrode is formed on one substrate and a Y electrode is formed on another substrate (in this mode, a configuration in which two substrates are bonded together is the basic configuration). Be done. Note that the configuration of the capacitive touch panel is publicly known, and the publicly known technology can be applied without any limitation in the embodiment of the present invention.

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed 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.
In addition, "part" is based on mass unless otherwise specified.

(Examples 1 to 12, Comparative Examples 1 to 3)
<Preparation of composition for forming photosensitive resin layer>
A composition for forming a photosensitive resin layer was prepared by stirring and mixing these components according to the formulations shown in Tables 1 and 2 below. Details of the compounds described in Table 1 and Table 2 are as shown below.
In Tables 1 and 2, the abbreviations in parentheses may be used.

-Black pigment dispersion: manufactured by Tokyo Ink Co., Ltd., black pigment dispersion FDK-911 (trade name: FDK-911)

(Preparation of Green Pigment Dispersion and Red Pigment Dispersion)
A Green pigment or Red pigment, a dispersant, a polymer and a solvent were mixed so as to have the following composition, and a pigment dispersion was obtained by using a three-roll and a bead mill.

(Pigment dispersion composition)
-The following Green pigment or Red pigment 13.1% by mass
Dispersant 1 [structure below] 0.65% by 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

-Green pigment: Pigment Green 58 (DIC Corporation, FASTOGEN Green A110)
Red pigment: Pigment Red 254 (BASF Corp., Irgaphor Red BT-CF)

-Polymerizable monomer-
・A-NOD-N (Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 226)
・A-DCP (Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 304)
8UX-015A (Taisei Fine Chemical Co., Ltd., 15 functional)
-75 mass% propylene glycol monomethyl ether acetate (PGMEA) solution of KAYARAD DPHA (trade name: Nippon Kayaku Co., Ltd., hexafunctional, molecular weight 579)-A-BPE-10 (Shin-Nakamura Chemical Co., Ltd., bifunctional )
・UA-32P (Shin-Nakamura Chemical Co., Ltd., 9 functional)

-Binder-
Acrybase FFS-6058 (Fujikura Kasei Co., Ltd., Acrybase (registered trademark) FFS-6058) (Mw: 5000)
-Akrit 8KB-001 (Taisei Fine Chemicals Co., Ltd., Akrit (registered trademark) 8KB-001) (Mw: 13000)
・Acrybase FF187 (Fujikura Kasei Co., Ltd., Acrybase (registered trademark) FF187) (Mw: 30000)

-Photopolymerization initiator-
Irgacure OXE-02 (manufactured by BASF, IRGACURE (registered trademark) OXE 02, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o -Acetyl oxime))
-Solvent-
-1-Methoxy-2-propyl acetate-Methyl ethyl ketone-surfactant-
-F-784-F (manufactured by DIC, Megafac (registered trademark) F-784-F)

<Production of transfer film>
A thermoplastic resin layer coating solution having the following formulation H1 was applied on a polyethylene terephthalate film temporary support having a thickness of 75 μm using a slit nozzle and dried to form a thermoplastic resin layer.
Next, a functional layer coating liquid having the following formulation P1 was applied onto the thermoplastic resin layer described above and dried to obtain a functional layer. Further, the above-mentioned composition for forming a photosensitive resin layer was applied onto the functional layer and dried to obtain a photosensitive resin layer.

By the method described above, a thermoplastic resin layer having a dry film thickness of 15.1 μm, a functional layer having a dry film thickness of 1.6 μm, and a photosensitive resin layer having a dry film thickness of 2.0 μm are formed on the temporary support. Finally, a protective film was pressure-bonded to the surface of the photosensitive resin layer. Thus, a transfer film having a temporary support, a thermoplastic resin layer, a functional layer (oxygen blocking film), a photosensitive resin layer containing the photosensitive resin composition described in each column of each Example or Comparative Example, and a protective film is obtained. , Respectively.
The following two types were used for the protective film.
・"Polypropylene" film: polypropylene film with a thickness of 12 µm ・"PET" film: polyethylene terephthalate film with a thickness of 16 µm

~ Thermoplastic resin layer coating liquid: 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 5.83 parts by mass (copolymerization composition ratio (molar ratio)=55/11.7) /4.5/28.8, weight average molecular weight=100,000, glass transition temperature (Tg)≈70° C.)
Styrene/acrylic acid copolymer 13.6 parts by mass (copolymerization composition ratio (molar ratio)=63/37, weight average molecular weight=10,000, Tg≈100° C.)
-2,2-bis[4-(methacryloxypolyethoxy)phenyl]propane (Shin-Nakamura Chemical Co., Ltd.) 9.1 parts by mass-Fluorosurfactant 0.54 parts by mass (solid content 30% by mass) Methyl ethyl ketone solution, DIC Corporation, Megafac (registered trademark) F780F)

~ Functional layer coating liquid: Formulation P1
-PVA205 32.2 parts by mass (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
-Polyvinylpyrrolidone 14.9 parts by mass (K-30, manufactured by ISPE Japan)
Distilled water 524 parts by mass Methanol 429 parts by mass

<Preparation of decorative pattern>
The protective films of the various transfer films produced above were peeled off, and the transfer films were stacked so that the photosensitive resin layer of the transfer films was in contact with the substrate (colorless polyester film having a thickness of 200 μm). It was a laminate having a resin layer.
A mask is placed on a temporary support that is placed on the opposite side of the photosensitive resin layer on the base material, and the metal halide lamp (wavelength: 365 nm) is used to sensitize the light from above the mask. The resin layer was exposed. After the exposure, the temporary support was peeled off, and the exposed photosensitive resin layer was immersed in a 1% by mass sodium carbonate aqueous solution for development.
Then, it was heated at 145° C. for 30 minutes in an oven and heat-treated at a low temperature to obtain a frame-shaped decorative pattern which is a cured product of the photosensitive resin layer.

<Evaluation>
Various evaluations were performed on the transfer film produced using the photosensitive resin composition of each of the examples and comparative examples, and the decorative pattern produced using the transfer film. The evaluation results are shown in Tables 1 and 2.

(Taper angle)
By slicing the frame-shaped decorative pattern to make a slice and observing the slice with a scanning electron microscope (SEM: manufactured by JEOL Ltd.), the angle at the end of the decorative pattern (angle θ in FIG. 3). ) Was measured and evaluated according to the following evaluation criteria. In addition, the angle at the end of the decorative pattern being less than 90° indicates that the decorative pattern has a tapered shape, and means that the tapered shape is formed by heat treatment at low temperature (low temperature baking). If the angle at the end of the decorative pattern exceeds 90°, it means that the decorative layer has an inverse tapered shape.
FIG. 3 is a diagram illustrating an angle (θ) at an end portion of the decorative pattern (decorative layer) 21 provided on the base material 22. In the evaluation criteria below, A to C are practical ranges.
<Evaluation criteria>
A: The angle (angle θ) at the end of the decorative pattern is 30° or more and less than 50°.
B: The angle (angle θ) at the end of the decorative pattern is 50° or more and less than 70°.
C: The angle (angle θ) at the end of the decorative pattern is 70° or more and less than 90°.
D: The angle (angle θ) at the end of the decorative pattern is 90° or more.

(Peelability)
The manner of peeling when the protective film was peeled from the photosensitive resin layer was observed. In the following evaluation criteria, A to C are practical ranges.
<Evaluation criteria>
A: When the protective film is peeled off, only the protective film can be peeled off without sound.
B: There is a slight noise when peeling off the protective film, but only the protective film can be peeled.
C: When the protective film is peeled off, a loud noise is generated, but only the protective film can be peeled off.
D: The photosensitive resin layer remains on the protective film after peeling off the protective film.

(Surface condition)
The surface inside the frame of the frame-shaped decorative pattern is observed using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 times), and the surface state of the surface of the decorative pattern in the visual field is observed. did. It is preferable that the surface looks smooth. A or B is in a practical range, and A is preferable.
<Evaluation criteria>
A: The observation range is very smooth and has no visible irregularities.
B: The observation range is smooth and has no visible irregularities.
C: Irregularities such as black dots (projections) or craters (recesses) can be visually recognized within the observation range.

(Edge roughness)
The inner surface of the frame of the frame-shaped decorative pattern was observed using a laser microscope (VK-9500, manufactured by KEYENCE CORPORATION; objective lens 50 times), and the most swollen part of the edge position in the visual field ( The absolute value of the difference between the peak part) and the most constricted part (valley bottom part) was obtained, and the average value of the five observed parts was calculated as the edge roughness.
The smaller the edge roughness, the sharper the outline of the decorative pattern and the better the linearity, and it is evaluated as preferable. In the following evaluation criteria, A to C are in a practical range, preferably A or B, and more preferably A.
<Evaluation criteria>
A: Edge roughness is less than 2 μm.
B: Edge roughness is 2 μm or more and less than 5 μm.
C: Edge roughness is 5 μm or more and less than 10 μm.
D: Edge roughness is 10 μm or more.

From the results of Tables 1 and 2, it can be seen that the transfer films of Examples have good releasability when the protective film is peeled from the photosensitive resin layer during transfer. Furthermore, it can be seen that the transfer film of the example can form a decorative pattern having a good taper angle, a surface shape, and a linearity of the pattern.

The disclosure of Japanese Patent Application No. 2016-109311 filed on May 31, 2016 is incorporated herein by reference in its entirety.
All publications, patent applications, and technical standards mentioned herein are to the same extent as if each individual publication, patent application, and technical standard were specifically and individually noted to be incorporated by reference, Incorporated herein by reference.

Claims (9)

A temporary support, a photosensitive resin layer provided on the temporary support, containing a binder, a polymerizable monomer, and a pigment, and a protective film provided in contact with the photosensitive resin layer,
The ratio of the content of the polymerizable monomer to the content of the binder in the photosensitive resin layer is 0.32 to 0.50 on a mass basis,
A transfer film in which the surface roughness Rz of the surface of the protective film on the side in contact with the photosensitive resin layer is less than 0.12 μm. The transfer film according to claim 1, wherein the protective film is a polyester film. The transfer film according to claim 1, wherein the pigment is a black pigment. The transfer film according to any one of claims 1 to 3, wherein the polymerizable monomer contains a bifunctional polymerizable monomer. The transfer film according to any one of claims 1 to 4, wherein the polymerizable monomer contains a polymerizable monomer having a molecular weight of 500 or less. The transfer film according to claim 1, wherein the binder contains a binder having a weight average molecular weight of 5,000 to 10,000. The transfer film according to any one of claims 1 to 6, further comprising a functional layer between the temporary support and the photosensitive resin layer. The transfer film according to any one of claims 1 to 7, wherein the surface roughness Rz is 0.01 µm or more and less than 0.12 µm. Wherein the ratio of the content of the polymerizable monomer is transferred fill beam according to any one of claims 1 to 8 is 0.40 less than 0.35 or more by weight with respect to the content of the binder.