CN114341733A - Transfer film, method for producing laminate, touch panel sensor, and touch panel - Google Patents

Abstract

The invention provides a transfer film which can form a laminated body with a conductive pattern with excellent adhesion between a pattern-shaped cured resin layer and a pattern-shaped conductive layer formed by exposure of a photosensitive resin layer. Also provided are a method for manufacturing a laminate, a touch panel sensor, and a touch panel. The transfer film includes a temporary support, a conductive layer, and a photosensitive resin layer, the photosensitive resin layer includes a binder polymer, a compound having an ethylenically unsaturated group, and a photopolymerization initiator, and the conductive layer includes an organic phosphorus compound having a P ═ O bond in a molecule.

Description

Transfer film, method for producing laminate, touch panel sensor, and touch panel

Technical Field

The present invention relates to a transfer film, a method for manufacturing a laminate, a touch panel sensor, and a touch panel.

Background

Liquid crystal display elements or touch panels are used for large-sized electronic devices such as personal computers and televisions, small-sized electronic devices such as car navigation devices, cellular phones, and electronic dictionaries, and display devices such as OA (office Automation) devices and FA (Factory Automation) devices. These liquid crystal display elements or touch panels have transparent electrodes.

As the touch panel, various systems have been put into practical use, and in recent years, a capacitive touch panel has been increasingly used.

As the transparent electrode, an electrode formed using a material such as ITO (Indium Tin Oxide), Indium Oxide, or Tin Oxide has been conventionally used, but instead of these, it has been proposed to use a conductive pattern formed from a photosensitive conductive film having a conductive layer containing conductive fibers by a photolithography process.

Patent document 1 describes a photosensitive conductive film (transfer film) including a temporary support, a conductive layer containing conductive fibers provided on the temporary support, and a photosensitive resin layer provided on the conductive layer. After the photosensitive conductive film is bonded to the support substrate on the surface on the photosensitive resin layer side, for example, in the case of negative development, the photosensitive resin layer disposed on the support substrate is exposed in a pattern form (pattern exposure), and the photosensitive resin layer and the conductive layer in the unexposed region are removed by development treatment after the exposure, whereby a conductive pattern substrate (a laminate having a conductive pattern) is obtained.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-049055

Disclosure of Invention

Technical problem to be solved by the invention

As a result of conducting studies on a laminate having a conductive pattern formed by a transfer film described in patent document 1, the present inventors have found that there is room for further improvement in adhesion between a patterned cured resin layer formed by exposure of a photosensitive resin layer and the patterned conductive layer.

Accordingly, an object of the present invention is to provide a transfer film that can form a laminate having a conductive pattern excellent in adhesion between a patterned cured resin layer formed by exposure of a photosensitive resin layer and a patterned conductive layer.

Another object of the present invention is to provide a method for manufacturing a laminate, a touch panel sensor, and a touch panel.

Means for solving the technical problem

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configurations, and have completed the present invention.

[ 1] A transfer film comprising a temporary support, a conductive layer and a photosensitive resin layer,

the photosensitive resin layer contains a binder polymer, a compound having an ethylenically unsaturated group, and a photopolymerization initiator,

the conductive layer contains an organic phosphorus compound having a P ═ O bond in the molecule.

The transfer film according to [ 1], which comprises the temporary support, the conductive layer, and the photosensitive resin layer in this order.

[ 3 ] the transfer film according to [ 1] or [ 2], wherein,

the conductive layer further contains silver nanowires.

[4 ] the transfer film according to any one of [ 1] to [ 3 ], wherein,

the organic phosphorus compound includes a compound represented by the following general formula (P1).

[ 5 ] the transfer film according to any one of [ 1] to [4 ], wherein,

the content of the organic phosphorus compound is 0.05-15.0 mass% of the total mass of the conductive layer.

[ 6 ] the transfer film according to any one of [ 1] to [ 5 ], wherein,

the photopolymerization initiator contains P ═ O bonds in the molecule.

[ 7 ] the transfer film according to [ 6 ], wherein,

the photopolymerization initiator is 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide.

[ 8 ] the transfer film according to any one of [ 1] to [ 7 ], wherein,

the content of the photopolymerization initiator is 0.05 to 0.5 by mass relative to the content of the compound having an ethylenically unsaturated group.

[9 ] the transfer film according to any one of [ 1] to [ 8 ], wherein,

the above-mentioned compound having an ethylenically unsaturated group contains an ester bond.

[ 10 ] the transfer film according to any one of [ 1] to [9 ], wherein,

the above-mentioned compound having an ethylenically unsaturated group contains 3 or 4 ethylenically unsaturated groups in the molecule.

[ 11 ] the transfer film according to any one of [ 1] to [ 10 ], wherein,

the photosensitive resin layer further contains a phosphate ester compound.

[ 12 ] the transfer film according to any one of [ 1] to [ 11 ], wherein,

the binder polymer contains at least 1 kind selected from structural units derived from methacrylic acid and structural units derived from alkyl methacrylate and at least 1 kind selected from structural units derived from acrylic acid and structural units derived from alkyl acrylate, and the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is 60/40-80/20 in terms of mass ratio relative to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

A method for producing a laminate having a substrate and a conductive pattern, the method comprising:

bonding the transfer film according to any one of [ 1] to [ 12 ] to the substrate by bringing the substrate into contact with a surface of the transfer film opposite to a surface on which the temporary support is disposed;

a step of pattern-exposing the upper photosensitive resin layer of the transfer film; and

and forming a patterned conductive layer by removing a part of the conductive layer included in the transfer film together with an unexposed portion of the photosensitive resin layer.

[ 14 ] A laminate produced by the production method according to [ 13 ], wherein,

the laminate comprises a substrate, a patterned conductive layer, and a patterned cured resin layer.

A touch panel sensor having the laminate according to [ 14 ].

A touch panel having the touch panel sensor of [ 15 ].

Effects of the invention

According to the present invention, it is possible to provide a transfer film capable of forming a laminate having a conductive pattern excellent in adhesion between a patterned cured resin layer formed by exposure of a photosensitive resin layer and a patterned conductive layer.

Further, according to the present invention, a method for manufacturing a laminate, a touch panel sensor, and a touch panel can be provided.

Drawings

Fig. 1 is a schematic diagram showing an example of the structure of a transfer film.

Fig. 2 is a schematic diagram showing another example of the structure of the transfer film.

Fig. 3A is a schematic diagram for explaining an example of a method for producing a laminate.

Fig. 3B is a schematic diagram for explaining an example of a method for producing a laminate.

Fig. 3C is a schematic diagram for explaining an example of a method for producing a laminate.

Detailed Description

The present invention will be described in detail below. The following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. Note that, although the description is made with reference to the drawings, the reference numerals may be omitted.

In the present specification, "to" indicating a numerical range is used in the sense of including numerical values described before and after the range as a lower limit value and an upper limit value.

In the labeling of a group (atomic group) in the present specification, a label which is not labeled with a substitution and an unsubstituted label includes not only a group having a substituent but also a group having no substituent. For example, the notation "alkyl" means to include not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, "(meth) acrylate" is a concept including both acrylate and methacrylate, and "(meth) acryloyl group" is a concept including both acryloyl group and methacryloyl group.

In the present specification, "organic group" means a group containing 1 or more carbon atoms.

In the present specification, "mass%" means the same as "weight%" and "parts by mass" means the same as "parts by weight".

In the present specification, the amount of each component in the composition refers to the total amount of a plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.

In the present specification, unless otherwise specified, the composition ratio of the polymer (composition ratio of the structural unit) is based on mass.

Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present specification are molecular weights obtained as follows: the conversion was carried out by using a Gel Permeation Chromatography (GPC: Gel Permeation Chromatography) analyzer using columns TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL and/or TSKgel Super HZM-N (each being a trade name manufactured by Tosoh Corporation), using a solvent THF (tetrahydrofuran), a differential refractometer for detection, and using polystyrene as a standard substance.

In the present specification, the term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when it is not clearly distinguished from other steps.

In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also imaging using a particle beam such as an electron beam or an ion beam. Examples of the light used for exposure include active rays (active energy rays) such as a bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (euv (extreme ultraviolet) light), and X-rays.

[ transfer film ]

The transfer film of the present invention comprises a temporary support, a conductive layer and a photosensitive resin layer,

the photosensitive resin layer contains a binder polymer, a compound having an ethylenically unsaturated group (hereinafter, also referred to as "ethylenically unsaturated compound"), and a photopolymerization initiator,

the conductive layer contains an organic phosphorus compound having a P ═ O bond in the molecule (hereinafter, also referred to as a "specific phosphorus compound").

The specific phosphorus compound is a compound containing P ═ O bonds and 1 or more carbon atoms in the molecule.

As a result of intensive studies, the present inventors have found that a laminate having a conductive pattern (hereinafter, also referred to as "laminate") formed by forming a patterned cured resin layer by exposure of a photosensitive resin layer and a patterned conductive layer have excellent adhesion, and that the conductive pattern is formed by: the conductive layer and the photosensitive resin layer are transferred onto the substrate by the transfer film having the above-described structure, the photosensitive resin layer disposed on the substrate is exposed in a pattern form, and the photosensitive resin layer and the conductive layer in the unexposed area are removed by development treatment after exposure.

The transfer film of the present invention has no mechanism for solving the problem of the present invention by the above-described structure, but the present inventors presume as follows.

In the specific phosphorus compound, a phosphorus atom having a P ═ O bond contained in a molecule is likely to electrically interact with a metal atom (particularly, a silver atom) in the conductive layer, and a carbon atom contained in a molecule has high affinity with a binder contained in the photosensitive resin layer, a compound having an ethylenically unsaturated group, or the like. That is, it is assumed that the specific phosphorus compound functions as a component for improving adhesion between a component contained in the conductive layer and a component in the photosensitive resin layer. In particular, when the specific phosphorus compound has a specific structure, the adhesion between the patterned cured resin layer formed by exposure of the photosensitive resin layer and the patterned conductive layer of the laminate to be formed is more excellent.

In addition, in the laminate formed by using the transfer film of the present invention, a case where the adhesion between the patterned cured resin layer formed by exposure of the photosensitive resin layer and the patterned conductive layer is excellent is also referred to as "excellent effects of the present invention" hereinafter.

The transfer film may have other layers than the temporary support, the conductive layer, and the photosensitive resin layer, or may be composed of only the temporary support, the conductive layer, and the photosensitive resin layer. Examples of the other layers than the temporary support, the conductive layer, and the photosensitive resin layer include a protective film, an adhesive layer, and a gas barrier layer.

Fig. 1 and 2 show a configuration example of a transfer film. However, the transfer film of the present invention is not limited to the transfer film having the structure shown in fig. 1 and 2.

Fig. 1 is a schematic diagram showing an example of the structure of a transfer film. In the transfer film 10 shown in fig. 1, a temporary support 1, a conductive layer 2, a photosensitive resin layer 3, and a protective film 4 are stacked in this order.

Fig. 2 is a schematic diagram showing another example of the structure of the transfer film. In the transfer film 20 shown in fig. 2, a temporary support 1, a photosensitive resin layer 3, a conductive layer 2, and a protective film 4 are stacked in this order.

The respective layers of the transfer film will be described in detail below.

[ thickness of layers ]

The thickness of each layer included in the transfer film is a value obtained as follows: a cross section including a direction perpendicular to the main surface of the layer was observed with a Scanning Electron Microscope (SEM), and the thickness of the layer was measured at 10 or more points from the obtained observation image to calculate an average value. The thickness of the photosensitive resin layer may be measured by a known apparatus such as a micromage gauge or a thickness gauge, in addition to a scanning electron microscope.

[ temporary support body ]

The transfer film of the present invention has a temporary support.

Examples of the temporary support include a glass substrate and a resin film, preferably a resin film, and more preferably a resin film having heat resistance and solvent resistance. The temporary support is preferably a film which is flexible and does not undergo significant deformation, shrinkage, or stretching under pressure or under pressure and heat.

Examples of such resin films include Polyethylene terephthalate (PET) films, Polyethylene films, polypropylene films, and polycarbonate films. Among them, a polyethylene terephthalate film is preferable in terms of more excellent transparency and heat resistance.

The surface of the resin film may be subjected to a release treatment to allow easy subsequent peeling from the photosensitive layer.

From the viewpoint of further improving the workability, the temporary support preferably has 10 particles having a diameter of 5 μm or more per mm on the surface opposite to the side on which the conductive layer is formed²More preferably, the amount of the surfactant is 10 to 120/mm². The upper limit of the diameter of the particles is, for example, 10 μm or less.

The thickness of the temporary support is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more, from the viewpoint of further excellent mechanical strength. By using the temporary support having a thickness of the above value or more, the temporary support can be prevented from being damaged in the step of applying the composition for forming a conductive layer to form a conductive layer, the step of applying the composition for forming a photosensitive resin layer to form a photosensitive resin layer, the exposure step, the development step, and the step of peeling the temporary support from the transferred transfer film.

When the photosensitive resin layer is irradiated with active light through the temporary support, the thickness of the temporary support is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less, from the viewpoint of further improving the resolution of the conductive pattern.

In view of the above, the thickness of the temporary support is preferably 5 to 300. mu.m, more preferably 10 to 200. mu.m, and still more preferably 15 to 100. mu.m.

The haze value of the temporary support is preferably 0.01 to 5.0%, more preferably 0.01 to 3.0%, even more preferably 0.01 to 2.0%, and particularly preferably 0.01 to 1.5%, from the viewpoint of further improving the exposure sensitivity of the photosensitive resin layer and the resolution of the conductive pattern.

The haze value can be measured by a method in accordance with JIS K7105 (method for testing optical properties of plastics), for example, by using a commercially available haze meter such as NDH-1001DP (NIPPON DENSHOKU INDUSTRIES Co., LTD, trade name).

From the viewpoint of further excellent exposure sensitivity of the photosensitive resin layer and resolution of the conductive pattern, the transmittance of the active light irradiated to the temporary support at a wavelength (more preferably, at a wavelength of 365nm) is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more.

The transmittance of the layer included in the transfer film is a ratio of the intensity of outgoing light emitted from the transmissive layer to the intensity of incident light when the light is incident in a direction (thickness direction) perpendicular to the main surface of the layer, and can be measured by MCPD Series manufactured by Otsuka Electronics co.

Further, the film used as the temporary support is preferably free from deformation such as wrinkles, scratches, and the like.

In view of more excellent pattern formability and transparency of the temporary support when pattern exposure is performed through the temporary support, the temporary support preferably contains a small number of fine particles, foreign substances, and defects. The number of fine particles, foreign matters and defects having a diameter of 1 μm or more is preferably 50 particles/10 mm²Hereinafter, more preferably 10 pieces/10 mm²Hereinafter, more preferably 3/10 mm²The following.

[ conductive layer ]

The transfer film of the present invention has a conductive layer.

The conductive layer is not particularly limited in structure as long as it can obtain conductivity in the plane direction, but conductive fibers are preferably in contact with each other to form a mesh structure.

The conductive layer may be disposed on the surface of the photosensitive resin layer facing the temporary support, or may be disposed on the surface of the photosensitive resin layer opposite to the surface facing the temporary support. After the transfer film is produced, a part of the components contained in the photosensitive resin layer (for example, a binder polymer) may permeate into the conductive layer.

< conductive fiber >

Examples of the conductive fibers included in the conductive layer include metal fibers such as gold, silver, and platinum, and carbon fibers such as carbon nanotubes. The conductive fibers may be used alone or in combination of 2 or more.

The conductive fiber is preferably a linear conductive material (hereinafter, also referred to as "silver nanowire") made of silver or an alloy (made of silver and a metal other than silver) in view of more excellent conductivity. The structure of the silver nanowire is not particularly limited, and for example, a structure in which a linear core portion made of silver is covered with a metal other than silver is preferable. Here, the structure coated with a metal other than silver includes not only a structure in which the entire surface of the silver nanowire serving as the core is coated, but also a structure in which a part of the silver nanowire is coated.

The metal other than silver is preferably a metal noble than silver, more preferably gold, platinum or palladium, and still more preferably gold.

The shape of the conductive fiber is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a cylindrical shape, a rectangular parallelepiped shape, and a columnar shape having a polygonal cross section.

The diameter of the conductive fiber is preferably 1 to 50nm, more preferably 2 to 20nm, and further preferably 3 to 10 nm. The length of the conductive fiber is preferably 1 to 100 μm, more preferably 2 to 50 μm, and still more preferably 3 to 10 μm.

The fiber diameter and the fiber length of the conductive fibers are values obtained by arbitrarily selecting 20 conductive fibers from an observation image including a plurality of conductive fibers obtained by a Scanning Electron Microscope (SEM) and arithmetically averaging the lengths of the short axis and the long axis of each conductive fiber.

When the conductive fiber is a metal fiber, examples of a method for producing the metal fiber include a method of reducing metal ions with a reducing agent such as NaBH4, a method of using a polyol method, and the like. Further, a method for producing a metal fiber nanowire is described in paragraphs 0019 to 0024 of Japanese patent application laid-open No. 2011-149092, the contents of which are incorporated in the present specification. When the conductive fiber is a carbon fiber such as a carbon nanotube, a commercially available product such as a Hipco single-walled carbon nanotube available from Unidym can be used as the carbon fiber.

The conductive layer may contain an organic conductor together with the conductive fibers. The organic conductor is not particularly limited, and examples thereof include organic conductors such as polymers of thiophene derivatives and aniline derivatives. More specifically, polyethylene dioxythiophene, polyhexylthiophene and polyaniline can be mentioned.

The thickness of the conductive layer varies depending on the application of the conductive pattern produced using the transfer film and the desired conductivity, but is preferably 1 μm or less, more preferably 1nm or more and 0.5 μm or less, and still more preferably 5nm or more and 0.1 μm or less. When the thickness of the conductive layer is 1 μm or less, the light transmittance in a wavelength region of 450 to 650nm is high, and the pattern formability is excellent, and the conductive layer is particularly suitable for producing a transparent electrode.

< organic phosphorus Compound having P ═ O bond in molecule >

The conductive layer contains an organophosphorus compound (specific phosphorus compound) having a P ═ O bond in the molecule.

The specific phosphorus compound is not particularly limited as long as it contains a P ═ O bond and 1 or more carbon atoms in the molecule, and examples thereof include compounds represented by the following general formula (P1).

[ chemical formula 1]

In the formula, R^X1～R^X3Each independently represents-L^X1-R^X4. L above^X1Represents a single bond or a 2-valent linking group. R is as defined above^X4Represents a hydrocarbon group. Wherein R is^X1～R^X3At least 1 of them represents-L^X1-an aromatic hydrocarbon group.

As the above-mentioned L^X1The 2-valent linking group is not particularly limited, and examples thereof include-O-, -CO-, and,A 2-valent aliphatic hydrocarbon group (e.g., an alkylene group, an alkenylene group (e.g., -CH ═ CH-), an alkynylene group (e.g., -C ≡ C-), or a combination thereof).

Wherein L is the above-mentioned^X1Preferably a single bond, -O-or-CO-, more preferably a single bond or-CO-.

As the above-mentioned R^X4Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic.

The aliphatic hydrocarbon group may further have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom.

The aromatic hydrocarbon group is not particularly limited, but is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a phenyl group.

The aromatic hydrocarbon group may further have a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms (which may be linear, branched, or cyclic).

Wherein, as R^X4The hydrocarbon group is preferably an aromatic hydrocarbon group, and more preferably a substituted or unsubstituted phenyl group, from the viewpoint of further improving the effect of the present invention.

The compound represented by the general formula (P1) is preferably R in view of further improving the effect of the present invention^X1～R^X3Each independently represents-L^X1-aromatic hydrocarbon radical, more preferably R^X1And R^X2Each independently represents an aromatic hydrocarbon group and R^X3Is represented by^X1-an aromatic hydrocarbon group.

As the compound represented by the general formula (P1), for example, 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenyl-phosphine oxide, ethyl phenyl (2, 4, 6-trimethylbenzoyl) phosphinate, and the like can be used.

The content of the specific phosphorus compound in the conductive layer is preferably 0.001 to 25.0 mass% with respect to the total mass of the conductive layer, and more preferably 0.05 to 15.0 mass% from the viewpoint of further excellent effects of the present invention.

The content of each component in the conductive layer can be determined from the content (mass%) of each component with respect to the total solid content of the composition for forming a conductive layer. For example, the content of the specific phosphorus compound in the conductive layer can be determined from the content (mass%) of the specific phosphorus compound with respect to the total solid content of the composition for forming the conductive layer. In the present specification, the "solid component" in the composition for forming a conductive layer refers to a component for forming a conductive layer, and does not contain a solvent. Further, as long as the component forming the conductive layer is a liquid, the component is considered to be a solid component.

< adhesive Polymer >

The conductive layer may comprise a binder polymer. The binder polymer is preferably a water-soluble resin, and examples thereof include polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), and the like. The water-soluble resin may be a component that can be used as a dispersant in the production of conductive fibers to be described later.

The binder polymer preferably contains polyvinylpyrrolidone (PVP) from the viewpoint of further improving the effect of the present invention. In addition, the content of polyvinylpyrrolidone (PVP) is preferably 60 mass% or more, more preferably 80 mass% or more, based on the total mass of the binder polymer, from the viewpoint that the effect of the present invention is more excellent. The upper limit is 100 mass%.

The content of the binder polymer in the conductive layer is preferably 20 to 70% by mass, and more preferably 30 to 55% by mass, based on the total mass of the conductive layer.

In view of further improving the effect of the present invention, the conductive layer is preferably disposed on the surface of the photosensitive resin layer facing the temporary support. That is, the transfer film of the present invention preferably includes a temporary support, a conductive layer, and a photosensitive resin layer in this order.

< method of formation >

Examples of the method for forming the conductive layer include the following methods: the conductive layer is formed by preparing a conductive layer-forming composition containing conductive fibers, applying the conductive layer-forming composition on the surface of a temporary support, a photosensitive resin layer, or the like, and then drying the coating film of the conductive layer-forming composition.

The content of the conductive fibers in the composition for forming a conductive layer is not limited as long as a coating film of the composition for forming a conductive layer can be formed, and is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the composition for forming a conductive layer.

The composition for forming a conductive layer preferably contains a solvent. Examples of the solvent include water and an organic solvent. The composition for forming the conductive layer preferably contains water as a solvent, and more preferably contains water and an organic solvent as solvents.

As the organic solvent, an alcohol solvent is preferable. The alcohol solvent is not particularly limited, and examples thereof include alcohols having 1 to 5 carbon atoms, ethylene glycol, polyethylene glycol alkyl ethers, glycerin, alkylene glycol propylene glycol having 3 to 6 carbon atoms, dipropylene glycol, 1-ethoxy-2-propanol, ethanolamine, and diethanolamine.

The water is not particularly limited, and preferably contains no impurities. Examples of the water include distilled water, ion-exchanged water, and pure water.

The composition for forming a conductive layer may contain at least 1 kind selected from the group consisting of the organic conductor and a dispersion stabilizer such as a surfactant.

The content of water in the composition for forming the conductive layer is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total mass of the composition for forming the conductive layer. The upper limit is not particularly limited, but is preferably 99.99% by mass or less, and more preferably 99.9% by mass or less, based on the total mass of the composition for forming a conductive layer.

When the composition for forming a conductive layer contains an organic solvent, the content of the organic solvent is preferably 0.01 to 20% by mass.

Examples of the coating method of the composition for forming a conductive layer include known methods such as a roll coating method, a comma blade coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method, but the coating method is not limited thereto.

The method of drying the coating film of the composition for forming a conductive layer is not particularly limited, and examples thereof include a method of blowing hot air at a temperature of 30 to 150 ℃ for 1 to 30 minutes by a hot air convection dryer.

[ photosensitive resin layer ]

The transfer film of the present invention includes a binder polymer, a compound having an ethylenically unsaturated group, and a photosensitive resin layer containing a photopolymerization initiator.

Hereinafter, each component included in the photosensitive resin layer will be described.

In addition, in general, when the transfer film of the present invention is exposed to an active light, the solubility of the exposed portion of the photosensitive resin layer in a developer is lowered by the exposure, and there is a possibility that the unexposed portion is removed by the development.

< adhesive Polymer >

Examples of the binder polymer include (meth) acrylic resins, styrene resins, epoxy resins, polyamide epoxy resins, alkyd resins, phenol resins, polyester resins, urethane resins, epoxy acrylate resins obtained by reaction of an epoxy resin with (meth) acrylic acid, and acid-modified epoxy acrylate resins obtained by reaction of an epoxy acrylate resin with an acid anhydride.

The binder polymer is preferably a (meth) acrylic resin in view of excellent alkali developability and film formability.

In the present specification, the (meth) acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, relative to all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin may be composed of only a structural unit derived from a (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than a (meth) acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100 mass% or less with respect to the total mass of the (meth) acrylic resin.

Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylonitriles.

Examples of the (meth) acrylate include alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, and 2,2, 3, 3-tetrafluoropropyl (meth) acrylate, and alkyl (meth) acrylate is preferable.

Examples of the (meth) acrylamide include acrylamides such as diacetone acrylamide.

Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.

The (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and more preferably methyl (meth) acrylate or ethyl (meth) acrylate.

Examples of the alkyl group include a chain alkyl group and a cyclic alkyl group. The chain alkyl group may be linear or branched, and the cyclic alkyl group may be monocyclic or polycyclic.

The (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.

The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic acid compound copolymerizable with the (meth) acrylic acid compound, and examples thereof include styrene compounds which may have a substituent at the α -position or at the aromatic ring, such as styrene, vinyltoluene and α -methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid and crotonic acid.

These polymerizable monomers may be used in 1 kind or in combination of 2 or more kinds.

Also, from the viewpoint of further improving the alkali developability, the (meth) acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonic acid group.

Among these, (meth) acrylic resins more preferably have a structural unit containing a carboxyl group, and still more preferably have a structural unit derived from the above (meth) acrylic acid.

The content of the structural unit having an acid group (preferably a structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is preferably 10% by mass or more with respect to the total mass of the (meth) acrylic resin from the viewpoint of excellent developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.

The (meth) acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth) acrylate.

The content of the structural unit derived from the alkyl (meth) acrylate in the (meth) acrylic resin is preferably 50 to 90% by mass, and more preferably 65 to 90% by mass, based on all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin is preferably a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate, and more preferably a resin composed of only a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate.

Further, as the (meth) acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

In addition, from the viewpoint of excellent peelability of the protective film and/or from the viewpoint of more excellent effects of the present invention, the (meth) acrylic resin preferably has at least 1 kind selected from a structural unit derived from methacrylic acid and a structural unit derived from alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from alkyl methacrylate.

The total content of the methacrylic acid-derived structural unit and the alkyl methacrylate-derived structural unit in the (meth) acrylic resin is preferably 40% by mass or more, more preferably 60% by mass or more, based on all the structural units of the (meth) acrylic resin, from the viewpoint of excellent peelability of the protective film and/or the viewpoint of more excellent effects of the present invention. The upper limit is not particularly limited, and may be 100 mass% or less, and is preferably 80 mass% or less from the viewpoint of further excellent developability of the photosensitive resin layer after transfer and lamination of the photosensitive resin layer.

In addition, from the viewpoint of more excellent effects of the present invention, the (meth) acrylic resin preferably further has at least 1 selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate and at least 1 selected from the group consisting of a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate.

From the viewpoint of further improving the effect of the present invention, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate is preferably 60/40 to 80/20 in terms of a mass ratio to the total content of the structural unit derived from acrylic acid and the structural unit derived from alkyl acrylate.

The (meth) acrylic resin preferably has an ester group at a terminal thereof in view of excellent developability of the photosensitive resin layer after transfer.

In addition, the terminal portion of the (meth) acrylic resin is constituted by a site derived from a polymerization initiator used for synthesis. The (meth) acrylic resin having an ester group at the terminal is synthesized by using a polymerization initiator that generates a radical having an ester group.

The weight average molecular weight Mw of the binder polymer is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, and even more preferably 30,000 to 100,000, from the viewpoint of more balanced mechanical strength, developer resistance and developability.

The photosensitive resin layer may contain only 1 kind of the above-mentioned resin, or 2 or more kinds of the above-mentioned resin as a binder polymer.

Examples of the 2 or more types of resins that can be contained in the photosensitive resin layer include 2 or more types of resins having different structural units, 2 or more types of resins having different weight average molecular weights, and 2 or more types of resins having different degrees of dispersion.

The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of further improving the strength of the cured film and the handling properties on the transfer film.

The content of each component in the photosensitive resin layer can be determined from the content (mass%) of each component with respect to the total solid content of the photosensitive resin layer forming composition. For example, the content of the binder polymer in the photosensitive resin layer can be determined from the content (mass%) of the binder polymer with respect to the total solid content of the photosensitive resin layer forming composition. In the present specification, the "solid component" in the composition for forming a photosensitive resin layer refers to a component for forming a photosensitive resin layer, and does not contain a solvent. Further, as long as the photosensitive resin layer is formed, the photosensitive resin layer is considered to be a solid component even if it is in a liquid state.

< Compound having ethylenically unsaturated group >

The photosensitive resin layer contains a compound having an ethylenically unsaturated group (ethylenically unsaturated compound).

The ethylenically unsaturated compound means a compound having 1 or more ethylenically unsaturated groups in the molecule. As the ethylenically unsaturated group, an acryloyl group or a methacryloyl group is preferable.

From the viewpoint of more excellent curability after curing and the viewpoint of more excellent effects of the present invention, the photosensitive resin layer preferably contains an ethylenically unsaturated compound having 2 or more functions, more preferably 3 or more functions, and still more preferably 3 or 4 functions as the ethylenically unsaturated compound. Here, for example, the 2-or more-functional ethylenically unsaturated compound means a compound having 2 or more ethylenically unsaturated groups in the molecule, and the 3-or 4-functional ethylenically unsaturated compound means a compound having 3 or 4 ethylenically unsaturated groups in the molecule.

Examples of the ethylenically unsaturated compound include a compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an α, β -unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond, an phthalic acid compound such as γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate and β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, and an alkyl (meth) acrylate.

These may be used alone or in combination of 2 or more.

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid include bisphenol a-based (meth) acrylate compounds such as 2, 2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypolypropoxy) phenyl) propane and 2, 2-bis (4- ((meth) acryloyloxypolyethoxypolypropoxy) phenyl) propane, polyethylene glycol di (meth) acrylates having 2 to 14 ethylene oxide groups, polypropylene glycol di (meth) acrylates having 2 to 14 propylene oxide groups, polyethylene glycol polypropylene glycol di (meth) acrylates having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups, trimethylolpropane di (meth) acrylates, and mixtures thereof, Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

Examples of the urethane monomer include a (meth) acrylic monomer having a hydroxyl group at the β -position, an addition reaction product of a diisocyanate compound such as isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, and 1, 6-hexamethylene diisocyanate, tris [ (meth) acryloyloxytetraethylene glycol isocyanate ] hexamethylene isocyanurate, an ethylene oxide-modified urethane di (meth) acrylate, and an ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate.

Examples of the ethylene oxide-modified urethane di (meth) acrylate include "UA-11" (trade name manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.). Further, as the ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate, for example, "UA-13" (trade name manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.).

Among the ethylenically unsaturated compounds, compounds containing an ester bond are preferable in terms of excellent developability of the photosensitive resin layer after transfer.

The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, and from the viewpoint of the excellent effect of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above tetramethylolmethane structure or trimethylolpropane structure.

Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.

From the viewpoint of imparting flexibility, the resin composition preferably contains an ethylenically unsaturated compound having a linear aliphatic group having 6 to 20 carbon atoms or the urethane monomer and an ethylenically unsaturated compound having the tetramethylolmethane structure or the trimethylolpropane structure.

Examples of the ethylenically unsaturated compound having a linear aliphatic group having 6 to 20 carbon atoms include 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate.

The photosensitive resin layer may contain only 1 kind of ethylenically unsaturated compound, or may contain 2 or more kinds.

The content of the ethylenically unsaturated compound is preferably 30 to 80 parts by mass, more preferably 30 to 70 parts by mass, based on 100 parts by mass of the total amount of the binder polymer and the ethylenically unsaturated compound. The amount of the photo-curing agent is preferably 30 parts by mass or more in view of excellent photo-curability and coatability on the formed conductive layer, and 80 parts by mass or less in view of excellent storage stability in the case of winding film formation.

The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.

The molecular weight of the ethylenically unsaturated compound (weight average molecular weight (Mw) when having a molecular weight distribution) is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

< photopolymerization initiator >

The photosensitive resin layer contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it is a compound capable of polymerizing an ethylenically unsaturated compound by irradiation with active light such as ultraviolet light, visible light, and X-ray to cure a photosensitive resin layer.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable in terms of more excellent photocurability.

Examples of the photo-radical polymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime ester compound"), a photopolymerization initiator having an α -aminoalkylphenone structure, a photopolymerization initiator having an α -hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based compound"), and a photopolymerization initiator having an N-phenylglycine structure.

More specific examples of the photo radical polymerization initiator include aromatic ketones such as benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone (michler's ketone), N' -tetraethyl-4, 4 '-diaminobenzophenone, 4-methoxy-4' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; oxime ester compounds such as 1, 2-octanedione-1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime) and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime); benzyl derivatives such as benzyl dimethyl ketal; 2, 4, 5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer; acridine derivatives such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane; n-phenylglycine, N-phenylglycine derivatives, coumarin-based compounds, and oxazole-based compounds; acylphosphine oxide-based compounds such as 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide.

The substituents of 2 aryl groups in 2, 4, 5-triarylimidazole may be the same or different. Further, as in the combination of diethylthioxanthone and dimethylaminobenzoic acid, a thioxanthone-based compound and a tertiary amine compound may be combined.

As the photo radical polymerization initiator, for example, the photo polymerization initiators described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-095716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-014783 can be used.

Among them, from the viewpoint of more excellent transparency and pattern forming ability of 10 μm or less, an oxime ester compound or an acylphosphine oxide compound is preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1, 2-octanedione-1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime) or 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide is more preferable.

Further, from the viewpoint of further improving the effects of the present invention, it is preferable that a photopolymerization initiator containing a P ═ O bond in the molecule is further contained as the photopolymerization initiator.

Examples of the photopolymerization initiator having a P ═ O bond in the molecule include acylphosphine oxide photopolymerization initiators and ethyl phenyl (2, 4, 6-trimethylbenzoyl) phosphinates, and specific examples thereof include 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, ethyl phenyl (2, 4, 6-trimethylbenzoyl) phosphinate, and the like.

The content of the photopolymerization initiator is preferably 0.05 to 0.5, more preferably 0.1 to 0.5, in terms of mass ratio to the content of the compound having an ethylenically unsaturated group.

The photosensitive resin layer may contain only 1 kind of photopolymerization initiator, or may contain 2 or more kinds.

The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass, based on the total mass of the photosensitive resin layer.

The content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the binder polymer and the ethylenically unsaturated compound. The amount of the photosensitive resin is preferably 0.1 part by mass or more in view of further excellent photosensitivity, and preferably 20 parts by mass or less in view of excellent photocurability in the photosensitive resin layer.

< leveling agent >

The photosensitive resin layer preferably contains a leveling agent in view of more excellent coatability of the composition for forming a photosensitive resin layer. Examples of the leveling agent include various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants, and silicone surfactants are preferable.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals thereof.

Specific examples of the leveling agent include DOWSIL8032ADDITIVE manufactured by DuPont Toray Specialty Materials K.K., and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515 and KF-6004 manufactured by Shin-Etsu Chemical Co.

In view of satisfying both the coatability of the composition for forming a photosensitive resin layer and the developability of the photosensitive resin layer after transfer, it is preferable to use a photopolymerization initiator containing P ═ O bonds in the molecule together with a silicone surfactant.

< phosphate ester Compound >

The photosensitive resin layer preferably contains a phosphate compound in order to further improve the adhesion of the photosensitive resin layer to the substrate.

The phosphate ester compound is phosphoric acid (O ═ p (oh))₃) At least 1 or more of the 3 hydrogens in (A) are substituted with an organic group, and examples thereof are not particularly limited, and examples thereof include Uni-Chemical Co., Ltd., the Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP) manufactured by Ltd, Nippon Kayaku Co., Kayamer series (KAYAMER PM-21, KAYAMER PM-2) manufactured by Ltd, and KYOEISHA CHEMICAL Co., LTD LIGHT ESTER series (LIGHT ESTER P-2M (trade name)) manufactured by KYOEISHA CHEMICAL Co., LTD.

The photosensitive resin layer may contain only 1 kind of the phosphate compound, or may contain 2 or more kinds.

The content of the phosphate compound is not particularly limited, but is preferably 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, and still more preferably 0.20 to 1.0% by mass, based on the total mass of the photosensitive resin layer.

When the photosensitive resin layer contains a phosphate compound, the content of the phosphate compound is not particularly limited, and is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the total of the binder polymer and the ethylenically unsaturated compound, from the viewpoint of further improving the adhesion of the photosensitive resin layer to the substrate. Further, it is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more.

< additives >

The photosensitive resin layer may contain various additives as necessary.

Examples of the additives include plasticizers such as p-toluenesulfonamide, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting agents, peeling promoters, antioxidants, perfumes, image forming agents, and thermal crosslinking agents.

The photosensitive resin layer may contain a photosensitive additive alone or in combination of 2 or more. The amount of these additives is preferably 0.01 to 20 parts by mass, respectively, based on 100 parts by mass of the total amount of the binder polymer and the ethylenically unsaturated compound.

< physical Properties, etc. >

The thickness of the photosensitive resin layer is not particularly limited, and is preferably 1 to 200 μm, more preferably 2 to 15 μm, and further preferably 3 to 10 μm in terms of the thickness after drying.

When the thickness of the photosensitive resin layer is 1 μm or more, it tends to be easy to form a layer by applying the composition for forming a photosensitive resin layer. Further, when the thickness of the photosensitive resin layer is 200 μm or less, it is preferable in terms of improvement in light transmittance and sensitivity and further excellent photocurability of the photosensitive resin layer.

< method of formation >

The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.

Examples of the method for forming the photosensitive resin layer include the following methods: a photosensitive resin layer-forming composition containing a binder polymer, an ethylenically unsaturated compound, a photopolymerization initiator and a solvent is prepared, the photosensitive resin layer-forming composition is applied to the surface of a temporary support, a conductive layer or the like, and then the coating film of the photosensitive resin layer-forming composition is dried to form a photosensitive resin layer.

The composition for forming a photosensitive resin layer preferably contains a solvent in order to adjust the viscosity of the composition for forming a photosensitive resin layer and facilitate the formation of a coating film.

The solvent contained in the composition for forming a photosensitive resin layer is not particularly limited as long as it can dissolve or disperse the binder polymer, the ethylenically unsaturated compound, the photopolymerization initiator, and the additives optionally contained therein, and examples thereof include toluene, xylene, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, hexane, benzene, and mixed solvents thereof. Among these solvents, n-propyl acetate, n-butyl acetate, isobutyl acetate, cyclohexane, or methylcyclohexane is preferable in terms of more excellent effects of the present invention.

When the photosensitive resin layer is formed using the photosensitive resin layer forming composition containing an organic solvent, the content of the organic solvent in the dried photosensitive resin layer is preferably 2 mass% or less with respect to the total mass of the photosensitive resin layer, in order to prevent the organic solvent from diffusing in the subsequent step.

The content of the solvent contained in the composition for forming a photosensitive resin layer is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and still more preferably 40 to 80% by mass, based on the total mass of the composition for forming a photosensitive resin layer, from the viewpoint that the developability of the photosensitive resin layer is more excellent.

Examples of the method for applying the composition for forming a photosensitive resin layer include known methods such as a roll coating method, a comma blade coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method, but the method is not limited thereto.

The method of drying the coating film of the composition for forming a photosensitive resin layer is not particularly limited, and examples thereof include a method of blowing hot air at a temperature of 70 to 150 ℃ for 5 to 30 minutes by a hot air convection dryer.

The minimum light transmittance in a wavelength region of 450 to 650nm (particularly, the minimum light transmittance when the thickness of the photosensitive layer is 1 to 10 μm) in a laminate (hereinafter, also referred to as "photosensitive layer") composed of the conductive layer and the photosensitive resin layer is preferably 80% or more, and more preferably 85% or more. When the photosensitive layer satisfies such conditions, the luminance of the display panel or the like can be easily increased.

[ protective film ]

The transfer film preferably has a protective film that is in contact with a surface that does not face the temporary support.

As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polyethylene terephthalate films, polypropylene films, and polyethylene films. As the protective film, a resin film made of the same material as the support film can be used.

Among these, polyolefin films are preferable, polypropylene films or polyethylene films are more preferable, and polyethylene films are further preferable.

The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of being relatively inexpensive.

The adhesion between the protective film and the photosensitive resin layer or the conductive layer is preferably smaller than the adhesion between the temporary support and the photosensitive resin layer or the conductive layer, so that the protective film can be easily peeled from the photosensitive resin layer.

Further, the number of fish eyes (fish eye) having a diameter of 80 μm or more contained in the protective film is preferably 5/m²The following. The term "fisheye" refers to a defect in which foreign matter, undissolved matter, oxidized and degraded matter, etc. of a material are taken into a film when the material is subjected to heat melting, kneading, extrusion, and film formation by a method such as biaxial stretching or casting.

The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm²Hereinafter, more preferably 10 pieces/mm²Hereinafter, more preferably 5 pieces/mm²The following. This can suppress defects caused by transfer of the irregularities caused by the particles contained in the protective film to the photosensitive resin layer or the conductive layer.

From the viewpoint of imparting windability, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the surface in contact with the photosensitive resin layer or the conductive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, the upper limit is preferably less than 0.50. mu.m, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

From the viewpoint of suppressing defects at the time of transfer, the arithmetic average roughness Ra of the surface of the protective film in contact with the photosensitive resin layer or the conductive layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, the upper limit is preferably less than 0.50. mu.m, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.

The transfer film may further include at least 1 layer selected from an adhesive layer and a gas barrier layer on the surface of the protective film.

[ method for manufacturing transfer film ]

The method for producing the transfer film of the present invention is not particularly limited, and for example, the transfer film can be produced by a method including a lamination step of forming the conductive layer and the photosensitive resin layer on the surface of the temporary support.

Hereinafter, a method for producing a transfer film will be described with reference to fig. 1 and 2.

As shown in fig. 1, a transfer film 10 having a temporary support 1, a conductive layer 2, and a photosensitive resin layer 3 in this order is produced, for example, by a method including the steps of: a step of forming the conductive layer 2 by applying the conductive layer forming composition to the surface of the temporary support 1 and then drying the coating film of the conductive layer forming composition; and a step of forming a photosensitive resin layer 3 by coating the photosensitive resin layer-forming composition on the surface of the conductive layer 2 and then drying the coating film of the photosensitive resin layer-forming composition.

The transfer film 10 shown in fig. 1 is manufactured by bonding a resin film to the surface of the photosensitive resin layer 3 of the laminate manufactured by the above-described manufacturing method to form a protective film 4.

On the other hand, a transfer film 20 shown in fig. 2, which includes the temporary support 1, the photosensitive resin layer 3, and the conductive layer 2 in this order, is produced, for example, by a method including the steps of: a step of forming a photosensitive resin layer 3 by applying a photosensitive resin layer-forming composition to the surface of the temporary support 1 and then drying the coating film of the photosensitive resin layer-forming composition; and a step of forming the conductive layer 2 by applying the conductive layer forming composition to the surface of the conductive layer 2 and then drying the coating film of the conductive layer forming composition.

A resin film is laminated on the surface of the conductive layer 2 of the laminate manufactured by the above-described manufacturing method to form a protective film 4, thereby manufacturing a transfer film 20 shown in fig. 2.

The order of the conductive layer and the photosensitive resin layer on the transfer film is not particularly limited, and the temporary support 1, the conductive layer 2, and the photosensitive resin layer 3 may be provided in this order as in the transfer film 10 shown in fig. 1, or the temporary support 1, the photosensitive resin layer 3, and the conductive layer 2 may be provided in this order as in the transfer film 20 shown in fig. 2.

From the viewpoint of further improving the effect of the present invention, a transfer film having a temporary support, a conductive layer, and a photosensitive resin layer in this order is preferable. In addition, the transfer film having the above structure is also excellent in lamination properties. This is because bubbles or floating between the substrate and the photosensitive resin layer at the time of transfer is suppressed because the photosensitive resin layer has higher flexibility than the conductive layer.

For example, the transfer film may be stored directly in a flat plate form or wound into a roll form by a cylindrical winding core. When the transfer film is wound in a roll form, the transfer film is preferably wound so that the temporary support is positioned at the outermost side.

When the transfer film does not have a protective film, the transfer film can be stored in a flat plate shape.

The winding core is not particularly limited as long as it is a conventionally used winding core. Examples of the material constituting the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

The end face separator is preferably provided on the end face of the transfer film wound in a roll shape in terms of protection of the end face, and more preferably provided in terms of more excellent resistance to edge fusion. When the transfer film is packaged, it is preferably packaged so as to be wrapped in a black sheet having excellent moisture permeability.

[ use ]

The application of the transfer film is not particularly limited, and the transferred photosensitive resin layer is excellent in developability, and therefore the transfer film is preferably used as a transfer film for a laminate having a conductive pattern obtained by patterning a conductive layer having silver nanowires, and more preferably used as a transfer film for a touch panel.

[ method for producing laminate ]

A method for producing a laminate having a substrate and a conductive pattern using the transfer film of the present invention will be described below.

Examples of the method for producing the laminate include a method including the steps of: a step of bonding the transfer film and the substrate by bringing the substrate into contact with a surface of the transfer film opposite to the surface on which the temporary support is arranged (hereinafter, also referred to as "transfer step"); a step of pattern-exposing the photosensitive resin layer of the transfer film (hereinafter, also referred to as "exposure step"); and a step (hereinafter, also referred to as "developing step") of removing a part of the conductive layer together with an unexposed portion of the photosensitive resin layer to form a patterned conductive layer (conductive pattern).

By the above-described manufacturing method, a laminate including a substrate, a cured resin layer (cured film) obtained by curing the patterned photosensitive resin layer, and a patterned conductive layer is manufactured.

[ substrate ]

The substrate of the laminate is not particularly limited, and examples thereof include a glass substrate and a plastic substrate such as polycarbonate.

The thickness of the substrate can be appropriately selected according to the purpose of use. Also, the substrate may be film-shaped. Examples of the film-like substrate include a polyethylene terephthalate film, a polycarbonate film, and a cycloolefin polymer film.

The minimum light transmittance of the substrate in a wavelength region of 450 to 650nm is preferably 80% or more. When the substrate satisfies such conditions, the luminance of the display panel or the like can be easily increased.

Hereinafter, each step of the method for manufacturing a laminate will be described with reference to fig. 3A, 3B, and 3C.

Fig. 3A, 3B, and 3C are schematic diagrams for explaining an example of a method for manufacturing a laminate using transfer films. In the following description, a method of manufacturing the transfer film 10 shown in fig. 1 is described, but the method of manufacturing the laminate is not limited to the method of manufacturing the transfer film having the structure shown in fig. 1.

[ transfer Process ]

As shown in fig. 3A, in the transfer step, the transfer film 10 and the substrate 25 are bonded to produce a laminate 30. At this time, the surface of the transfer film 10 opposite to the temporary support 1 (i.e., the surface of the photosensitive resin layer 3) is in contact with the substrate 25.

In addition, in the case where the protective film 4 is provided as in the transfer film 10 shown in fig. 1, after removing the protective film 4, 3 layers of the temporary support 1, the conductive layer 2, and the photosensitive resin layer 3 are transferred onto the substrate 25.

In the transfer step, it is preferable that the photosensitive resin layer side of the transfer film is pressed against the substrate while heating the photosensitive resin layer and/or the substrate. In this case, the heating temperature and the pressure are not particularly limited, but the heating temperature is preferably 70 to 130 ℃ and the pressure is preferably 0.1 to 1.0MPa (1 to 10 kgf/cm)²Degree). Further, from the viewpoint of more excellent adhesiveness and conformability, it is preferable to carry out the reaction under reduced pressure.

In addition, a preheating treatment of the substrate may be performed before the transfer step instead of the heating treatment of the photosensitive resin layer and/or the substrate in the transfer step, so as to further improve the adhesion.

[ Exposure procedure ]

In the exposure step, pattern exposure is performed on the photosensitive resin layer 3 after the transfer step.

In the exposure step shown in fig. 3B, a part of the photosensitive resin layer 3 is exposed by irradiating actinic light L in an image-like manner through a mask pattern 5 called a stencil (artwork).

In the photosensitive resin layer 3, the photosensitive resin layer 3 is cured in a region (exposed portion) irradiated with the active light L to form a cured film 3 a. On the other hand, in the region (unexposed portion) not irradiated with the active light L, the photosensitive resin layer 3 is not cured.

As the light source of the active light in the exposure step, a known light source can be mentioned.

The light source is not particularly limited as long as it is a light source that efficiently irradiates light (for example, 365nm or 405nm) having a wavelength capable of exposing the photosensitive resin layer, and examples thereof include a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, and a xenon lamp.

Further, as the light source, an Ar ion laser and a semiconductor laser may be used, and a flood lamp for photography and a solar lamp may be used.

Further, by a direct imaging method using a laser exposure method or the like, a method of irradiating active light in an image form without using the mask pattern 5 can be employed.

The exposure amount in the exposure step varies depending on the apparatus used and the composition of the photosensitive resin layer, but is preferably 5 to 1000mJ/cm²More preferably 10 to 700mJ/cm². From the viewpoint of excellent photocurability, 10mJ/cm is preferable²As described above, from the viewpoint of resolution, 1000mJ/cm is preferable²The following.

The exposure environment in the exposure step is not particularly limited, and can be performed in air, nitrogen, or vacuum.

< stripping Process >

In the present manufacturing method, a peeling step of peeling the temporary support 1 from the laminate 30 is performed after the exposure step and before the development step. The peeling method is not particularly limited, and a known method can be appropriately used.

In the embodiment shown in fig. 3A, 3B, and 3C, the peeling step is performed after the exposure step of pattern-exposing the photosensitive resin layer 3 through the temporary support 1, but the peeling step of peeling the temporary support 1 from the laminate 30 may be performed before the exposure step.

It is preferable to perform pattern exposure through the temporary support 1 in order to prevent contamination due to contact between the conductive layer 2 and the mask pattern 5 and to avoid the influence of foreign matter adhering to the mask pattern 5 on the exposure. In other words, in the method for producing a laminate, the peeling step is preferably performed after the exposure step.

[ development procedure ]

In the developing step, the unexposed portions of the photosensitive resin layer 3 and a part of the conductive layer 2 are removed, whereby a patterned conductive layer (conductive pattern 2a) is formed.

Specifically, the uncured portion (unexposed portion) of the photosensitive resin layer 3 is removed by bringing the developer into contact with the exposed surface of the laminate 30 exposed by peeling of the temporary support 1. At this time, the region of the conductive layer 2 that contacts the unexposed portion is also removed together with the unexposed portion of the photosensitive resin 3. Thereby, the conductive pattern 2a composed of the patterned conductive layer 2 is formed, and the laminate 30 having the substrate 25, the conductive pattern 2a, and the cured film (cured resin pattern 3a) of the patterned photosensitive resin layer 3 is manufactured.

Examples of the developing solution include an aqueous alkaline solution, an aqueous developing solution, and an organic solvent developing solution. For example, the developing treatment in the developing step is carried out by a known method such as spraying, dipping by shaking, brushing, or doctor blade coating using these developing solutions.

The developer is preferably an alkaline aqueous solution because it is safe, stable and easy to handle. The alkaline aqueous solution is preferably 0.1 to 5 mass% sodium carbonate aqueous solution, 0.1 to 5 mass% potassium carbonate aqueous solution, 0.1 to 5 mass% sodium hydroxide aqueous solution, or 0.1 to 5 mass% sodium tetraborate aqueous solution.

The pH of the alkaline aqueous solution used as the developer is preferably in the range of 9 to 11. The temperature of the developing solution is adjusted according to the developability of the photosensitive resin layer. The alkaline aqueous solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like.

As the developer, an aqueous developer composed of water or an alkaline aqueous solution and 1 or more kinds of organic solvents can be used. Here, examples of the alkali contained in the aqueous alkali solution include sodium carbonate, potassium carbonate, sodium hydroxide, and sodium tetraborate as described above, and further include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, 3-propanediol, 1, 3-diaminopropanol-2, and morpholine.

Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. These may be used alone or in combination of 2 or more.

The content of the organic solvent in the aqueous developer is preferably 2 to 90% by mass based on the total mass of the aqueous developer. The temperature of the aqueous developing solution is adjusted according to the developability of the photosensitive resin layer. The pH of the aqueous developer is not particularly limited as long as the photosensitive resin layer can be developed, but is more preferably 8 to 12, and still more preferably 9 to 10.

The aqueous developer may contain a small amount of additives such as a surfactant and an antifoaming agent.

Examples of the organic solvent-based developer include 1, 1, 1-trichloroethane, N-methylpyrrolidone, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ -butyrolactone. In order to prevent the occurrence of fire, the organic solvent-based developer preferably contains water in an amount of 1 to 20% by mass.

The developing solution may be used in combination of 2 or more kinds as necessary.

Examples of the developing method include a dipping method, a spin immersion method, a spray method, a brush coating method, and a bar coating method (slapping). Among these, the use of the high-pressure spray method is preferable because the resolution is further improved.

In the method for manufacturing the laminated body 30 having the conductive pattern 2a, after the developing process, heating at 60 to 250 ℃ or exposure of 0.2 to 10J/cm can be performed as required²To further cure the conductive pattern 2 a.

[ use ]

The laminate having the conductive pattern obtained by the above-described production method can be suitably used for various applications. Examples of applications of the laminate having a conductive pattern include a touch panel (touch panel sensor), a semiconductor Chip, various electric wiring boards, an FPC (Flexible printed circuit), a COF (Chip on Film), a TAB (Tape Automated Bonding), an antenna, a multilayer wiring board, and a motherboard, and are preferably used for the touch panel sensor.

When the laminate is applied to a touch panel sensor, the conductive pattern of the laminate functions as a detection electrode or a lead line in the touch panel sensor.

The touch panel is not particularly limited as long as it has the touch panel sensor, and examples thereof include a touch panel sensor combined with various display devices (e.g., a liquid crystal display device and an organic EL (electro-luminescence) display device).

Known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method can be used as the touch panel sensor and the detection method in the touch panel. Among them, electrostatic capacitance type touch panel sensors and touch panels are preferable.

Examples of touch panel types include the so-called in-cell type (e.g., touch panels described in FIGS. 5, 6, 7, and 8 of Japanese patent laid-open No. 2012-517051), the so-called on-cell type (e.g., touch panel described in FIG. 19 of Japanese patent laid-open No. 2013-168125, and touch panels described in FIGS. 1 and 5 of Japanese patent laid-open No. 2012-089102), the OGS (One Glass Solution) type, TOL (Touch-on-Lens: cover Touch) type (e.g., Touch panel described in FIG. 2 of Japanese patent laid-open publication No. 2013-054727), various out-cell types (so-called GG, G1-G2, GFF, GF2, GF1, G1F, etc.), and other structures (e.g., Touch panel described in FIG. 6 of Japanese patent laid-open publication No. 2013-164871).

Examples of the touch panel include the touch panel described in paragraph 0229 of japanese patent application laid-open No. 2017-120345.

The method for manufacturing the touch panel is not particularly limited, and a known method for manufacturing a touch panel may be used except for using the touch panel sensor having the laminate.

Examples

The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the treatments, the procedures of the treatments, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the embodiments shown below. Unless otherwise specified, "part(s)" and "%" are based on mass.

[ preparation of coating liquid for Forming conductive layer (silver nanowire layer) (preparation of coating liquid for Forming conductive layer used in examples 1 to 22 and comparative example 1) ]

[ preparation of additive solution A ]

Silver nitrate powder (0.51 g) was dissolved in 50mL of pure water. 1mol/L of aqueous ammonia was added to the obtained liquid until the liquid became transparent. Then, pure water was added to the obtained liquid until the total amount of the liquid became 100mL, thereby preparing additive liquid a.

[ preparation of addition solution G ]

0.5G of glucose powder was dissolved in 140mL of pure water, whereby additive solution G was prepared.

[ preparation of addition solution H ]

HTAB (hexadecyl-trimethylammonium bromide) powder (0.5 g) was dissolved in 27.5mL of pure water, thereby preparing additive solution H.

[ preparation of coating liquid for Forming conductive layer (silver nanowire layer) ]

After pure water (410mL) was added to the three-necked flask, additive solution H (82.5mL) and additive solution G (206mL) were added to the flask via a funnel while stirring at 20 ℃. To the obtained liquid, additive solution A (206mL) was added at a flow rate of 2.0 mL/min and a stirring speed of 800rpm (fluctuations per minute). After 10 minutes, 82.5mL of additive solution H was added to the obtained liquid. After that, the obtained liquid was heated to an internal temperature of 75 ℃ at 3 ℃/min. Thereafter, the stirring speed was slowed down to 200rpm and heated for 5 hours. The obtained liquid was cooled, placed in a stainless steel cup, and subjected to ultrafiltration using an ultrafiltration apparatus in which an ultrafiltration module SIP1013 (manufactured by Asahi Kasei Corporation, molecular weight cut-off of 6,000), a magnetic pump, and a stainless steel cup were connected via a silicon tube. At the point when the filtrate from the module reached 50mL, 950mL of distilled water was added to the stainless steel cup and washed. After repeating the above washing 10 times, the mixture was concentrated until the liquid volume reached 50 mL. In addition, the additive solution a, the additive solution G, and the additive solution H were repeatedly prepared by the above method and used for preparing the silver nanowire solution.

To the silver nanowire solution prepared as described above, an aqueous solution (concentration 5 mass%) of polyvinyl alcohol (corresponding to PVA. kuraray co., manufactured by ltd. "PVA 204") in a desired ratio, an aqueous solution (concentration 5 mass%) of polyvinylpyrrolidone (corresponding to pvp. nippon SHOKUBAI co., manufactured by ltd., manufactured by "PVPK 30") in a desired ratio, a methanol solution (concentration 0.1 mass%) of 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (corresponding to "Omnirad TPO H" manufactured by TPO. IGM Resins b.v., manufactured by table), bis (2, 4, 6-trimethylbenzoyl) phenyl-phosphine oxide (corresponding to "Omnirad 819 b.v. manufactured by Omnirad 819) in a desired ratio (concentration 0.1 mass%) were added, and water and the methanol solution were further added to adjust the mass concentration, finally, water/methanol was set to 60/40 (mass ratio), thereby preparing coating liquid (a) for forming a conductive layer. The coating liquids (a) for forming a conductive layer obtained were used in examples 1 to 22 and comparative example 1.

[ preparation of coating liquid for Forming conductive layer (silver nanowire layer) (B) (preparation of coating liquid for Forming conductive layer used in comparative example 2) ]

To a 2000ml 3-neck flask, 500ml of ethylene glycol was added, and the mixture was heated to 160 ℃ by an oil bath under nitrogen atmosphere with stirring by a magnetic stirrer. To this was added dropwise 2mg of PtCl prepared separately₂Dissolved in 50ml of ethylene glycol. After 4-5 minutes, 5g of AgNO was added₃A solution dissolved in 300ml of ethylene glycol and 5g of polyvinylpyrrolidone having a weight average molecular weight of 4 ten thousand (manufactured by FUJIFILM Wako Pure Chemical Corporation) dissolved in 150ml of ethylene glycol were dropped from the respective dropping funnels for 1 minute, followed by stirring at 160 ℃ for 60 minutes.

The reaction solution was left at 30 ℃ or lower, diluted 10-fold with acetone, and centrifuged at 2000 rpm for 20 minutes by a centrifuge, whereby the supernatant was decanted. After acetone was added to the precipitate and stirred, centrifugation was performed under the same conditions as described above, and the acetone was decanted. Thereafter, the silver nanowires were obtained by performing centrifugal separation 2 times with distilled water as well.

An aqueous solution (concentration 5 mass%) of polyvinylpyrrolidone (corresponding to pvp. nippon SHOKUBAI co., ltd. "PVPK 30") and the obtained silver nanowires were added to pure water in a desired ratio, and water and methanol solution were further added to adjust the mass concentration, so that the water/methanol ratio was 60/40 (mass ratio), thereby preparing a coating liquid (B) for forming a conductive layer.

The coating liquid (B) for forming a conductive layer obtained was used in comparative example 2.

[ Synthesis of Polymer ]

[ raw materials ]

According to the following method, a polymer was synthesized. In the synthesis of the polymer, the following compounds were used.

< solvent >

N-propyl acetate

PGMEA: propylene glycol monomethyl ether acetate

Toluene

< polymerizable monomer >

Table 1 shows the composition of a monomer mixture containing a polymerizable monomer used for synthesizing a polymer. The polymerizable monomers used in each monomer mixture are as follows.

Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[ Table 1]

< polymerization initiator >

AIBN: azobisisobutyronitrile (V-60, manufactured by FUJIFILM Wako Pure Chemical Corporation)

[ measurement ]

The polymer synthesized in the present example was measured by a Gel Permeation Chromatography (GPC) method under the following conditions, and the value of the weight average molecular weight Mw was obtained by conversion using polystyrene as a standard substance.

< GPC conditions >

The device comprises the following steps: tosoh High Speed GPC apparatus HLC-8220GPC (trade name), manufactured by Tosoh Corporation

Protection of the column: HZ-L manufactured by Tosoh Corporation

Separating the column: series connection of 3 TSK gel Super HZM-N (trade name) manufactured by Tosoh Corporation

Measuring temperature: 40 deg.C

Eluent: THF (tetrahydrofuran)

Flow rate: sample pump 0.35 mL/min, control pump 0.20 mL/min

Injection amount: 10 μ L

A detector: differential refractometer

[ Synthesis of Polymer A1 ]

The mixed solution 1(100.0 parts), AIBN (1.0 part) and n-propyl acetate (12.4 parts) were mixed, and stirred at room temperature for 1 hour to dissolve solid AIBN, thereby preparing solution 1.

N-propyl acetate (111.6 parts) was added to the flask, and the temperature was raised to 80 ℃ under a nitrogen atmosphere. While maintaining the liquid temperature under stirring, the 1 st liquid was added to n-propyl acetate in the flask over 4 hours using a dropping pump. After the completion of the addition, the liquid temperature of the mixture was maintained at 80 ℃ with stirring to further react for 6 hours, whereby polymer a1 was synthesized. The weight average molecular weight of the obtained polymer a1 was 65,000.

[ Synthesis of Polymer A2 ]

Polymer a2 was synthesized in the same manner as in the synthesis of polymer A1, except that the mixed solution 1 was changed to mixed solution 2. The weight average molecular weight of the obtained polymer a2 was 65,000.

[ Synthesis of Polymer A3 ]

Polymer A3 was synthesized in the same manner as in the synthesis of polymer a1, except that the mixed solution 1 was changed to mixed solution 3. The weight average molecular weight of the obtained polymer a3 was 65,000.

[ Synthesis of Polymer A4 ]

PGMEA (55.8 parts) and toluene (55.8 parts) were mixed to prepare solution 1. Then, the mixed solution 1(100.0 parts), AIBN (1.0 part), PGMEA (6.2 parts), and toluene (6.2 parts) were mixed, and stirred at room temperature for 1 hour to dissolve solid AIBN, thereby preparing a solution 2.

The flask was charged with solution 1, and the temperature was raised to 80 ℃ under a nitrogen atmosphere. While maintaining the liquid temperature under stirring, the 2 nd liquid was added to the 1 st liquid in the flask over 4 hours by using a dropping pump. After the completion of the addition, the liquid temperature of the mixture was maintained at 80 ℃ with stirring to further react for 6 hours, whereby polymer a4 was synthesized. The weight average molecular weight of the obtained polymer a4 was 65,000.

[ example 1]

[ preparation of composition for negative photosensitive resin layer formation ]

A negative photosensitive resin layer forming composition was obtained by adding 63 parts by mass of polymer a1 as a binder polymer in terms of solid content, 37 parts by mass of pentaerythritol triacrylate ("a-TMM-3 LM-N" manufactured by ltd.) (corresponding to PETA in the table), SHIN-NAKAMURA CHEMICAL co., ltd., "a-TMM-3 LM-N") as a compound having an ethylenically unsaturated group, 10 parts by mass of 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (corresponding to Omnirad TPO H. igm Resins b.v. manufactured by Omnirad TPO h.v. in the table) as a photopolymerization initiator, 0.06 parts by mass of polyether modified silicone (DuPont Toray Specialty Materials k.k.k. manufactured by 8032ADDITIVE ") as a surfactant (leveling agent), and 100 parts by mass of N-propyl acetate.

[ transfer film production ]

As a temporary support, a particle having a thickness of 16 μm and a diameter of 5 μm or more on one surface was preparedAt 10 pieces/mm²The PET film of the above layer. After the composition for forming the negative photosensitive resin layer obtained above was stirred, 10 particles having a diameter of 5 μm or more existed per mm uniformly coated on the temporary support²The surface on the opposite side of the above surface. The obtained coating film was dried with hot air at 100 ℃ for 10 minutes by a hot air convection dryer, thereby forming a photosensitive resin layer.

Subsequently, the coating liquid (A) for forming a conductive layer (silver nanowire layer) obtained above was uniformly applied on the surface of the photosensitive resin layer obtained above until 25g/m was obtained²The obtained coating film was dried with hot air at 100 ℃ for 10 minutes by a hot air convection dryer. Thereby, a conductive layer containing silver nanowires as conductive fibers was formed on the photosensitive resin layer. The thickness of the conductive layer after drying was about 0.01. mu.m.

A protective film made of polyethylene (trade name "NF-13" manufactured by ltd.) was attached to the surface of the formed conductive layer to form a protective film, thereby obtaining a transfer film. The total thickness of the conductive layer and the photosensitive resin layer after drying was about 5 μm.

[ example 2]

[ adjustment of composition for negative-type photosensitive resin layer formation ]

A negative photosensitive resin layer forming composition was obtained by adding 63 parts by mass of polymer a1 as a binder polymer in terms of solid content, 37 parts by mass of pentaerythritol triacrylate ("a-TMM-3 LM-N" manufactured by ltd.) (corresponding to PETA in the table), SHIN-NAKAMURA CHEMICAL co., ltd., "a-TMM-3 LM-N") as a compound having an ethylenically unsaturated group, 10 parts by mass of bis (2, 4, 6-trimethylbenzoyl) phenyl-phosphine oxide (corresponding to Omnirad 819. IGM Resins b.v. manufactured by ltd., "Omnirad 819") as a photopolymerization initiator, 0.06 parts by mass of 8032ADDITIVE (polyether-modified silicone) as a surfactant (leveling agent), and 100 parts by mass of N-propyl acetate.

[ transfer film production ]

As a temporary supportParticles having a thickness of 16 μm and a diameter of 5 μm or more on one surface were prepared and present at 10 particles/mm²The PET film of the above layer. The temporary support has 10 particles with diameter of 5 μm or more per mm²The surface on the opposite side to the above surface was uniformly coated with the coating liquid (A) for forming a conductive layer obtained above until the coating liquid became 25g/m²The obtained coating film was dried with hot air at 100 ℃ for 10 minutes by a hot air convection dryer. After drying, the mixture was pressurized at room temperature (25 ℃ C.) with a linear pressure of 10 kg/cm. Thereby, a conductive layer containing silver nanowires as conductive fibers is formed on the temporary support. The thickness of the conductive film after drying was about 0.01 μm.

Next, the negative photosensitive resin layer-forming composition obtained above was stirred and then uniformly applied to the surface of the formed conductive layer. The obtained coating film was dried with hot air at 100 ℃ for 10 minutes by a hot air convection dryer, thereby forming a photosensitive resin layer.

A protective film made of polyethylene (trade name "NF-13" manufactured by ltd.) was attached to the surface of the formed photosensitive resin layer to form a protective film, thereby obtaining a transfer film.

The total thickness of the conductive layer and the photosensitive resin layer after drying was about 5 μm.

[ examples 3 to 22]

Transfer films of examples 3 to 22 were produced in the same manner as in example 2 except that the composition of the coating liquid (a) for forming a conductive layer and the composition for forming a negative photosensitive resin layer were changed to the compositions shown in table 2.

Comparative example 1

A transfer film of comparative example 1 was produced in the same manner as in example 2 except that the composition of the coating liquid (a) for forming a conductive layer and the composition of the negative photosensitive resin layer were changed to the compositions shown in table 2.

Comparative example 2

A transfer film of comparative example 2 was produced in the same manner as in example 2, except that the coating liquid (a) for forming a conductive layer was changed to the coating liquid (B) for forming a conductive layer, and the compounding ratio of the negative photosensitive resin layer-forming composition was changed to the compounding ratio shown in table 2.

[ analysis of Components in the conductive layer and the photosensitive resin layer in examples 1 to 22 and comparative examples 1 and 2]

Next, it was confirmed by the following method whether or not an organic phosphorus compound containing P ═ O in the molecule existed in the conductive layer and the photosensitive resin layer.

The detection of an organophosphorus compound containing P ═ O in the molecule was carried out by the following method: by using Ar⁺The cluster ion gun was passed through a time-of-flight secondary ion mass spectrometer ("SIMS 5" manufactured by TOF-SIMS, ionto GmbH) while cutting the film in the depth direction, and the peak intensity of the specific fragment ion caused by the molecule present in the film thickness direction from the surface of the photosensitive resin layer of the transfer film to the surface of the conductive layer facing the temporary support was measured (in addition, in example 1, the peak intensity of the specific fragment ion caused by the molecule present in the depth direction from the surface of the conductive layer on the side opposite to the temporary support to the conductive layer and the photosensitive resin layer was measured, and in examples 2 to 22 and comparative examples 1 and 2, the peak intensity of the specific fragment ion caused by the molecule present in the depth direction from the surface of the photosensitive resin layer on the side opposite to the temporary support to the surfaces of the photosensitive resin layer and the conductive layer facing the temporary support was measured).

More specifically, in example 1, measurement was performed from the conductive layer side, and in the obtained silver distribution in the depth direction, it was measured whether or not the peak of the P (phosphorus) segment was detected in a region between a position of the intensity (hereinafter, also referred to as "maximum value") at which the secondary ion intensity derived from silver became maximum and a position closer to the photosensitive resin layer side than the maximum value and equal to or less than a value half the maximum value (that is, a region corresponding to the half-width half-maximum portion of the intensity (maximum value) at which the secondary ion intensity derived from silver became maximum).

In examples 2 to 22 and comparative examples 1 and 2, measurement was performed from the photosensitive resin layer side, and in the obtained silver distribution in the depth direction, whether or not the peak of the P (phosphorus) fragment was detected was measured in a region between a position closer to the photosensitive resin layer side than the intensity (maximum value) at which the secondary ion intensity derived from silver became maximum and equal to or less than a value half of the maximum value and a position closer to the temporary support side than the intensity (maximum value) at which the secondary ion intensity derived from silver became maximum and equal to or less than a value half of the maximum value (that is, a region corresponding to a full width half maximum portion of the intensity (maximum value) at which the secondary ion intensity derived from silver became maximum).

< detection of organic phosphorus Compound containing P ═ O in the molecule >

Within the range of the measurement region specified by TOF-SIMS, it was confirmed whether or not a fragment derived from P ═ O was detected, and classification was performed according to the following criteria. The results are shown in Table 2.

"A": detect the presence of

"B": not detected

[ evaluation ]

[ production of a laminate having a conductive pattern ]

< formation of conductive Pattern >

The transfer films of the examples and comparative examples from which the protective film was peeled were laminated to a transparent film substrate (cycloolefin polymer film, thickness: 38 μm, refractive index: 1.53) (transfer step), to produce a laminate.

Vacuum laminator made of MCK co, LTD, at the temperature of the transparent film substrate: 40 ℃ and temperature of rubber roller: 100 ℃, line pressure: 3N/cm and conveying speed: the transfer step was performed at 2 m/min. In the transfer step, the surface exposed by peeling the protective film from the transfer film is brought into contact with the surface of the transparent film substrate.

< production of transparent electrode Pattern film >

Using the obtained laminate, a transparent electrode pattern film was produced in the following order.

An exposure mask having a mask pattern (quartz exposure mask having a pattern for forming a transparent electrode) was brought into close contact with the temporary support, and then the temporary support was subjected to an ultrahigh pressureProximity exposure machine for mercury lamp [ manufactured by Hitachi High-Tech Corporation, exposure main wavelength: 365nm (i-ray), and exposing to an exposure dose of 100mJ/cm through an exposure mask and a temporary support²Pattern exposure was performed.

After the exposure step, the temporary support is peeled from the laminate (peeling step).

After the stripping step, a development treatment (development step) was performed for 60 seconds using a1 mass% aqueous solution of sodium carbonate having a liquid temperature of 32 ℃. By this development treatment, the unexposed photosensitive resin layer and the conductive layer laminated on the unexposed photosensitive resin layer are removed from the laminate.

After the development treatment, the surface of the laminate on the side where the photosensitive resin layer and the conductive layer are formed is sprayed with ultrapure water from an ultrahigh-pressure cleaning nozzle, whereby the residue of the photosensitive resin layer is removed from the surface of the transparent film substrate. The laminate from which the residue was removed was subjected to air blowing to remove moisture and then dried, thereby obtaining each of the transparent electrode pattern films (corresponding to the laminate having the conductive pattern) of the examples and comparative examples having the substrate, the transparent electrode pattern containing the silver nanowires, and the cured film obtained by curing the composition for forming the photosensitive resin layer. The transparent electrode pattern film having the patterned silver nanowire layer is a so-called circuit substrate.

< evaluation of adhesion >

Using the obtained transparent electrode pattern film (corresponding to a laminate having a conductive pattern), reference is made to JIS-K5400: 1990, a 100-grid cutting test was performed. A cutting mark of a checkerboard pattern of 1mm square was cut into the surface of the transparent electrode pattern film with an art knife. Subsequently, a transparent adhesive tape #600(3M Japan Limited) was strongly pressure-bonded to the surface of the transparent electrode pattern film cut into the cut mark, and then the transparent adhesive tape was peeled off in the 180 ℃ direction. The state of the checkerboard after the peeling was observed, and the adhesion between the conductive layer and the cured film formed of the photosensitive resin layer was evaluated according to the following evaluation criteria. The results are shown in Table 2.

"A": almost 100% of the total area is coherent.

"B": a portion of 80% or more and less than 100% of the total area remains coherent.

"C": a portion of 40% or more and less than 80% of the total area remains coherent.

"D": less than 40% of the total area remains coherent.

Table 2 is shown below.

The abbreviations for the respective components shown in table 2 are as follows.

(conductive layer)

"AgNW": silver nanowires

"PVA": polyvinyl alcohol

"PVP": polyvinylpyrrolidone

"Omnirad 819": bis (2, 4, 6-trimethylbenzoyl) phenyl-phosphine oxide (Omnirad 819, manufactured by IGM Resins B.V.)

"Omnirad TPO H": 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.)

(photosensitive resin layer)

"MEK": methyl ethyl ketone

"PGMEA": propylene glycol monomethyl ether acetate

"PETA": pentaerythritol triacrylate (SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd. "A-TMM-3 LM-N")

"TMPTA": trimethylolpropane triacrylate (SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd. "A-TMPT")

"NDA": 1, 9-nonanediol diacrylate (SHIN-NAKAMURA CHEMICAL Co., Ltd. "A-NOD-N" manufactured by Ltd.)

"Omnirad 819": bis (2, 4, 6-trimethylbenzoyl) phenyl-phosphine oxide (Omnirad 819, manufactured by IGM Resins B.V.)

"Omnirad TPO H": 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.)

"Omnirad 379 EG": 2-dimethylamino-2- (4-methoxy-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (IGM Resins B.V. "Omnirad 379 EG" manufactured)

"8032 addition": polyether modified Silicone (DuPont Toray Specialty Materials K.K. product.)

"PM-21": KAYAMER PM-21 (methacryloyl group-containing phosphate ester Compound Nippon Kayaku Co., Ltd., manufactured by Ltd.)

In the column of "layer structure" in table 2, "a" means a transfer film in which a temporary support, a photosensitive resin layer, and a conductive layer are sequentially stacked, and "B" means a transfer film in which a temporary support, a conductive layer, and a photosensitive resin layer are sequentially stacked.

In table 2, "the content (mass%) of the P ═ O compound in the conductive layer" means the content (mass%) of the organic phosphorus compound having P ═ O bonds in the molecule based on the total mass of the conductive layer. The content (mass%) of the organic phosphorus compound having P ═ O bonds in the molecule based on the total solid content of the conductive layer forming coating liquid.

The content of each component in the column of "coating liquid for forming conductive layer" in table 2 means the solid content concentration (mass%).

The content of each component in the column of "composition for forming negative photosensitive resin layer" in table 2 is based on parts by mass. The content of each component other than the solvent is a content of a solid component. In addition, if a photosensitive resin layer is formed, the photosensitive resin layer is considered to be a solid component even if it is in a liquid state.

In table 2, "detection of P ═ O compound in the conductive layer (TOF-SIMS)" means the result of detection of a phosphorus compound containing P ═ O bond in the molecule in the measurement by TOF-SIMS, and "a" indicates the case of detection and "B" indicates the case of no detection.

As is clear from the results in table 2, the transfer film according to the example exhibited excellent adhesion between the patterned cured resin layer formed by exposure of the photosensitive resin layer and the patterned conductive layer in the formed conductive pattern.

Further, as is clear from a comparison between example 1 and example 3, when the transfer film has a structure in which the temporary support, the conductive layer, and the photosensitive resin layer are provided in this order, the adhesion is further excellent.

Further, as is clear from comparison between example 2 and example 3, the specific phosphorus compound contained in the conductive layer is represented by the general formula (P1) and R^X1And R^X2Each independently represents an aromatic hydrocarbon group, R^X3Is represented by^X1An aromatic hydrocarbon group-containing compound is more excellent in adhesion.

Further, as is clear from the comparison of examples 3 to 8, when the content of the specific phosphorus compound in the conductive layer is 0.05 to 15.0 mass% with respect to the total mass of the conductive layer, the adhesion is more excellent.

As is clear from comparison among examples 3, 9, 10, 16, and 17, when the content of PVP in the conductive layer is 60 mass% or more (preferably 80 mass% or more) with respect to the total mass of the binder polymer, the adhesion is more excellent.

As is clear from comparison among examples 3, 18, and 19, the binder polymer in the photosensitive resin layer contains at least 1 kind selected from structural units derived from methacrylic acid and structural units derived from alkyl methacrylate and at least 1 kind selected from structural units derived from acrylic acid and structural units derived from alkyl acrylate, and the adhesion is more excellent when the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is 60/40 to 80/20 in terms of a mass ratio with respect to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

As is clear from comparison among examples 3, 11 and 20, when the photosensitive resin layer contains an ethylenically unsaturated compound having 3 or more functions (preferably, a 3-or 4-functional ethylenically unsaturated compound), the adhesiveness is more excellent.

On the other hand, the transfer film of the comparative example was found to be unsatisfactory.

In comparative example 1 and comparative example 2, it was confirmed that no P ═ O compound was detected in the conductive layer by measurement based on TOF-SIMS. That is, it was confirmed that the P ═ O compound "Omnirad TPO H" contained in the photosensitive resin layer was not impregnated into the conductive layer.

[ confirmation of touch Panel operation ]

Touch panels were produced using the transfer films of examples 1 to 22.

In place of the transparent film substrate, a transparent electrode pattern film was produced in the procedure described in [ production of laminate having conductive pattern ] above, except that a cycloolefin polymer film (thickness: 38 μm, refractive index: 1.53) having a copper electrode as extraction wiring on the surface thereof was used, and the surface exposed by peeling off the protective film in the transfer step was brought into contact with the surface of the cycloolefin polymer film on the side where the copper electrode was formed.

An electrostatic capacitance type touch panel sensor was produced by using the obtained transparent electrode pattern film in accordance with the method described in japanese patent No. 6173831. The operation of the touch panel sensor thus fabricated was confirmed and all the sensors were operated normally.

Description of the symbols

1-temporary support, 2-conductive layer, 2 a-conductive pattern, 3-photosensitive resin layer, 3 a-cured resin pattern, 4-protective film, 5-mask pattern, 10, 20-transfer film, 25-substrate, 30-laminate, L-active ray.

Claims (16)

1. A transfer film having a temporary support, a conductive layer and a photosensitive resin layer,

the photosensitive resin layer contains a binder polymer, a compound having an ethylenically unsaturated group, and a photopolymerization initiator,

the conductive layer contains an organophosphorus compound containing a P ═ O bond in the molecule.

2. The transfer film according to claim 1, which comprises the temporary support, the conductive layer, and the photosensitive resin layer in this order.

3. The transfer film according to claim 1 or 2,

the conductive layer further contains silver nanowires.

4. The transfer film according to any one of claims 1 to 3,

the organophosphorus compound includes a compound represented by the following general formula (P1),

in the formula, R^X1And R^X2Each independently represents an aromatic hydrocarbon group, R^X3Is represented by^X1-aromatic hydrocarbon radical, L^X1Represents a single bond or a 2-valent linking group.

5. The transfer film according to any one of claims 1 to 4,

the content of the organic phosphorus compound is 0.05 to 15.0 mass% with respect to the total mass of the conductive layer.

6. The transfer film according to any one of claims 1 to 5,

the photopolymerization initiator contains a P ═ O bond in the molecule.

7. The transfer film according to claim 6,

the photopolymerization initiator is 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide.

8. The transfer film according to any one of claims 1 to 7,

the content of the photopolymerization initiator is 0.05-0.5 by mass relative to the content of the compound having an ethylenically unsaturated group.

9. The transfer film according to any one of claims 1 to 8,

the compound having an ethylenically unsaturated group contains an ester bond.

10. The transfer film according to any one of claims 1 to 9,

the compound having an ethylenically unsaturated group contains 3 or 4 ethylenically unsaturated groups in the molecule.

11. The transfer film according to any one of claims 1 to 10,

the photosensitive resin layer further contains a phosphate ester compound.

12. The transfer film according to any one of claims 1 to 11,

the binder polymer contains at least 1 kind selected from structural units derived from methacrylic acid and structural units derived from alkyl methacrylate and at least 1 kind selected from structural units derived from acrylic acid and structural units derived from alkyl acrylate, and the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is 60/40-80/20 in terms of mass ratio relative to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.

13. A method for manufacturing a laminate having a substrate and a conductive pattern, the method comprising:

bonding the transfer film according to any one of claims 1 to 12 to the substrate by bringing the substrate into contact with a surface of the transfer film opposite to a surface on which the temporary support is arranged;

a step of pattern-exposing the photosensitive resin layer of the transfer film; and

and a step of forming a patterned conductive layer by removing a part of the conductive layer included in the transfer film together with an unexposed portion of the photosensitive resin layer.

14. A laminate produced by the production method according to claim 13,

the laminate comprises a substrate, a patterned conductive layer, and a patterned cured resin layer.

15. A touch panel sensor having the laminate according to claim 14.

16. A touch panel having the touch panel sensor of claim 15.

Images