CN113994262A

CN113994262A - Photosensitive transfer member, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel

Info

Publication number: CN113994262A
Application number: CN202080044332.3A
Authority: CN
Inventors: 两角一真; 有富隆志; 藤本进二
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2019-08-20
Filing date: 2020-06-29
Publication date: 2022-01-28
Also published as: WO2021033429A1; JP7312258B2; JPWO2021033429A1

Abstract

The invention provides a photosensitive transfer member with excellent resolution and high-speed lamination performance, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel. The photosensitive transfer member comprises a temporary support, an intermediate layer and a photosensitive resin layer in this order, wherein the intermediate layer comprises a thermoplastic resin layer, the thickness of the photosensitive resin layer is less than 5 [ mu ] m, and the total thickness of the temporary support and the intermediate layer is 35 [ mu ] m or less.

Description

Photosensitive transfer member, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel

Technical Field

The present invention relates to a photosensitive transfer member, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.

Background

In a display device (such as an organic Electroluminescence (EL) display device and a liquid crystal display device) including a touch panel such as a capacitive input device, a conductive layer pattern such as a sensor electrode pattern corresponding to a visual recognition portion, a peripheral wiring portion, and a wiring for a lead-out wiring portion is provided inside the touch panel.

In general, in the formation of a patterned layer, since the number of steps for obtaining a desired pattern shape is small, a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate through a mask having a desired pattern by using a photosensitive transfer member and then developing the layer is widely used.

For example, patent document 1 discloses a pattern forming material having a buffer layer and a photosensitive resin layer in this order on a support.

Patent document 2 discloses a photosensitive resin laminate including an intermediate layer and a photosensitive resin layer, each of which has a layer thickness of 0.1 to 10 μm, on a support film.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2007-178459

Patent document 2: international publication No. 2007/125992

Disclosure of Invention

Technical problem to be solved by the invention

As a result of an investigation of the photosensitive transfer member described in patent document 1, the inventors of the present invention have determined that there is room for improvement in resolution particularly when a pattern having a high resolution of 10 μm or less is formed.

Further, in the field of dry films, a method of producing the film by a roll-to-roll method is known, and in recent years, a dry film capable of being laminated at a high speed is required for improving productivity.

The inventors of the present invention have found that there is a problem in the lamination property at high speed as a result of an investigation of the photosensitive transfer member described in patent document 2.

Accordingly, an object of the present invention is to provide a photosensitive transfer member having excellent resolution and high-speed laminatability, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.

Means for solving the technical problem

The inventors of the present invention have conducted extensive studies to achieve the above object and, as a result, have found that a photosensitive transfer member having a temporary support, an intermediate layer including at least a thermoplastic resin layer, and a photosensitive resin layer in this order and having a thickness of the photosensitive resin layer and a total thickness of the temporary support and the intermediate layer adjusted within a predetermined range is excellent in resolution and high-speed laminatability, and have completed the present invention.

That is, the present inventors have found that the above-mentioned problems can be achieved by the following constitution

[1] A photosensitive transfer member comprising a temporary support, an intermediate layer and a photosensitive resin layer in this order,

the intermediate layer has a thermoplastic resin layer,

the thickness of the photosensitive resin layer is less than 5 [ mu ] m, and the total thickness of the temporary support and the intermediate layer is 35 [ mu ] m or less.

[2] The photosensitive transfer member according to [1], wherein,

the intermediate layer further has a water-soluble resin layer,

the water-soluble resin layer is between the thermoplastic resin layer and the photosensitive resin layer.

[3] The photosensitive transfer member according to [1] or [2], wherein,

the thickness of the thermoplastic resin layer is 10 [ mu ] m or less.

[4] The photosensitive transfer member according to any one of [1] to [3], wherein,

the ratio of the total thickness of the temporary support and the intermediate layer to the thickness of the photosensitive resin layer is 6.0 to 12.0.

[5] The photosensitive transfer member according to any one of [1] to [4], wherein,

the glass transition temperature of the thermoplastic resin contained in the thermoplastic resin layer is 100 ℃ or lower.

[6] The photosensitive transfer member according to any one of [1] to [5], wherein,

the thermoplastic resin layer has a plasticizer.

[7] The photosensitive transfer member according to any one of [1] to [6], wherein,

the viscosity of the thermoplastic resin layer is lower than that of the photosensitive resin layer at 70 ℃.

[8] The photosensitive transfer member according to any one of [1] to [7], wherein,

the thickness of the temporary support is 25 μm or less.

[9] The photosensitive transfer member according to any one of [1] to [8], wherein,

the temporary support has a haze of 0.5 or less.

[10] The photosensitive transfer member according to any one of [1] to [9], wherein,

the temporary support has a layer containing particles on the surface on the opposite side of the intermediate layer,

the particles contained in the particle-containing layer have an average particle diameter of 30 to 600 nm.

[11] The photosensitive transfer member according to any one of [1] to [10], wherein,

the photosensitive resin layer is a negative photosensitive resin layer.

[12] A method of manufacturing a resin pattern, comprising: a step of bringing a surface of the photosensitive resin layer of the photosensitive transfer member according to any one of [1] to [11], which surface is opposite to the intermediate layer, into contact with a substrate having a conductive layer and bonding the substrate;

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

and developing the exposed photosensitive resin layer to form a resin pattern.

[13] A method of manufacturing a circuit wiring, comprising: a step of bringing a surface of the photosensitive resin layer of the photosensitive transfer member according to any one of [1] to [11], which surface is opposite to the intermediate layer, into contact with a substrate having a conductive layer and bonding the substrate;

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

a step of forming a resin pattern by developing the exposed photosensitive resin layer; and

and etching the substrate in a region where the resin pattern is not disposed.

[14] A method of manufacturing a touch panel, comprising: a step of bringing a surface of the photosensitive resin layer of the photosensitive transfer member according to any one of [1] to [11], which surface is opposite to the intermediate layer, into contact with a substrate having a conductive layer and bonding the substrate;

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

and etching the substrate in a region where the resin pattern is not disposed.

Effects of the invention

According to the present invention, it is possible to provide a photosensitive transfer member excellent in resolution and high-speed laminatability, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of an embodiment of the photosensitive transfer member of the present invention.

Fig. 2 is a schematic view showing the pattern a.

Fig. 3 is a schematic view showing the pattern B.

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.

In the present specification, the numerical range expressed by the term "to" means a range in which the numerical values before and after the term "to" are included as the lower limit value and the upper limit value.

In the present specification, one kind of substance corresponding to each component may be used alone for each component, or two or more kinds may be used simultaneously. Here, when two or more substances are used together for each component, the content of the component refers to the total content of the substances used together unless otherwise specified.

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

[ photosensitive transfer Member ]

The photosensitive transfer member of the present invention comprises a temporary support, an intermediate layer, and a photosensitive resin layer in this order.

Here, the intermediate layer means all layers located between the temporary support and the photosensitive resin layer, and the photosensitive transfer member of the present invention includes at least a thermoplastic resin layer.

In the photosensitive transfer member of the present invention, the thickness of the photosensitive resin layer is less than 5 μm, and the total thickness of the temporary support and the intermediate layer is 35 μm or less.

The photosensitive transfer member of the present invention having such a structure is excellent in resolution and high-speed lamination properties.

Although the specific reason is not clear, the inventors of the present invention speculate as follows.

In a film having a photosensitive resin layer of less than 5 μm, when a photosensitive transfer member is laminated on a substrate at high speed, air bubbles generated between the photosensitive transfer member and the substrate may be occluded to cause pattern failure. However, it is considered that by forming the photosensitive transfer member to have the temporary support, the thermoplastic resin layer, and the photosensitive resin layer in this order, bubbling when laminating the photosensitive transfer member on the substrate can be reduced, and the photosensitive resin layer can follow the substrate, so that the lamination property at high speed can be improved.

In the present disclosure, the lamination property at a high speed is preferably lamination conditions at a line speed of 2.0 m/min or more, and more preferably lamination conditions at a line speed of 4.0m/min or more.

Further, it is considered that by setting the thickness of the photosensitive resin layer to less than 5 μm, development proceeds rapidly even in the case of a fine pattern, and a pattern having excellent resolution can be formed without causing a pattern collapse or a connection phenomenon.

Further, it is considered that when the total thickness of the temporary support and the intermediate layer is set to 35 μm or less, diffraction of light occurring in the distance from the mask to the photosensitive resin layer can be suppressed at the time of pattern exposure, and the pattern becomes clear and a high-resolution pattern can be formed.

[ temporary support body ]

The photosensitive transfer member of the present invention has a temporary support.

The temporary support is a releasable support.

In the case where the photosensitive resin layer is pattern-exposed, the temporary support used in the present invention preferably has light transmittance from the viewpoint that the photosensitive resin layer can be exposed through the temporary support.

Having light transmittance means that the transmittance of the dominant wavelength of light used in pattern exposure is 50% or more, and from the viewpoint of improving exposure sensitivity, the transmittance of the dominant wavelength of light used in pattern exposure is preferably 60% or more, and more preferably 70% or more. As a method for measuring the transmittance, a method of measuring the transmittance using OTSUKA ELE CTRONICS co.

Examples of the temporary support include a glass substrate, a resin film, and paper, and the resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, and a polyimide film. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is preferably 25 μm or less, more preferably 20 μm or less, for the reason that the resolution of the photosensitive transfer member can be favorably changed. From the viewpoint of transportability and supportability, the lower limit is preferably 5 μm or more, and more preferably 10 μm or more.

The thickness of the temporary support can be measured by the following method.

In the observation image of the cross section of the temporary support in the thickness direction, the arithmetic mean of the thicknesses of the temporary supports measured at 10 points selected at will was obtained, and the obtained value was taken as the thickness of the temporary support. A cross-sectional observation image of the temporary support in the thickness direction can be obtained by a Scanning Electron Microscope (SEM).

The haze of the temporary support is preferably 0.5 or less, more preferably 0.4 or less, and further preferably 0.3 or less, for the reason that the resolution of the photosensitive transfer member is favorably changed. The lower limit is not particularly limited, and may be more than 0.0.

The haze of the temporary support can be measured as the total haze using a haze meter (apparatus name: NDH2000, NIPPON DE NSHOKU INDUSTRIES Co., LTI).

The temporary support preferably has a layer containing particles on the surface on the side opposite to the intermediate layer. The average particle diameter of the particles contained in the particle-containing layer is preferably 30 to 600nm, more preferably 30 to 200nm, and still more preferably 40 to 100 nm. When the average particle diameter of the particles contained in the particle-containing layer is 30nm or more, the lamination property of the photosensitive transfer member at high speed is favorably changed, and when the average particle diameter of the particles contained in the particle-containing layer is 600nm or less, the resolution of the photosensitive transfer member is more excellent.

The average particle diameter of the particles contained in the particle-containing layer can be measured by the following method.

In the cross-sectional observation image of the temporary support in the thickness direction, the layer containing the particles is determined as a layer containing the particles.

Next, a Transmission Electron Microscope (TEM) was used to photograph any 5 positions of the cross section of the particle-containing layer at a magnification of 20000 times and an acceleration voltage of 100kV, and a cross-sectional photograph was obtained. The diameters of all the particles in the obtained cross-sectional photograph were measured, and the average value (arithmetic mean particle diameter) was obtained as the mean particle diameter of the particles. In addition, significantly large aggregates (foreign matter, garbage, etc.) are not counted.

Examples of the particles contained in the particle-containing layer include inorganic particles and organic particles.

Examples of the inorganic particles include silica (silica) particles, titania (titania) particles, zirconia (zirconium) particles, magnesia (magnesia) particles, alumina (alumina) particles, and the like, and among these, silica particles are particularly preferable.

Examples of the organic particles include acrylic resin particles, polyester particles, polyurethane particles, polycarbonate particles, polyolefin particles, and polystyrene particles.

The particle-containing layer may contain 1 kind of the particles alone, or may contain 2 or more kinds of the particles.

The content of the particles in the particle-containing layer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 5% by mass, from the viewpoints of ease of surface roughness control and wrinkle generation suppression during transportation.

The particles in the particle-containing layer may be present inside the particle-containing layer or may be partially exposed on the surface of the particle-containing layer. For example, in the case where the surface of the temporary support opposite to the intermediate layer has the layer containing the particles, the particles may be exposed to the surface of the temporary support opposite to the intermediate layer.

The material other than the particles contained in the particle-containing layer is not particularly limited, and may include, for example, the same material as that of the temporary support. The particle-containing layer preferably contains a resin, and particularly preferably contains an acrylic resin. The particle-containing layer may contain 1 kind of resin alone, or 2 or more kinds of resins.

The thickness of the particle-containing layer is preferably 5 to 300nm, more preferably 10 to 100nm, and particularly preferably 30 to 70nm, from the viewpoint of improving the resolution and the high-speed lamination property of the photosensitive transfer member. The particle-containing layer may be 1 layer or 2 layers. In the case where the particle-containing layer is 2 or more layers, a preferable thickness of the particle-containing layer is a preferable thickness of the particle-containing layer for each layer.

The thickness of the particle-containing layer can be measured by the same method as the thickness of the temporary support.

Examples of commercially available temporary supports having the particle-containing layer include lumiror (registered trademark), 12QS62, lumiror 16KS40, and 16FB40 (both manufactured by "inlet INDUSTRIES").

Further, it is preferable that the film used as the temporary support is free from deformation, damage, and the like such as wrinkles.

From the viewpoint of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, or defects contained in the temporary support is preferably small. The number of particles or foreign matter or defects having a diameter of 1 μm or more is preferably 50/10 mm²Hereinafter, more preferably 10 pieces/10 mm²Hereinafter, more preferably 3/10 mm²The average particle size is preferably 0/10 mm²。

Preferable examples of the temporary support are described in paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of International patent application laid-open No. 2012/081680, and paragraphs 0029 to 0040 of International patent application laid-open No. 2018/179370, the contents of which are incorporated herein by reference.

[ intermediate layer ]

The photosensitive transfer member of the present invention has an intermediate layer including at least a thermoplastic resin layer between a temporary support and a photosensitive resin layer.

The thickness of the intermediate layer may be set to a thickness of 35 μm or less in total of the temporary support and the intermediate layer, but is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less, from the viewpoint of excellent development speed of the photosensitive transfer member and favorable change in resolution. The lower limit is preferably 2 μm or more, and more preferably 4 μm or more, because the change in the laminatability of the photosensitive transfer member at high speed is favorable.

In the present invention, as described above, the total thickness of the temporary support and the intermediate layer may be 35 μm or less, but is preferably 34 μm or less, and more preferably 32 μm or less. The lower limit is preferably 10 μm or more because the change in the lamination property at high speed of the photosensitive transfer member is good.

In the present invention, the ratio (thickness B/thickness a) of the total thickness (hereinafter, abbreviated as "thickness B") of the temporary support and the intermediate layer to the thickness (hereinafter, abbreviated as "thickness a") of the photosensitive resin layer described later is preferably 6.0 to 12.0, more preferably 7.0 to 11.5, and further more preferably 8.0 to 10.5, from the viewpoint of better resolution of the photosensitive transfer member.

The thicknesses of the intermediate layer and the photosensitive resin layer can be measured by the same method as the thickness of the temporary support.

< thermoplastic resin layer >

As described above, the intermediate layer has at least a thermoplastic resin layer.

The thermoplastic resin layer preferably has no photosensitivity, and preferably has no photopolymerization initiator.

(thermoplastic resin)

The thermoplastic resin layer preferably has a thermoplastic resin.

The thermoplastic resin is not particularly limited as long as it is a resin plasticized by heat, and examples thereof include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, polyalkylene glycols, and the like. Among them, the thermoplastic resin is preferably an acrylic resin from the viewpoint of developability and transferability.

Here, the acrylic resin means a resin having at least 1 structural unit selected from the group consisting of a structural unit formed by (meth) acrylic acid, a structural unit formed by (meth) acrylic acid ester, and a structural unit formed by (meth) acrylic acid amide, and the content of the structural unit is preferably 50% by mass or more with respect to the total mass of the resin.

The thermoplastic resin preferably contains a polymer having an acid group because the developing speed is improved.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonate group, and among them, a carboxyl group is preferably used.

From the viewpoint of improving the developing speed, the acid value of the polymer having an acid group as the thermoplastic resin is preferably 60mgKOH/g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more.

The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins. For example, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of Japanese patent application laid-open No. 2011-95716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of Japanese patent application laid-open No. 2010-237589, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the binder polymer described in paragraphs 0053 to 0068 of Japanese patent application laid-open No. 2016-224162 are preferable.

The copolymerization ratio of the monomer having a carboxyl group in the above-mentioned carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

From the viewpoint of alkali developability, the acid value of the thermoplastic resin is preferably 60mgKOH/g to 200mgKOH/g, and more preferably 60mgKOH/g to 180 mgKOH/g.

Here, the acid value is the mass [ mg ] of potassium hydroxide required for neutralizing 1g of the sample, and the unit is referred to as mgKOH/g in the present specification. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The weight average molecular weight of the thermoplastic resin is preferably 2,000 or more, more preferably 1 ten thousand to 10 ten thousand, and further preferably 2 ten thousand to 7 ten thousand.

Here, the weight average molecular weight (Mw) is a molecular weight as follows: the Gel Permeation Chromatography (GPC) analysis apparatus using a column of TSKgel GMHxL, TSKg el G4000HxL, and TSKgel G2000HxL (each being a trade name manufactured by TOSOH CORPORATION) was used to perform detection using a solvent THF (tetrahydrofuran) and a differential refractometer, and polystyrene was used as a standard substance for conversion.

The thermoplastic resin layer may contain 1 kind of thermoplastic resin alone, or may contain 2 or more kinds of thermoplastic resins.

From the viewpoint of improving the resolution and the laminatability at high speed, the content of the thermoplastic resin is preferably 10 mass% or more and 99 mass% or less, more preferably 20 mass% or more and 90 mass% or less, and still more preferably 30 mass% or more and 80 mass% or less, based on the total mass of the thermoplastic resin layers.

The glass transition temperature (Tg) of the thermoplastic resin contained in the thermoplastic resin layer is preferably 100 ℃ or lower, because the lamination property at high speed of the photosensitive transfer member is more excellent.

The glass transition temperature was measured as follows.

Specifically, the measurement can be performed according to the measurement method described in JIS K7121 (1987). The glass transition temperature in the present disclosure uses an extrapolated glass transition initiation temperature (hereinafter, sometimes referred to as Tig).

The method for measuring the glass transition temperature will be described more specifically.

In the case of calculating the glass transition temperature, after being held at a temperature about 50 ℃ lower than the predicted Tg of the polymer until the device is stable, it is heated at a heating rate of 20 ℃/min to a temperature about 30 ℃ higher than the temperature at the end of the glass transition, and a DTA curve or a DSC curve is depicted.

The glass transition initiation temperature (Tig), i.e., the glass transition temperature Tg in the present specification, is calculated as the temperature of the intersection point where the straight line extending from the base line on the lower temperature side to the higher temperature side in the DTA curve or the DSC curve and the tangent line are drawn at the position where the gradient of the curve in the stepwise change portion of the glass transition becomes maximum. A differential scanning calorimeter (manufactured by Seiko Instruments inc., DSC6200) was used in the analysis apparatus.

The lower limit of the glass transition temperature of the thermoplastic resin is preferably 40 ℃ or higher for the reason of suppressing the phenomenon that the resin composition oozes from the end face of the roll when stored in a rolled form, i.e., edge fusion.

(plasticizer)

The thermoplastic resin layer preferably contains a plasticizer because the lamination property at high speed of the photosensitive transfer member is more excellent.

Preferably, the molecular weight or weight average molecular weight of the plasticizer is less than that of the thermoplastic resin.

The plasticizer preferably has a molecular weight of 200 to 2,000.

The plasticizer is not particularly limited as long as it is a compound that is compatible with the thermoplastic resin and exhibits plasticity, and from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer is more preferably a polyethyleneoxy structure or a polypropyleneoxy structure.

The plasticizer preferably contains a (meth) acrylate compound, and from the viewpoint of compatibility, resolution, and adhesion to a substrate, the thermoplastic resin is more preferably an acrylic resin, and the plasticizer contains a (meth) acrylate compound.

In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylic acid" means acrylic acid or methacrylic acid.

The (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound contained in a polymerizable compound in the photosensitive resin layer described later, and a polyfunctional (meth) acrylate compound, a (meth) acrylate compound having an acid group, a urethane (meth) acrylate compound, or the like can be suitably used.

In particular, from the viewpoint of storage stability, it is preferable that the same (meth) acrylate compound is contained in each of the thermoplastic resin layer and the photosensitive resin layer. By including the same (meth) acrylate compound in each of the two layers of the thermoplastic resin layer and the photosensitive resin layer, diffusion of components between the layers is suppressed, and storage stability is improved.

When the plasticizer contains a (meth) acrylate compound, it is preferable that the (meth) acrylate compound is not polymerized in the thermoplastic resin layer even in an exposed portion after exposure from the viewpoint of resolution.

The thermoplastic resin layer may contain 1 kind of the plasticizer alone, or may contain 2 or more kinds of the plasticizer.

When the thermoplastic resin layer contains a plasticizer, the content of the plasticizer is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint that the lamination property at high speed of the photosensitive transfer member is more excellent.

(other Components)

The thermoplastic resin layer may contain, in addition to the thermoplastic resin and the plasticizer, other components such as an acid-reactive dye or a base-reactive dye (hereinafter, abbreviated as "dye B"), a photoacid generator or a photobase generator, a surfactant, a sensitizer, a polymerization inhibitor, and a rust inhibitor.

(pigment B)

The thermoplastic resin layer preferably contains an acid-reactive dye or a base-reactive dye (dye B). The dye B represents a dye whose maximum absorption wavelength changes due to an acid or a base. The maximum absorption wavelength in the wavelength range of 400nm to 780nm in the color development of the dye B is preferably 450nm or more.

Here, the "dye whose maximum absorption wavelength changes with an acid or a base" may mean any one of a mode in which a dye in a colored state is decolored with an acid or a base, a mode in which a dye in a decolored state is colored with an acid or a base, and a mode in which a dye in a colored state changes with an acid or a base to a colored state of another color.

The dye B is preferably a dye whose maximum absorption wavelength changes with an acid, and particularly preferably a dye B in which the maximum absorption wavelength changes with an acid and a photoacid generator described later is used together, from the viewpoint of visibility and resolution of the exposed portion and the unexposed portion.

Examples of the coloring mechanism of the dye B in the present disclosure include a method in which a photoacid generator or a photobase generator is added to a thermoplastic resin layer, and an acid or a base generated from the photoacid generator or the like after exposure develops color of an acid-reactive dye or a base-reactive dye (e.g., leuco dye).

The maximum absorption wavelength was measured as follows: the transmission spectrum was measured at 25 ℃ in an atmospheric atmosphere using a spectrophotometer (apparatus name: UV3100, manufactured by Shimadzu corporation) in the range of 400nm to 780nm, and the wavelength at which the intensity of light becomes extremely small (maximum absorption wavelength) was measured.

Examples of the dye B include a leuco compound, diarylmethane-based dye, oxazine-based dye, xanthene-based dye, iminonaphthoquinone-based dye, azomethine-based dye, anthraquinone-based dye, and the like, and a leuco compound is preferable from the viewpoint of visibility of an exposed portion and a non-exposed portion.

Preferable examples of the pigment B include those similar to the specific latent pigments described in paragraphs 0023 to 0039 of International publication No. 2019/022089.

Specific examples of the pigment B include brilliant green, ethyl violet, methyl green, crystal violet, basic magenta, methyl violet 2B, methyl azonaphthalene red, rose bengal, m-amine yellow, thymol blue, xylenol blue, methyl orange, p-methyl red, congo red, benzo red violet 4B, d-naphthalene red, nile blue 2B, nile blue a, methyl violet, malachite green, parafuchsin (parafuuchsin), victoria pure blue-alkyl naphthalene sulfonate, victoria pure blue BOH (manufactured by Hodogaya Chemical Co., ltd.), oil blue #603 (manufactured by organic Chemical Industries Co., ltd.), oil powder #312 (manufactured by 0 Chemical Industries Co., ltd.), oil red 5B (organic chemicals Co., ltd., manufactured), oil red #308 (organic chemicals Co., ltd., manufactured), oil red (organic Chemical Industries Co., ltd.rr.), ltd., manufactured), oil green #502 (organic Chemical Industries Co, ltd., manufactured), Spilon Red BEH Special (Hodogaya Chemical Co., manufactured by ltd.), m-cresol purple, cresol Red, rhodamine B, rhodamine 6G, sulforhodamine B, basic sophorae yellow, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilide-4-p-diethylaminophenylimino naphthoquinone, 2-carboxyoctadecylamino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone, and other dyes or p, colorless compounds such as p ', p' -hexamethyltriaminotriphenylmethane (colorless crystal violet) and Pergascript Blue SRB (Ciba-Geigy).

The pigment B may be used alone in 1 kind, or in 2 or more kinds.

When the thermoplastic resin layer contains the pigment B, the content of the pigment B is preferably 0.01 mass% or more, and more preferably 0.02 to 6 mass% with respect to the total mass of the thermoplastic resin layer, from the viewpoint of the visibility of the exposed portion and the unexposed portion.

(photoacid generators or photobase generators)

The thermoplastic resin layer is preferably used together with the pigment B and contains a photoacid generator or a photobase generator for the reason of improving the visibility of the exposed portion and the unexposed portion. A more preferred embodiment is an embodiment including an acid-reactive dye and a photoacid generator.

The photoacid generator or the photobase generator used in the present invention is a compound that can generate an acid or a base by irradiation with an activated light such as ultraviolet light, far ultraviolet light, X-ray, or electron beam.

The photoacid generator or the photobase generator used in the present invention is preferably a compound that generates an acid or a base by sensing an activating light having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure thereof is not limited. Further, a photoacid generator or a photobase generator which does not directly sense an activating light beam having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as the compound senses an activating light beam having a wavelength of 300nm or more by using the sensitizer together and generates an acid or a base.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Among these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.

The ionic photoacid generator described in paragraphs 0114 to 0133 of Japanese patent application laid-open No. 2014-85643 can also be preferably used.

Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Specific examples of the trichloromethyl s-triazine, diazomethane compound and imide sulfonate compound include those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion.

As the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be preferably used.

The thermoplastic resin layer may use 1 kind of photoacid generator or photobase generator alone, or may use 2 or more kinds.

(surfactant)

The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.

Examples of the surfactant include anionic, cationic, Nonion (nonionic) and amphoteric surfactants. Preferred surfactants are nonionic surfactants.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants, and a fluorine surfactant can be preferably used.

Examples of the surfactant include surfactants described in paragraphs 0120 to 0125 of international publication No. 2018/179640, paragraphs 0017 of japanese patent No. 4502784, and paragraphs 0060 to 0071 of japanese patent application laid-open No. 2009-237362.

As a commercially available surfactant, Megafac F-552 or F-554 (manufactured by DIC corporation, supra) can be used, for example.

When the thermoplastic resin layer contains a surfactant, the content of the surfactant is preferably 0.001 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may use 1 kind of surfactant alone, or may use 2 or more kinds.

Further, other additives than the above may be contained in the thermoplastic resin layer. The other additives are not particularly limited, and known additives can be used.

Further, as a preferable embodiment of the thermoplastic resin layer, reference can be made to stages 0189 to 0193 of japanese patent laid-open publication No. 2014-85643.

The thickness of the thermoplastic resin layer is preferably 18 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 6 μm or less, from the viewpoint of excellent development speed of the photosensitive transfer member and favorable change in resolution. If the thermoplastic resin layer is too thick, it takes time to develop, and therefore, residue remains between the formed pattern and the pattern, and the resolution may be lowered. The lower limit is preferably 0.5 μm or more because the laminating property at high speed of the photosensitive transfer member is more excellent.

The thickness of the thermoplastic resin layer can be measured by the same method as the thickness of the temporary support described above.

The viscosity of the thermoplastic resin layer is preferably lower than that of the photosensitive resin layer at 70 ℃. When the viscosity of the thermoplastic resin layer is lower than that of the photosensitive resin layer at 70 ℃, the photosensitive resin layer is not deformed, and the thermoplastic resin layer is deformed to follow the substrate, so that the resolution and the lamination property at high speed are more excellent.

The viscosity of the thermoplastic resin layer at 70 ℃ and the viscosity of the photosensitive resin layer described later were measured by the following methods using a rheometer.

First, the thermoplastic resin layer or the photosensitive resin layer is taken out from the photosensitive transfer member as a sample.

Then, a sample was placed on the Peltier plate, and the Gap between the 20mmf parallel plate and the Peltier plate was set to 0.25 to 0.40 mm. After dissolving or softening a sample at 90 ℃. + -. 5 ℃, the sample is cooled to 50 ℃ at a cooling rate of 5 ℃/min, and the viscosity is measured by heating the sample at a temperature of 50 to 100 ℃ in a Gap-defined mode at a heating rate of 5 ℃/min, a frequency of 1Hz, and a strain of 0.5%.

The ratio (viscosity a/viscosity C) of the viscosity of the thermoplastic resin layer (hereinafter, abbreviated as "viscosity C") to the viscosity of the photosensitive resin layer (hereinafter, abbreviated as "viscosity a") is preferably 1 or more, more preferably 1 to 10, and further preferably 1 to 5.

< Water-soluble resin layer >

In the present invention, the intermediate layer preferably has a water-soluble resin layer, and more preferably has a water-soluble resin layer between the thermoplastic resin layer and the photosensitive resin layer, for the reason of suppressing mixing of the thermoplastic resin layer and the photosensitive resin layer.

The water-soluble resin layer preferably contains a water-soluble resin.

Here, the term "water-soluble" means that the solubility to 100g of water having a pH of 7.0 at 22 ℃ is 0.1g or more.

Examples of the water-soluble resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

In the production of the photosensitive transfer member, the water-soluble resin is preferably a resin different from the thermoplastic resin contained in the thermoplastic resin layer, from the viewpoint of suppressing mixing of the components of the thermoplastic resin layer and the water-soluble resin layer described later.

Among them, from the viewpoint of oxygen barrier properties and suppression of mixing with components of adjacent layers, the water-soluble resin preferably contains polyvinyl alcohol, and particularly preferably contains polyvinyl alcohol and polyvinyl pyrrolidone.

The water-soluble resin layer may contain 1 kind of the resin alone, or may contain 2 or more kinds of the above-mentioned resins.

The content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, with respect to the total mass of the water-soluble resin layer, from the viewpoints of oxygen barrier properties and suppression of mixing with components of adjacent layers.

An additive such as a surfactant may be added to the water-soluble resin layer as needed.

The thickness of the water-soluble resin layer may be set so that the total thickness of the temporary support and the intermediate layer is 35 μm or less, but is preferably 5 μm or less, more preferably 3 μm or less, for the reason that the change in the lamination properties at high speed is good. The lower limit is not particularly limited, but is preferably 0.1 μm or more.

The thickness of the water-soluble resin layer can be measured by the same method as the thickness of the temporary support described above.

[ photosensitive resin layer ]

The photosensitive transfer member of the present invention has a photosensitive resin layer.

The thickness of the photosensitive resin layer may be less than 5 μm, but is preferably 4 μm or less, more preferably 3 μm or less, from the viewpoint of excellent development speed of the photosensitive transfer member and favorable resolution change. The lower limit is not particularly limited, but is 0.1 μm or more.

The photosensitive resin layer is not particularly limited, and a known photosensitive resin layer can be used, but a negative photosensitive resin layer is preferable from the viewpoint of more excellent laminatability at high speed.

Here, the negative photosensitive resin layer refers to a photosensitive resin layer whose solubility in a developer is reduced by exposure to light.

From the viewpoint of pattern formability, the photosensitive resin layer preferably contains a polymerizable compound, a polymer having an acid group, and a photopolymerization initiator.

The photosensitive resin layer may be, for example, the photosensitive resin layer described in Japanese patent laid-open No. 2016-224162.

(polymerizable Compound)

The photosensitive resin layer preferably contains a polymerizable compound.

The polymerizable compound is a component contributing to the photosensitivity (i.e., photocurability) of the negative photosensitive resin layer and the strength of the cured film.

The polymerizable compound is preferably an ethylenically unsaturated compound, and more preferably an ethylenically unsaturated compound having 2 or more functions.

Here, the ethylenically unsaturated compound means a compound having one or more ethylenically unsaturated groups, and the ethylenically unsaturated compound having 2 or more functions means a compound having two or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable.

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The 2-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds. Specifically, tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1, 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like can be given.

Further, as the 2-functional ethylenically unsaturated compound, a 2-functional ethylenically unsaturated compound having a bisphenol structure can be preferably used.

Examples of the 2-functional ethylenically unsaturated compound having a bisphenol structure include those described in paragraphs 0072 to 0080 of Japanese patent laid-open publication No. 2016-224162.

Specifically, alkylene oxide-modified bisphenol a di (meth) acrylate may be mentioned, and preferable examples thereof include 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane, 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, and polyethylene glycol dimethacrylate (BPE-500, manufactured by Shin-Nakamura Chemical co., ltd.) in which ethylene oxide is added to each end of bisphenol a in an amount of 5 moles on average.

The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and can be appropriately selected from known compounds. Examples thereof include (meth) acrylate compounds having a pentaerythritol (tri/tetra) (meth) acrylate, a trimethylolpropane tri (meth) acrylate, a ditrimethylolpropane tetra (meth) acrylate, an isocyanuric acid (meth) acrylate, and a glycerol tri (meth) acrylate skeleton.

Here, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., DPCA-20 (registered trademark) manufactured by Ltd., Shin-Nakamura Chemical Co., Ltd., A-9300-1CL manufactured by Ltd.), alkylene oxide-modified (meth) acrylate compounds (e.g., Nippon Kayaku Co., manufactured by Ltd., KAYARAD RP-1040 (registered trademark), Shin-Nakamura Chemical Co., ATM-35E, A-9300 (manufactured by Ltd.), DAICEL-ALLNEX LTD., EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (e.g., Shin-Nakamura Co., Ltd., A-GLY-9E manufactured by Ltd.), ARONIX (registered trademark) TO-2349(TOAGOSEI CO., LTD.manufactured by LTD.), ARONIX-520 (TOAGCO., manufactured by TOONEI., AGM.270, ARONEI., AGCO., manufactured by LTD., AGM.510 or ARONEI., ltd. manufacture), and the like.

As the ethylenically unsaturated compound, a urethane (meth) acrylate compound (preferably a 3-or more-functional urethane (meth) acrylate compound) can be used, and examples thereof include 8UX-015A (TAISEI FINE CHEMICAL CO, manufactured by LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

Further, as the ethylenically unsaturated compound, the polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese patent laid-open No. 2004-239942 may be used.

The polymerizable compound used in the present invention preferably has a weight average molecular weight (Mw) of 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.

The polymerizable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive resin layer contains a polymerizable compound, the content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.

(Polymer having acid group)

The photosensitive resin layer preferably contains a polymer having an acid group.

The preferred embodiment of the polymer having an acid group contained in the photosensitive resin layer is the same as that of the polymer having an acid group exemplified as the thermoplastic resin contained in the thermoplastic resin layer.

The photosensitive resin layer may contain 1 kind of the photosensitive resin alone, or may contain 2 or more kinds of the polymers having an acid group.

When the photosensitive resin layer contains a polymer having an acid group, the content of the polymer having an acid group is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass or less, with respect to the total mass of the photosensitive resin layer, from the viewpoint of photosensitivity.

(photopolymerization initiator)

The photosensitive resin layer preferably contains a photopolymerization initiator.

The photopolymerization initiator receives an activating light such as ultraviolet light or visible light to start the polymerization of the polymerizable compound.

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

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.

Further, the photopolymerization initiator in the photosensitive resin layer preferably contains at least 1 selected from the group consisting of 2, 4, 5-triarylimidazole dimer and derivatives thereof from the viewpoint of photosensitivity and resolution.

Further, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-95716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-014783 can be used.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio) ] -1, 2-octanedione-2- (0-benzoyloxime) [ trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (0-acetoxime) [ trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF corporation, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone [ trade name: IRGACURE (registered trademark) 379EG manufactured by BASF corporation, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [ trade name: IRGACURE (registered trademark) 907, manufactured by BASF corporation), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one [ trade name: IRGACURE (registered trademark) 127, manufactured by BASF corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 [ trade name: IRGACURE (registered trademark) 369 manufactured by BASF corporation, 2-hydroxy-2-methyl-1-phenylpropan-1-one [ trade name: IRGACURE (registered trademark) 1173, manufactured by BASF corporation, 1-hydroxycyclohexyl phenyl ketone [ trade name: IRGACURE (registered trademark) 184, manufactured by BASF corporation), 2-dimethoxy-1, 2-diphenylethan-1-one [ trade name: IRGA CURE 651, manufactured by BASF corporation), and oxime ester [ trade name: lunar (registered trademark) 6, DKSH Management ltd.

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

When the photosensitive resin layer contains a photopolymerization initiator, the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, based on the total mass of the photosensitive resin layer.

The content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

(other additives)

The photosensitive resin layer may contain known additives as needed, in addition to the above components.

As other additives, known additives can be used, and examples thereof include a polymerization inhibitor, a plasticizer, a sensitizer, a hydrogen donor, a heterocyclic compound, a color developer, a decolorant, and a solvent.

As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of japanese patent No. 4502784 can be used. Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, and still more preferably 0.01 to 0.8% by mass, based on the total mass of the photosensitive resin layer.

Examples of the sensitizer include known sensitizers, dyes, pigments, and the like.

Examples of the plasticizer and the heterocyclic compound include plasticizers and heterocyclic compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International publication No. 2018/179640.

As the color-developer, for example, the color-developer described in 0417 of jp 2007-178459 a can be used, and leuco crystal violet, crystal violet lactone, victoria pure blue-naphthalenesulfonate, and the like are more preferably used.

When the photosensitive resin layer contains a color developer, the content of the color developer is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive resin layer, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

In addition, known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents may be added to the photosensitive resin layer of the present invention.

Preferable examples of the other components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-85643, the contents of which are incorporated in the present specification.

< cover film >

The photosensitive transfer member according to the present disclosure preferably has a cover film on the surface of the photosensitive resin layer of the photosensitive transfer member opposite to the intermediate layer.

The cover film includes a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.

The thickness of the coating film is not particularly limited, and is preferably 1 μm to 2mm, for example.

[ other layers ]

The photosensitive transfer member according to the present invention may have a layer other than the above (hereinafter, simply referred to as "other layer"). Examples of the other layers include a contrast enhancement layer, an easy-peeling layer, a BARC layer (bottom anti-reflection film), and the like.

A preferred embodiment of the contrast enhancement layer is described in paragraph 0134 of international publication No. 2018/179640, the contents of which are incorporated in the present specification.

Here, referring to fig. 1, an example of the layer structure of the photosensitive transfer member according to the present invention is schematically shown.

The photosensitive transfer member 100 shown in fig. 1 is formed by laminating a temporary support 10, a thermoplastic resin layer 12, a water-soluble resin layer 14, a photosensitive resin layer 16, and a cover film 18 in this order.

In fig. 1, the intermediate layer 15 is a layer composed of the thermoplastic resin layer 12 and the water-soluble resin layer 14.

[ method for producing photosensitive transfer Member ]

The method for producing the photosensitive transfer member of the present invention is not particularly limited, and a known production method can be used.

Specifically, a photosensitive transfer member having a temporary support, an intermediate layer having at least a thermoplastic resin layer, and a photosensitive resin layer in this order can be obtained by preparing a composition such as a thermoplastic resin composition by mixing the above-described constituent components of each layer and a solvent, and coating the composition on the temporary support or the cover film.

Among them, as a method for producing a photosensitive transfer member according to the present disclosure, a method including the following steps is preferably exemplified: a step of applying the thermoplastic resin composition onto a temporary support and drying the composition to form a thermoplastic resin layer; a step of forming a water-soluble resin layer by applying a water-soluble resin composition onto a thermoplastic resin layer and drying the composition; and a step of forming a photosensitive resin layer by applying the photosensitive resin composition to the water-soluble resin layer and drying the composition.

The method for manufacturing a photosensitive transfer member according to the present invention preferably further includes a step of providing a cover film on the photosensitive resin layer after the step of forming the photosensitive resin layer.

[ method for producing resin Pattern ]

The method for producing a resin pattern of the present invention is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer member according to the present disclosure, but preferably includes the following steps in order: the method for manufacturing a photosensitive transfer member includes a step of bringing a surface of a photosensitive resin layer of the photosensitive transfer member opposite to an intermediate layer into contact with a substrate having a conductive layer to bond the surface to the substrate (hereinafter, simply referred to as a "bonding step"), a step of pattern-exposing the photosensitive resin layer (hereinafter, simply referred to as an "exposure step"), and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, simply referred to as a "developing step").

When the photosensitive transfer member has a cover film, the surface of the photosensitive resin layer on the side opposite to the intermediate layer is the surface of the photosensitive resin layer exposed when the cover film is peeled off. In the case where the BARC layer is provided between the photosensitive resin layer and the cover film, the surface of the photosensitive resin layer opposite to the intermediate layer is the surface of the BARC layer exposed when the cover film is peeled off.

[ method for manufacturing Circuit Wiring ]

The method for manufacturing a circuit wiring of the present invention may be a method using the photosensitive transfer member according to the present disclosure, but preferably includes the following steps in order: a step of bonding a surface of the photosensitive resin layer of the photosensitive transfer member, the surface being on the opposite side to the intermediate layer, to a substrate having a conductive layer; a step of pattern-exposing the photosensitive resin layer of the bonded photosensitive transfer member; a step of forming a resin pattern by developing the photosensitive resin layer subjected to pattern exposure; and a step of etching the substrate in a region where the resin pattern is not arranged (hereinafter, simply referred to as "etching step").

[ attaching Process ]

The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure preferably includes a step (bonding step) of bringing a surface of the photosensitive resin layer of the photosensitive transfer member opposite to the intermediate layer into contact with a substrate having a conductive layer and bonding the surface to the substrate.

In the bonding step, the conductive layer is preferably pressure-bonded so as to be in contact with a surface of the photosensitive resin layer of the photosensitive transfer member opposite to the intermediate layer. In the above aspect, the photosensitive resin layer having a pattern formed after exposure and development can be preferably used as an etching resist in etching the conductive layer.

The method for pressure-bonding the substrate and the photosensitive transfer member is not particularly limited, and a known transfer method and lamination method can be used.

The photosensitive transfer member is preferably bonded to the substrate as follows: the surface of the photosensitive resin layer of the photosensitive transfer member opposite to the intermediate layer is superposed on the substrate, and pressure and heat are applied by a roller or the like. For the bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving productivity can be used.

The method of manufacturing the circuit wiring according to the present invention is preferably performed by a roll-to-roll method. Therefore, the base material constituting the substrate is preferably a resin film.

Hereinafter, a roll-to-roll system will be described.

The roll-to-roll method is as follows: the substrate used as the substrate is a substrate that can be wound and unwound, and includes a step of winding out the substrate or a structure including the substrate before any step included in a method for manufacturing a circuit wiring (also referred to as a "winding-out step"), and a step of winding up the substrate or the structure including the substrate after any step (also referred to as a "winding-up step"), and at least any step (preferably all steps) is performed while carrying the substrate or the structure including the substrate.

The winding-out method in the winding-out step and the winding-up method in the winding-up step are not particularly limited, and a known method may be used in a manufacturing method to which the roll-to-roll method is applied.

The substrate used in the present invention is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material.

The substrate may have a conductive layer on a base material such as glass, silicon, or a film, and an arbitrary layer may be formed as necessary.

A preferred embodiment of the substrate is described in, for example, paragraph 0140 of international publication No. 2018/155193, which is incorporated herein.

From the viewpoint of performing the bonding step in a roll-to-roll manner, the substrate having the conductive layer on the base is preferably a film base. In the method for manufacturing a circuit wiring according to the present invention, in the case of a circuit wiring for a touch panel, the base material is preferably a sheet-like resin composition.

The conductive layer of the substrate is preferably at least 1 layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and particularly preferably a copper layer or a silver layer, from the viewpoint of conductivity and thin line formability.

The substrate may have 1 conductive layer or 2 or more conductive layers. When the conductive layer is 2 or more layers, conductive layers having different materials are preferable.

A preferred embodiment of the conductive layer is described in, for example, paragraph 0141 of international publication No. 2018/155193, which is incorporated herein.

[ Exposure procedure ]

The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.

In the present invention, the detailed configuration and specific dimensions of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention and to reduce the area occupied by a lead-out wiring as much as possible, at least a part of the pattern (particularly, an electrode pattern of a touch panel and a portion of the lead-out wiring) is preferably a thin line of 20 μm or less, and more preferably a thin line of 10 μm or less.

Preferable examples of the light source, the exposure amount, and the exposure method used for the exposure are described in, for example, paragraphs 0146 to 0147 of International publication No. 2018/155193, which are incorporated herein by reference.

[ development procedure ]

The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step (developing step) of forming a resin pattern by developing the exposed photosensitive resin layer after the exposure step.

In the case where the photosensitive transfer member has a water-soluble resin layer, the thermoplastic resin layer and the water-soluble resin layer in the unexposed portion are also removed together with the photosensitive resin layer in the unexposed portion in the developing step. Further, in the developing step, the thermoplastic resin layer and the water-soluble resin layer in the exposed portion may be removed in the form of being dissolved or dispersed in the developing solution.

The development of the exposed photosensitive resin layer in the developing step can be performed using a developer.

The developing solution and the developing method are not particularly limited as long as the non-image portion of the photosensitive resin layer can be removed, and known developing solutions and developing methods can be used. As a developer that can be suitably used in the present disclosure, for example, a developer described in section 0194 of international publication No. 2015/093271 can be cited, and as a development method that can be suitably used, for example, a development method described in section 0195 of international publication No. 2015/093271 can be cited.

[ etching Process ]

The method for manufacturing a circuit wiring according to the present invention preferably includes a step (etching step) of etching the substrate in a region where the resin pattern is not arranged.

In the etching step, the conductive layer is etched using the pattern formed by the photosensitive resin layer in the developing step as an etching resist.

As a method of the etching treatment, known methods such as the method described in paragraphs 0209 to 0210 of japanese patent application laid-open No. 2017-120435, the method described in paragraphs 0048 to 0054 of japanese patent application laid-open No. 2010-152155, and the method of dry etching such as known plasma etching can be applied.

[ removal Process ]

The method for manufacturing a circuit wiring according to the present invention preferably performs a step of removing the resin pattern (hereinafter, simply referred to as "removing step").

The removal step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.

The method of removing the remaining photosensitive resin layer is not particularly limited, and a method of removing by a chemical treatment, particularly a method using a removing liquid, can be preferably used.

As a method for removing the photosensitive resin layer, a method of immersing a substrate having the photosensitive resin layer or the like in a removing solution which is stirred preferably at 30 to 80 ℃, more preferably at 50 to 80 ℃ for 1 to 30 minutes can be cited.

Examples of the removing solution include a solution obtained by dissolving an inorganic base component such as sodium hydroxide or potassium hydroxide or an organic base component such as a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.

The removal liquid may be used for removal by a spray method, a shower method, a spin coating and immersion method, or the like.

[ other procedures ]

The method of manufacturing a circuit wiring according to the present invention may include any process (other process) other than the above. For example, when the photosensitive transfer member has a cover film, there are a step of peeling off the cover film of the photosensitive transfer member, a step of reducing the visible light reflectance described in paragraph 0172 of international publication No. 2019/22089, and a step of forming a new conductive layer on the insulating film described in paragraph 0172 of international publication No. 2019/22089, but the steps are not limited to these steps.

Further, as examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of jp 2006-23696 a can be preferably used in the present invention.

The circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention can be applied to various devices. Examples of the device including the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention include an input device, and the like, and preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[ method for manufacturing touch Panel ]

The method for manufacturing a touch panel of the present invention may be a method using the photosensitive transfer member according to the present disclosure, but preferably includes the following steps in order: the method for manufacturing the semiconductor device includes a bonding step (bonding step) of bonding a substrate having a conductive layer by bringing a surface of a photosensitive resin layer of a photosensitive transfer member opposite to an intermediate layer into contact with the substrate, a step (exposure step) of pattern-exposing the photosensitive resin layer, a step (developing step) of developing the exposed photosensitive resin layer to form a resin pattern, and a step (etching step) of etching the substrate in a region where the resin pattern is not arranged.

In the method for manufacturing a touch panel according to the present invention, the specific embodiments of the respective steps, the order of performing the respective steps, and the like are the same as those described in the above-mentioned "method for manufacturing a circuit wiring".

In addition to the above, a known method for manufacturing a touch panel can be used as the method for manufacturing a touch panel according to the present invention.

The method of manufacturing a touch panel according to the present invention may include any process (other process) other than the above process.

Fig. 2 and 3 show an example of a mask pattern used in the method for manufacturing a touch panel according to the present invention.

In the pattern a shown in fig. 2 and the pattern B shown in fig. 3, SL and G are image portions (openings), and DL virtually represents an alignment frame. In the method of manufacturing a touch panel according to the present invention, for example, a touch panel in which circuit wirings having patterns a corresponding to SL and G are formed can be manufactured by exposing a photosensitive resin layer through a mask having the pattern a shown in fig. 2.

The touch panel according to the present invention is a touch panel including at least a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention. The touch panel according to the present invention preferably includes at least a transparent substrate, an electrode, an insulating layer, or a protective layer.

The detection method in the touch panel according to the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include a so-called embedded type (described in, for example, fig. 5, 6, 7, and 8 of jp 2012-517051 a), a so-called external embedded type (described in, for example, fig. 19 of jp 2013-168125 a, fig. 1 and 5 of jp 2012-89102 a), an OGS (One Glass Solution: One-chip Touch technology), a TOL (Touch-on-Lens) type (described in, for example, fig. 2 of jp 2013-16487127 a), and other structures (described in, for example, fig. 6 of jp 2013-164871 a), and various external hanging types (so-called GG, G1-G2, GFF, 2, GF1, G1F, etc.).

The touch panel according to the present invention includes, for example, the touch panel described in paragraph 0229 of japanese patent application laid-open No. 2017-120345.

Examples

The present invention will be described in more detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the processing steps, and the like shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. The scope of the invention should therefore not be construed in a limiting sense by the examples shown below.

< preparation of temporary support >

Production example 1

The temporary support was produced by the following method.

[ preparation of layer-Forming composition containing particles 1]

The components were mixed in the following formulation to obtain a particle-containing layer-forming composition 1. After the preparation of the particle-containing layer-forming composition 1, filtration was performed using a 6 μm filter (F20, manufactured by MAHLE Japan ltd.), followed by membrane degassing using 2x6Radial Flow suppobic (manufactured by Polypore International, inc.).

167 parts of a propylene polymer (AS-563A, manufactured by DAICEL FINECHEM LTD., solid content 27.5 mass%)

0.7 part of a nonionic surfactant (NAROACTY CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass)

114.4 parts of an anionic surfactant (RAPISOL A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1 mass%) by weight

7 parts of a basmati palm wax dispersion (Cellosol 524, ChuKYO YUSHI CO., LTD., solid content 30 mass%)

20.9 parts of carbodiimide compound (manufactured by CARBODILITE V-02-L2, Nisshinbo Co., Ltd., diluted with water to a solid content of 10% by mass)

Flatting agent (Snowtex XL, manufactured by Nissan Chemical Corporation, 40% by mass of solid content, average particle diameter 50nm)2.8 parts

690.2 parts of water

[ extrusion Molding ]

Polyethylene terephthalate pellets containing a citric acid-chelated organic titanium complex as a polymerization catalyst as described in Japanese patent No. 5575671 were dried to a water content of 50ppm or less, and then put into a hopper of a single-screw kneading extruder having a diameter of 30mm, and then melted and extruded at 280 ℃. After passing the melt (melt) through a filter (pore size: 3 μm), the melt was extruded from a die onto a cooling roll at 25 ℃ to obtain an unstretched film. The extruded melt was brought into close contact with a cooling roll by an electrostatic application method.

[ stretching, coating ]

The unstretched film extruded and solidified on the cooling roll by the above-described method was subjected to successive biaxial stretching by the following method to obtain a temporary support having a polyester film with a thickness of 25 μm and a particle-containing layer with a thickness of 40 nm.

(a) Longitudinal stretching

The unstretched film was passed between 2 pairs of nip rollers having different peripheral speeds and stretched in the longitudinal direction (carrying direction). The preheating temperature was 75 ℃, the stretching temperature was 90 ℃, the stretching ratio was 3.4 times, and the stretching speed was 1300%/sec.

(b) Coating of

On one surface of the longitudinally stretched film, the particle-containing layer-forming composition 1 was applied by a bar coater so as to have a thickness of 40nm after film formation.

(c) Stretching in transverse direction

The film subjected to the longitudinal stretching and coating was subjected to transverse stretching using a tenter under the following conditions.

Transverse stretching conditions

Preheating temperature: 110 deg.C

Stretching temperature: 120 deg.C

Stretching ratio: 4.2 times of

Stretching speed: 50%/second

[ thermal fixation, thermal relaxation ]

Next, the biaxially stretched film after completion of the longitudinal stretching and the transverse stretching was heat-set under the following conditions. After the heat-setting, the width of the tenter was reduced, and the heat relaxation was performed under the following conditions.

Thermal fixing conditions

Thermal fixing temperature: 227 deg.C

Thermal fixation time: 6 seconds

Thermal relaxation conditions

Thermal relaxation temperature: 190 deg.C

Thermal relaxation rate: 4 percent of

[ coiling ]

After the heat fixing and the heat relaxation, both ends were trimmed, and after the end portion was subjected to extrusion processing (knurling processing) with a width of 10mm, winding was performed with a tension of 40 kg/m. The width was 1.5m, and the roll length was 6300 m. The obtained film roll was used as a temporary support in production example 1.

The haze of the resulting temporary support was 0.2. The haze was measured as a total haze using a haze meter (NIPPON DENSHOKU industies co., ltd., NDH 2000).

The heat shrinkage ratio by heating at 150 ℃ for 30 minutes was 1.0% on the MD (Machine Direction) side and 0.2% on the TD (Transverse Direction) side.

The thickness of the layer containing the particles was 40nm as measured from the cross-sectional TEM photograph. As for the average particle diameter of the particles contained in the particle-containing layer, the result of measurement using a Transmission Electron Microscope (TEM) type HT-7700 manufactured by Hitachi High-Technologies Corporation and by the above-mentioned method was 50 nm.

Production example 2

A temporary support of production example 2 was obtained in the same manner as in production example 1, except that the stretching ratio of production example 1 was changed and the thickness of the polyester film after film formation was changed from 25 μm to 28 μm.

(production example 3)

The temporary support of production example 3 was obtained in the same manner as in production example 1, except that the amount of the matting agent in the particle-containing layer forming composition 1 was increased, and the thickness of the particle-containing layer after film formation was changed from 40nm to 50nm by adjusting the bar at the time of applying the particle-containing layer forming composition 1.

Production example 4

A temporary support of production example 4 was obtained in the same manner as in production example 1, except that the stretching ratio of production example 1 was changed and the thickness of the polyester film after film formation was changed from 25 μm to 20 μm.

Production example 5

A temporary support of production example 5 was obtained in the same manner as in production example 1, except that the stretching ratio of production example 1 was changed and the thickness of the polyester film after film formation was changed from 25 μm to 35 μm.

(production example 6)

A temporary support of production example 6 was obtained in the same manner as in production example 1, except that the stretching ratio of production example 1 was changed and the thickness of the polyester film after film formation was changed from 25 μm to 16 μm.

< production of Polymer >

In the following synthesis examples, the following abbreviations respectively represent the following compounds.

St: styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

MAA: methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

MMA: methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

BzMA: benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

AA: acrylic acid (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

MEK: methyl ethyl ketone (SANKYO CHEMICAL Co., Ltd.; manufactured by Ltd.)

V-601: dimethyl-2, 2' -azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

< Synthesis of Polymer A-1 >

PGMEA (116.5 parts) was added to a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution to which St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601(4.0 parts) and PGMEA (116.5 parts) were added was added dropwise over 2 hours to a three-necked flask solution maintained at 90 ℃. + -. 2 ℃. After completion of the dropwise addition, the mixture was stirred at 90 ℃. + -. 2 ℃ for 2 hours, whereby polymer A-1 (solid content concentration: 30.0%) was obtained.

< Synthesis of Polymer A-2 >

The polymer was synthesized in the same manner as in the polymer a-1 under the same conditions except for the change in the kind of the monomer and the like as shown in table 1 below. The solid content concentration of the polymer A-2 was 30% by mass.

The unit of the amount of the monomer in table 1 is mass%.

[ Table 1]

	Polymer A-1	Polymer A-2
			St	52
BzMA		75
			MAA	29	10
AA		15
			MMA	19
Weight average molecular weight (Mw)	60,000	30,000
			Tg	122	75
Acid value	189	186

< preparation of photosensitive resin composition 1 >

The following components were mixed to prepare a photosensitive resin composition 1. The unit of the amount of each component is part by mass.

Polymer A-1 (solid content concentration 30.0%): 21.87 parts

B-2: LCV (leuco crystal violet, YAMADA CHEMICAL co., ltd. manufactured, pigment developed by free radicals): 0.053 portion

C-2: B-CIM (photo radical polymerization initiator, 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, manufactured by Hampford Co., Ltd.): 0.89 part

C-3: EAB-F (photo radical polymerization initiator (sensitizer), 4' -bis (diethylamino) benzophenone, manufactured by Tokyo Chemical Industry co., ltd.): 0.05 part

D-1: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, Shin-Nakamura Chemical Co., Ltd.): 4.85 parts of

D-2: ARONIX M-270 (polypropylene glycol diacrylate, TOAGOSEI C0., ltd.): 0.51 part

Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.025 parts

1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.001 portion

E-1(Megafac F552 (manufactured by DIC Corporation)): 0.02 portion

Methyl ethyl ketone (SANKYO CHEMICAL co., ltd.): 30.87 parts

PGMEA (SHOWA DENKO k.k.): 33.92 parts

Tetrahydrofuran (manufactured by Mitsubishi Chemical corporation): 6.93 parts

The prepared photosensitive resin composition 1 was applied to the temporary support prepared in production example 1 using a slit nozzle so that the width was 1.0m and the thickness was 3.0 μm, and the resultant was passed through a drying zone at 80 ℃ for 40 seconds, thereby obtaining a photosensitive resin layer. The obtained photosensitive resin layer was measured for viscosity at 70 ℃ and found to be 36000 pas. The viscosity was determined by the method described above. As an apparatus, a rheometer DHR-2 manufactured by TA Instruments was used.

< preparation of photosensitive resin composition 2 >

Polymer A-1 (solid content concentration 30.0%): 25.2 parts of

B-2: LCV (leuco crystal violet, YAMADA CHEMICAL co., ltd. manufactured, pigment developed by free radicals): 0.06 part

C-2: B-CIM (photoradical generator, 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, manufactured by Hampford Co., Ltd.): 1.03 parts

C-3: EAB-F (photo radical polymerization initiator (sensitizer), 4' -bis (diethylamino) benzophenone, manufactured by Tokyo Chemical Industry co., ltd.): 0.045 parts

C-4 (N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)): 0.02 portion

D-1: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, Shin-Nakamura Chemical Co., Ltd.): 5.61 parts

D-2: ARONIX M-270 (polypropylene glycol diacrylate, TOAGOSEI co., ltd.): 0.58 portion

F-1 (phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation)): 0.040 parts

F-2(CBT-1 (JOOKU CHEMICAL CO., LTD) 0.015 part

4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.002 part

E-1(Megafac F552 (manufactured by DIC Corporation)): 0.048 portion

Methyl ethyl ketone (MEK, SANKYO CHEMICAL co., ltd.): 43.8 parts

PGMEA (SHOWA DENKO k.k.): 19.7 parts of

MFG (Nippon Nyukazai Co, manufactured by Ltd): 3.89 parts

The prepared photosensitive resin composition 2 was applied to the temporary support prepared in production example 1 using a slit nozzle so that the width was 1.0m and the thickness was 2.0 μm, and the resultant was passed through a drying zone at 80 ℃ for 40 seconds, thereby obtaining a photosensitive resin layer. The obtained photosensitive resin layer was measured for viscosity at 70 ℃ and found to be 37,000 pas.

< preparation of Water-soluble resin composition 1 >

The following components were mixed to prepare a water-soluble resin composition. The unit of the amount of each component is part by mass.

Ion exchange water: 38.12 parts

Methanol (manufactured by Mitsubishi Gas Chemical Company, inc.): 57.17 parts

Kuraray Poval PVA-205 (polyvinyl alcohol, Kuraray co., ltd., manufactured): 3.22 parts of

Polyvinylpyrrolidone K-30(NIPPON shokubali co., ltd.): 1.49 parts

Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0015 part

< preparation of Water-soluble resin composition 2 >

Ion exchange water: 38.12 parts

Methanol (manufactured by Mitsubishi Gas Chemical Company, inc.): 57.17 parts

Kuraray Poval 4-88LA (polyvinyl alcohol, Kuraray co., ltd.): 3.22 parts of

Polyvinylpyrrolidone K-30(NIPPON shokubali co., ltd.): 1.49 parts

Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 portions

< production of thermoplastic resin compositions 1 to 7 >

The following components were mixed in the mass parts shown in table 2 below to prepare a thermoplastic resin composition.

[ Table 2]

In table 2, abbreviations respectively represent the following compounds.

B-1: compound having the structure shown below (dye which develops color by acid)

[ chemical formula 1]

C-1: a compound having a structure shown below (photoacid generator, the compound described in paragraph 0227 of Japanese patent laid-open publication No. 2013-47765, synthesized according to the method described in paragraph 0227.)

[ chemical formula 2]

C-2: a compound having a structure shown below (photoacid generator synthesized according to the method described in paragraph 0210 of Japanese patent laid-open No. 2014-197155.)

[ chemical formula 3]

D-3: NK ester A-DCP (Dicidol diacrylate, Shin-Nakamura Chemical Co., Ltd.)

D-4: 8UX-015A (multifunctional urethane acrylate Compound, TAISEI FINE CHEMICAL CO, LTD, manufactured)

D-5: ARONIX TO-2349 (multifunctional acrylate Compound having carboxyl group, TOAGOSEI CO., LTD., manufactured)

E-1: megafac F552 (manufactured by DIC Corporation)

The prepared thermoplastic resin composition 1 was applied to the temporary support prepared in production example 1 using a slit nozzle so that the width was 1.0m and the thickness was 3.0 μm, and the resultant was passed through a drying zone at 80 ℃ for 40 seconds, thereby obtaining a thermoplastic resin layer 1. Thermoplastic resin layers 2 to 7 were obtained in the same manner as the thermoplastic resin layer 1 except that the thermoplastic resin composition 1 was changed to the thermoplastic resin compositions 2 to 7. The dynamic viscoelasticity of the obtained thermoplastic resin layers 1 to 7 was measured in the same manner as in the photosensitive resin layer. The melt viscosity was measured by the method described above.

(example 1)

< production of photosensitive transfer Member >

The temporary support prepared in production example 1 was prepared.

Next, on the surface of the temporary support on the side opposite to the particle-containing layer, the thermoplastic composition 1 was applied using a slit nozzle so that the application width became 1.0m and the thickness became 4 μm, and the thermoplastic composition was passed through a drying zone at 80 ℃ for 40 seconds, thereby forming a thermoplastic resin layer.

Then, a water-soluble resin composition was applied onto the thermoplastic resin layer using a slit nozzle so that the application width was 1.0m and the thickness was 1.1 μm, and the resultant was passed through a drying zone at 80 ℃ for 40 seconds to form a water-soluble resin layer.

Further, a negative photosensitive resin layer was formed by applying the photosensitive resin composition 1 on the water-soluble resin layer using a slit nozzle so that the application width became 1.0m and the thickness became 3.0 μm, and passing the coating through a drying zone at 80 ℃ for 40 seconds.

Next, a PET film (lumiror 16KS40, manufactured by Toray Industries inc.) was pressure-bonded as a cover film on the negative photosensitive resin layer to prepare a photosensitive transfer member, and the photosensitive transfer member was wound up to be formed into a roll shape.

< evaluation of resolution >

A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering, thereby preparing a PET substrate having a copper layer.

After the produced photosensitive transfer member was taken out, it was laminated on the above-mentioned PET substrate with a copper layer under lamination conditions of a roll temperature of 100 ℃, a line pressure of 1.0MPa and a line speed of 4.0 m/min. The temporary support was not peeled off, and was exposed to light using an ultra-high pressure mercury lamp through a line-and-space pattern mask (Duty ratio 1: 1, line width 1 μm to 20 μm, stepwise changed at intervals of 1 μm), and then the temporary support was peeled off and developed. For development, development was performed by shower development using a 1.0% sodium carbonate aqueous solution at 25 ℃ for 30 seconds.

When a line and space pattern of 20 μm was formed by the above method, the residue in the space was observed by a Scanning Electron Microscope (SEM), and when exposure was performed with an exposure dose at which the resist line width became 20 μm, the minimum line width at which the resist pattern could be resolved without peeling and without residue was evaluated as the resolution. The higher the score, the better the resolution, and preferably 3 or more.

5: resolution less than 5 μm

4: resolution of 5 μm or more and less than 7 μm

3: resolution of 7 μm or more and less than 9 μm

2: resolution of 9 μm or more and less than 11 μm

1: resolution of 11 μm or more

< evaluation of developing speed >

After the produced photosensitive transfer member was taken out, it was laminated on the above-mentioned PET substrate with a copper layer under lamination conditions of a roll temperature of 100 ℃, a line pressure of 1.0MPa and a line speed of 4.0 m/min. The temporary support was peeled off and subjected to spray development using a 1.0% aqueous solution of sodium carbonate at 25 ℃. The time for which the photosensitive transfer member was completely dissolved was measured and evaluated. The higher the score is, the better the development speed is, and preferably 3 or more.

5: completely dissolved in less than 10 seconds

4: the time for complete dissolution exceeds 10 seconds, but complete dissolution is within 15 seconds

3: the time for complete dissolution exceeds 15 seconds, but the complete dissolution is within 20 seconds

2: the time for complete dissolution exceeds 20 seconds, but the complete dissolution is within 30 seconds

1: can not be completely dissolved in 30 seconds

< evaluation of lamination Property at high speed >

The photosensitive transfer member thus prepared was wound up and then laminated on the above-mentioned PET substrate with a copper layer under lamination conditions of a roll temperature of 90 ℃, a line pressure of 1.0MPa and a line speed of 4.0 m/min.

The substrate was observed visually and with an optical microscope, and evaluated as follows. Higher score indicates better lamination, and is preferably 3 or more.

[ evaluation criteria ]

5: no laminated bubbles were observed on the PET substrate, and the visual planarity was not problematic.

4: slight laminated bubbles were observed on the PET substrate, but when autoclave treatment was performed under condition I (30 ℃, 0.5MPa, 2 hours), the bubbles disappeared, and thus there was no problem.

3: slight laminated bubbles were observed on the PET substrate, and the foam did not disappear even when the autoclave treatment was performed by the treatment I, but the foam disappeared when the autoclave treatment was performed under the condition II (50 ℃, 0.5MPa, 2 hours), and thus there was no problem.

2: laminated bubbles were observed on the PET substrate, and even when autoclave treatment was performed under the above-mentioned condition II (50 ℃, 0.5MPa, 2 hours), the bubbles were not lost.

1: laminated bubbles were observed on the entire surface of the PET substrate, and even when autoclave treatment was performed under the above-described condition II (50 ℃, 0.5MPa, 2 hours), the bubbles were not lost.

The laminated bubble means that air bubbles are mixed between the photosensitive transfer member and the PET substrate with the copper layer.

(examples 2 to 14 and comparative examples 1 to 6)

Photosensitive transfer members of examples 2 to 14 and comparative examples 1 to 6 were produced and evaluated in the same manner as in example 1, except that the thicknesses of the temporary support, the thermoplastic resin composition, the water-soluble resin composition, the photosensitive resin composition, and the layers were changed as shown in table 3. The evaluation results are summarized and shown in table 3.

As shown in table 3, it was confirmed that the photosensitive transfer member without the thermoplastic resin layer had poor resolution and poor lamination property at high speed (comparative examples 1 and 6).

Further, it was confirmed that the photosensitive transfer member had a photosensitive resin layer thickness of 5 μm or more and had poor resolution (comparative examples 2 and 5).

Further, it was confirmed that the resolution of the photosensitive transfer member was poor when the total thickness of the temporary support and the intermediate layer exceeded 35 μm (comparative examples 3 and 4).

On the other hand, it was confirmed that a photosensitive transfer member having a temporary support, an intermediate layer including at least a thermoplastic resin layer, and a photosensitive resin layer in this order was excellent in resolution and high-speed laminatability, and the photosensitive resin layer had a thickness of less than 5 μm, and the total thickness of the temporary support and the intermediate layer was 35 μm or less (examples 1 to 14).

In particular, it was confirmed that the photosensitive transfer member in which the glass transition temperature of the thermoplastic resin contained in the thermoplastic resin layer was 100 ℃ or lower was more excellent in resolution (examples 1 and 5 to 6).

Further, it was confirmed that the photosensitive transfer member having a viscosity of the thermoplastic resin layer at 70 ℃ lower than that of the photosensitive resin layer was further excellent in the lamination property at high speed (examples 1 and 5 to 6).

Further, it was confirmed that the resolution of the photosensitive transfer member was further improved when the haze of the temporary support was 0.5 or less (examples 1, 4, and 9).

(example 101)

ITO was formed on a 100 μm thick PET substrate by sputtering to a thickness of 150nm as a second conductive layer, and copper was formed thereon by vacuum deposition to a thickness of 200nm as a first conductive layer to form a circuit forming substrate.

The photosensitive transfer member obtained in example 1 was peeled off from the cover film on the copper layer, and was bonded to a substrate under the following lamination conditions to obtain a laminate.

The obtained laminate was subjected to contact pattern exposure using a photomask provided with a pattern a as shown in fig. 2, which has a structure in which the temporary support is not peeled off and the conductive layer pads are connected in one direction. For the exposure, a high-pressure mercury lamp having i-ray (365nm) as an exposure main wavelength was used.

After that, the temporary support is peeled off, and development and water washing are performed to obtain a pattern a.

Next, after the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., product of inc., Cu-02), the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., product of inc., IT0-02), thereby obtaining a substrate in which both copper and ITO were drawn using pattern a.

Next, the photosensitive transfer member obtained in example 1 was peeled off from the cover film, and was again attached to the remaining resist (cured negative photosensitive layer) under the following lamination conditions.

In the aligned state, pattern exposure was performed using a photomask provided with the pattern B shown in fig. 3 without peeling the temporary support, and then the temporary support was peeled off, and development and water washing were performed to obtain the pattern B.

Next, the copper wiring was etched using Cu-02, and the remaining cured negative photosensitive layer was peeled off using a peeling liquid (KANTO CHEMICAL co., inc., product KP-301), to obtain a circuit wiring board.

The obtained circuit wiring board was observed with a microscope, and was a perfect pattern without peeling, chipping, and the like.

< lamination conditions >

Temperature of laminating roller: 100 deg.C

Line pressure: 0.8MPa

Line speed: 3.0 m/min

Description of the symbols

10-temporary support, 12-thermoplastic resin layer, 14-water-soluble resin layer, 15-intermediate layer, 16-photosensitive resin layer, 18-cover film, 100-photosensitive transfer member, SL-image section (exposed section), G-image section (exposed section), DL-alignment frame.

Claims

1. A photosensitive transfer member comprising a temporary support, an intermediate layer and a photosensitive resin layer in this order,

the intermediate layer has a thermoplastic resin layer,

2. The photosensitive transfer member according to claim 1,

the intermediate layer also has a water-soluble resin layer,

3. The photosensitive transfer member according to claim 1 or 2,

the thickness of the thermoplastic resin layer is 10 [ mu ] m or less.

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

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

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

the thermoplastic resin layer has a plasticizer.

7. The photosensitive transfer member according to any one of claims 1 to 6,

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

the thickness of the temporary support is 25 [ mu ] m or less.

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

the temporary support has a haze of 0.5 or less.

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

the temporary support has a layer containing particles on the surface thereof on the side opposite to the intermediate layer,

the average particle diameter of the particles contained in the particle-containing layer is 30nm to 600 nm.

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

the photosensitive resin layer is a negative photosensitive resin layer.

12. A method of manufacturing a resin pattern, comprising in order:

a step of bringing a surface of the photosensitive resin layer of the photosensitive transfer member according to any one of claims 1 to 11, which surface is opposite to the intermediate layer, into contact with a substrate having a conductive layer and bonding the substrate;

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

and forming a resin pattern by developing the exposed photosensitive resin layer.

13. A method of manufacturing a circuit wiring, comprising in sequence:

a step of pattern-exposing the photosensitive resin layer;

developing the exposed photosensitive resin layer to form a resin pattern; and

and etching the substrate in a region where the resin pattern is not disposed.

14. A method of manufacturing a touch panel, comprising in order:

a step of pattern-exposing the photosensitive resin layer;

developing the exposed photosensitive resin layer to form a resin pattern; and

and etching the substrate in a region where the resin pattern is not disposed.