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

Abstract

The present invention aims to provide a photosensitive transfer member having excellent resolution and high-speed lamination, 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 sequence, wherein the intermediate layer comprises a thermoplastic resin layer, 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 less than 35 μm.

Description

Technical Field

[0001] 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 Art

[0002] In a display device (such as an organic electroluminescent (EL) display device and a liquid crystal display device) having a touch panel with an electrostatic capacitive input device, a conductive layer pattern including an electrode pattern of a sensor corresponding to a visual recognition portion, a peripheral wiring portion, and wiring of a lead-out wiring portion is provided inside the touch panel.

[0003] Generally, in forming a patterned layer, the number of steps for obtaining a desired pattern shape is small, and therefore a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate through a mask having a desired pattern using a photosensitive transfer member and then developing the exposed layer is widely used.

[0004] For example, Patent Document 1 discloses a pattern forming material including a buffer layer and a photosensitive resin layer in this order on a support.

[0005] Patent Document 2 discloses a photosensitive resin laminate including an intermediate layer and a photosensitive resin layer having a thickness of 0.1 μm to 10 μm in this order on a support film.

[0006] Previous technical literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2007-178459

[0009] Patent Document 2: International Publication No. 2007 / 125992 Summary of the invention

[0010] Technical issues to be solved by the invention

[0011] The inventors of the present invention have studied the photosensitive transfer member described in Patent Document 1 and have found that the resolution has room for improvement, particularly when forming a high-resolution pattern of 10 μm or less.

[0012] In the field of dry films, a method of producing by a roll-to-roll method is known, but in recent years, in order to improve productivity, a dry film that can cope with high-speed lamination has been required.

[0013] The inventors of the present invention studied the photosensitive transfer member described in Patent Document 2 and found that there was a problem in lamination properties at high speed.

[0014] Therefore, an object of the present invention is to provide a photosensitive transfer member having excellent resolution and lamination properties at high speed, a method for producing a resin pattern, a method for producing a circuit wiring, and a method for producing a touch panel.

[0015] Means for solving technical problems

[0016] As a result of intensive research conducted by the inventors of the present invention to achieve the above-mentioned problems, it was found that a photosensitive transfer component having a temporary support body, an intermediate layer including at least a thermoplastic resin layer, and a photosensitive resin layer in sequence, and in which the thickness of the photosensitive resin layer and the total thickness of the temporary support body and the intermediate layer are adjusted within a prescribed range, has excellent resolution and lamination properties at high speed, thereby completing the present invention.

[0017] That is, the inventors of the present invention have found that the above-mentioned problem can be achieved by the following structure:

[0018] [1] A photosensitive transfer member comprising a temporary support, an intermediate layer, and a photosensitive resin layer in this order, wherein:

[0019] The intermediate layer comprises a thermoplastic resin layer.

[0020] The photosensitive resin layer has a thickness of less than 5 μm, and the total thickness of the temporary support and the intermediate layer is 35 μm or less.

[0021] [2] The photosensitive transfer member according to [1], wherein

[0022] The intermediate layer further comprises a water-soluble resin layer.

[0023] The water-soluble resin layer is between the thermoplastic resin layer and the photosensitive resin layer.

[0024] [3] The photosensitive transfer member according to [1] or [2], wherein

[0025] The thermoplastic resin layer has a thickness of 10 μm or less.

[0026] [4] The photosensitive transfer member according to any one of [1] to [3], wherein

[0027] 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.

[0028] [5] The photosensitive transfer member according to any one of [1] to [4], wherein

[0029] The glass transition temperature of the thermoplastic resin contained in the thermoplastic resin layer is 100° C. or lower.

[0030] [6] The photosensitive transfer member according to any one of [1] to [5], wherein

[0031] The thermoplastic resin layer contains a plasticizer.

[0032] [7] The photosensitive transfer member according to any one of [1] to [6], wherein

[0033] At 70° C., the viscosity of the thermoplastic resin layer is lower than the viscosity of the photosensitive resin layer.

[0034] [8] The photosensitive transfer member according to any one of [1] to [7], wherein

[0035] The temporary support has a thickness of 25 μm or less.

[0036] [9] The photosensitive transfer member according to any one of [1] to [8], wherein

[0037] The temporary support has a haze of 0.5 or less.

[0038]

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

[0039] The temporary support has a layer containing particles on a surface opposite to the intermediate layer.

[0040] The average particle size of the particles contained in the particle-containing layer is 30 to 600 nm.

[0041]

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

[10] , wherein

[0042] The photosensitive resin layer is a negative photosensitive resin layer.

[0043]

[12] A method for producing a resin pattern, comprising: bringing a surface of a photosensitive resin layer of the photosensitive transfer member described in any one of [1] to

[11] , which is opposite to an intermediate layer, into contact with and laminating a substrate having a conductive layer;

[0044] A step of exposing the photosensitive resin layer to a pattern; and

[0045] A step of developing the exposed photosensitive resin layer to form a resin pattern.

[0046]

[13] A method for manufacturing a circuit wiring, comprising: a step of bringing a surface of a photosensitive resin layer of the photosensitive transfer member described in any one of [1] to

[11] , which is opposite to an intermediate layer, into contact with and laminating a substrate having a conductive layer;

[0047] A step of exposing the photosensitive resin layer to a pattern; and

[0048] A step of developing the exposed photosensitive resin layer to form a resin pattern; and

[0049] A step of etching the substrate in a region where the resin pattern is not disposed.

[0050]

[14] A method for manufacturing a touch panel, comprising: bringing a surface of a photosensitive resin layer of the photosensitive transfer member described in any one of [1] to

[11] , opposite to the intermediate layer, into contact with a substrate having a conductive layer for bonding;

[0051] A step of exposing the photosensitive resin layer to a pattern; and

[0052] A step of developing the exposed photosensitive resin layer to form a resin pattern; and

[0053] A step of etching the substrate in a region where the resin pattern is not disposed.

[0054] Effects of the Invention

[0055] According to the present invention, a photosensitive transfer member having excellent resolution and high-speed lamination properties, a method for producing a resin pattern, a method for producing a circuit wiring, and a method for producing a touch panel can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 This is a schematic cross-sectional view showing an example of an embodiment of the photosensitive transfer member of the present invention.

[0057] Figure 2 Schematic diagram showing pattern A.

[0058] Figure 3 It is a schematic diagram showing pattern B. DETAILED DESCRIPTION

[0059] Hereinafter, the present invention will be described in detail.

[0060] Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.

[0061] In addition, in the present specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0062] Furthermore, in this specification, each component may use a substance corresponding to each component alone, or may use two or more substances simultaneously. Here, regarding each component, when two or more substances are used simultaneously, unless otherwise specified, the content of the component refers to the total content of the substances used simultaneously.

[0063] Furthermore, unless otherwise specified, in this specification, "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 light used for exposure generally include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, activation light (active energy rays) such as electron beams, and the like.

[0064] [Photosensitive transfer member]

[0065] The photosensitive transfer member of the present invention includes a temporary support, an intermediate layer, and a photosensitive resin layer in this order.

[0066] Here, the intermediate layer refers to all layers located between the temporary support and the photosensitive resin layer, and the photosensitive transfer member of the present invention has at least a thermoplastic resin layer.

[0067] Furthermore, 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.

[0068] The photosensitive transfer member of the present invention having such a structure has good resolution and high-speed lamination properties.

[0069] Although the specific reason is not clear, the inventors of the present invention presume as follows.

[0070] In a film having a photosensitive resin layer of less than 5 μm, when the photosensitive transfer member is laminated on a substrate at high speed, bubbles generated between the photosensitive transfer member and the substrate may be bitten and pattern failure may occur. However, it is believed that by forming the photosensitive transfer member to have a temporary support, a thermoplastic resin layer and a photosensitive resin layer in sequence, bubbles generated when the photosensitive transfer member is laminated on the substrate can be reduced, and the photosensitive resin layer can follow the substrate, thereby improving the lamination property at high speed.

[0071] In the present disclosure, regarding the lamination property at a high speed, a lamination condition of a line speed of 2.0 m / min or more is preferred, and a lamination condition of a line speed of 4.0 m / min or more is more preferred.

[0072] Furthermore, it is considered that by setting the thickness of the photosensitive resin layer to less than 5 μm, development can proceed quickly even in the case of a fine pattern, and a pattern with excellent resolution can be formed without causing the pattern to collapse or connect.

[0073] Furthermore, it is considered that by setting the total thickness of the temporary support and the intermediate layer to 35 μm or less, diffraction of light occurring in the distance from the mask to the photosensitive resin layer during pattern exposure can be suppressed, and a clear pattern can be formed with high resolution.

[0074] Temporary support

[0075] The photosensitive transfer member of the present invention has a temporary support.

[0076] The temporary support is a peelable support.

[0077] From the viewpoint of enabling the photosensitive resin layer to be exposed via the temporary support when the photosensitive resin layer is pattern-exposed, the temporary support used in the present invention preferably has light-transmitting properties.

[0078] Having light transmittance means that the transmittance of the main wavelength of light used in pattern exposure is 50% or more. From the viewpoint of improving exposure sensitivity, the transmittance of the main 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 using MCPD Series manufactured by OTSUKA ELE CTRONICS CO., LTD. can be cited.

[0079] As the temporary support, for example, a glass substrate, a resin film, and paper can be cited, and a resin film is particularly preferred from the viewpoint of strength and flexibility. As the resin film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, a polyimide film, etc. can be cited. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferred.

[0080] The thickness of the temporary support is preferably 25 μm or less, more preferably 20 μm or less, because the resolution change of the photosensitive transfer member is good. From the viewpoint of transportability and supportability, the lower limit is preferably 5 μm or more, more preferably 10 μm or more.

[0081] The thickness of the temporary support can be measured by the following method.

[0082] The arithmetic mean of the thicknesses of the temporary support measured at 10 randomly selected locations in the cross-sectional observation image in the thickness direction of the temporary support is calculated and the obtained value is defined as the thickness of the temporary support. The cross-sectional observation image in the thickness direction of the temporary support can be obtained using a scanning electron microscope (SEM).

[0083] 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, because the resolution change of the photosensitive transfer member is good. The lower limit is not particularly limited, but may be more than 0.0.

[0084] The haze of the temporary support can be measured as total light haze using a haze meter (device name: NDH2000, manufactured by NIPPON DE NSHOKU INDUSTRIES Co., LTD.).

[0085] It is preferred that a layer containing particles is provided on the surface of the temporary support body on the side opposite to the above-mentioned intermediate layer. The average particle size of the particles contained in the above-mentioned layer containing particles is preferably 30 to 600 nm, more preferably 30 to 200 nm, and further preferably 40 to 100 nm. If the average particle size of the particles contained in the layer containing particles is 30 nm or more, the lamination property of the photosensitive transfer member at high speed is changed well, and if the average particle size of the particles contained in the layer containing particles is 600 nm or less, the resolution of the photosensitive transfer member is more excellent.

[0086] The average particle size of the particles contained in the particle-containing layer can be measured by the following method.

[0087] In the cross-sectional observation image of the temporary support in the thickness direction, the layer including the particles is identified as the particle-containing layer.

[0088] Next, using a transmission electron microscope (TEM), at a magnification of 20,000 times and an accelerating voltage of 100 kV, photograph any five locations of the cross section of the layer containing the particles to obtain a cross-sectional photograph. The diameters of all the particles in the obtained cross-sectional photographs were measured, and the average value (arithmetic mean particle diameter) was calculated and used as the average particle diameter of the particles. In addition, obviously large aggregates (foreign matter, garbage, etc.) were not counted.

[0089] Examples of the particles contained in the particle-containing layer include inorganic particles and organic particles.

[0090] Examples of the inorganic particles include silicon oxide (silicon dioxide) particles, titanium oxide (titania) particles, zirconium oxide (zirconium) particles, magnesium oxide (magnesium oxide) particles, aluminum oxide (alumina) particles, and the like. Among these, silicon oxide particles are particularly preferred.

[0091] Examples of the organic particles include acrylic resin particles, polyester particles, polyurethane particles, polycarbonate particles, polyolefin particles, and polystyrene particles.

[0092] The particle-containing layer may contain one type of the particles alone, or may contain two or more types of the particles.

[0093] From the viewpoint of easy control of surface roughness and suppression of wrinkles during transportation, 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.

[0094] Furthermore, 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, when the surface of the temporary support body opposite to the intermediate layer has the particle-containing layer, the particles may also be exposed on the surface of the temporary support body on the opposite side.

[0095] The material other than the above-mentioned particles contained in the above-mentioned particle-containing layer is not particularly limited, and for example, the material same as the material of the above-mentioned temporary support can be included. The above-mentioned particle-containing layer preferably includes a resin, and particularly preferably includes an acrylic resin. The above-mentioned particle-containing layer can contain one alone, or can contain two or more resins.

[0096] The thickness of the particle-containing layer is preferably 5 to 300 nm, more preferably 10 to 100 nm, and particularly preferably 30 to 70 nm, because the resolution of the photosensitive transfer member and the lamination properties at high speed are improved. In addition, the particle-containing layer may be one layer or two layers. When the particle-containing layer is two or more layers, the preferred thickness of the particle-containing layer is the preferred thickness of each particle-containing layer.

[0097] The thickness of the particle-containing layer can be measured by the same method as the thickness of the temporary support.

[0098] Examples of commercially available temporary supports having the above-mentioned particle-containing layer include LUMIRROR (registered trademark, hereinafter the same) 12QS62, LUMIRROR 16KS40, and 16FB40 (all manufactured by TORAY INDUSTRIES, INC.).

[0099] Furthermore, it is preferred that the film used as a temporary support body does not have deformation such as wrinkles, damage, or the like.

[0100] From the viewpoint of pattern formation during pattern exposure via a temporary support and the transparency of the temporary support, it is preferred that the number of particles, foreign matter or defects contained in the temporary support is small. The number of particles, foreign matter or defects with a diameter of 1 μm or more is preferably 50 / 10 mm. 2 Below, more preferably 10 / 10mm 2 Below, more preferably 3 / 10mm 2 Below, especially preferably 0 / 10mm 2 .

[0101] Preferred forms of temporary supports are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Publication No. 2016-27363, paragraphs 0041 to 0057 of International Publication No. 2012 / 081680, and paragraphs 0029 to 0040 of International Publication No. 2018 / 179370, and the contents of these publications are incorporated into this specification.

[0102] 〔Middle layer〕

[0103] The photosensitive transfer member of the present invention has an intermediate layer including at least a thermoplastic resin layer between the temporary support and the photosensitive resin layer.

[0104] The thickness of the intermediate layer can be set to a thickness that sets the total thickness of the temporary support and the intermediate layer to 35 μm or less, but is preferably 20 μm or less, more preferably 15 μm or less, and further preferably 10 μm or less because the development speed of the photosensitive transfer member is excellent and the resolution is well changed. As a lower limit, it is preferably 2 μm or more, and more preferably 4 μm or more because the lamination property of the photosensitive transfer member at a high speed is well changed.

[0105] In the present invention, as described above, the total thickness of the temporary support and the intermediate layer may be 35 μm or less, preferably 34 μm or less, and more preferably 32 μm or less. The lower limit is preferably 10 μm or more because the lamination properties of the photosensitive transfer member at high speeds are improved.

[0106] In the present invention, from the reason that the resolution of the photosensitive transfer component becomes better, the ratio (thickness B / thickness A) of the total thickness of the above-mentioned temporary support body and the above-mentioned intermediate layer (hereinafter, simply referred to as "thickness B") to the thickness of the photosensitive resin layer described later (hereinafter, simply referred to as "thickness A") is preferably 6.0 to 12.0, more preferably 7.0 to 11.5, and further preferably 8.0 to 10.5.

[0107] The thickness of the intermediate layer and the photosensitive resin layer can be measured by the same method as the thickness of the above-mentioned temporary support.

[0108] <Thermoplastic Resin Layer>

[0109] As described above, the intermediate layer includes at least a thermoplastic resin layer.

[0110] The thermoplastic resin layer preferably has no photosensitivity, and more preferably has no photopolymerization initiator.

[0111] (Thermoplastic resin)

[0112] The thermoplastic resin layer preferably includes a thermoplastic resin.

[0113] The thermoplastic resin is not particularly limited as long as it is a resin that is plasticized by heat, and examples thereof include acrylic resin, polystyrene resin, styrene-acrylic acid copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyacrylamine, polyalkylene glycol, etc. Among them, the thermoplastic resin is preferably an acrylic resin from the viewpoint of developability and transferability.

[0114] Here, the acrylic resin refers to a resin having at least one structural unit selected from the group consisting of a structural unit formed by (meth)acrylic acid, a structural unit formed by (meth)acrylic ester, and a structural unit formed by (meth)acrylic amide, and the content of the above structural unit is preferably 50% by mass or more relative to the total mass of the resin.

[0115] The thermoplastic resin preferably contains a polymer having an acid group because the developing speed becomes good.

[0116] Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group, and a phosphonic acid group. Among them, a carboxyl group is preferably used.

[0117] The acid value of the polymer having an acid group as the thermoplastic resin is preferably 60 mgKOH / g or more, and is more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more, because the developing speed becomes good.

[0118] As the acrylic resin containing carboxyl groups with an acid value of 60 mgKOH / g or more, there is no particular limitation, and it can be appropriately selected from known resins for use. For example, preferably, an acrylic resin containing carboxyl groups with an acid value of 60 mgKOH / g or more in a polymer described in paragraph 0025 of Japanese Patent Publication No. 2011-95716, an acrylic resin containing carboxyl groups with an acid value of 60 mgKOH / g or more in a polymer described in paragraphs 0033 to 0052 of Japanese Patent Publication No. 2010-237589, and an acrylic resin containing carboxyl groups with an acid value of 60 mgKOH / g or more in a binder polymer described in paragraphs 0053 to 0068 of Japanese Patent Publication No. 2016-224162 can be cited.

[0119] The copolymerization ratio of the monomer having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

[0120] From the viewpoint of alkali developability, the acid value of the thermoplastic resin is preferably 60 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 180 mgKOH / g.

[0121] Here, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and in this specification, the unit is expressed as mgKOH / g. The acid value can be calculated from the average content of the acid group in the compound, for example.

[0122] The weight average molecular weight of the thermoplastic resin is preferably 2,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 70,000.

[0123] Here, the weight average molecular weight (Mw) is a molecular weight measured by a gel permeation chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION), using a solvent of THF (tetrahydrofuran) and a differential refractometer, and converted using polystyrene as a standard substance.

[0124] The thermoplastic resin layer may contain one type of thermoplastic resin alone, or may contain two or more types of thermoplastic resins.

[0125] From the viewpoint of improving resolution and lamination properties at high speed, the content of the thermoplastic resin is preferably 10% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 90% by mass or less, and further preferably 30% by mass or more and 80% by mass or less, relative to the total mass of the thermoplastic resin layer.

[0126] The glass transition temperature (Tg) of the thermoplastic resin contained in the thermoplastic resin layer is preferably 100° C. or lower because the photosensitive transfer member has better lamination properties at high speed.

[0127] The glass transition temperature can be measured by the following method.

[0128] Specifically, it can be measured according to the measuring method described in JIS K 7121 (1987). As the glass transition temperature in the present disclosure, an extrapolated glass transition initiation temperature (hereinafter, sometimes referred to as Tig) is used.

[0129] The method for measuring the glass transition temperature will be described in more detail.

[0130] When calculating the glass transition temperature, after holding at a temperature about 50°C lower than the predicted Tg of the polymer until the device is stable, heating is performed at a heating rate of 20°C / min to a temperature about 30°C higher than the temperature at which the glass transition ends, and a DTA curve or a DSC curve is plotted.

[0131] The extrapolated glass transition initiation temperature (Tig), that is, the glass transition temperature Tg in this specification is calculated as the temperature of the intersection of a straight line extending the baseline on the low temperature side of the DTA curve or the DSC curve to the high temperature side and a tangent line drawn at the position where the gradient of the curve of the step-like change part of the glass transition becomes the maximum. A differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.) was used as the analysis device.

[0132] The lower limit of the glass transition temperature of the thermoplastic resin is preferably 40° C. or higher for the purpose of suppressing a phenomenon in which the resin composition oozes out from the end surface of a roll when the roll is stored in a roll form, namely, edge fusion.

[0133] (Plasticizer)

[0134] The thermoplastic resin layer preferably contains a plasticizer because the lamination properties of the photosensitive transfer member at high speed are more excellent.

[0135] The plasticizer preferably has a molecular weight or a weight average molecular weight smaller than that of the thermoplastic resin.

[0136] The molecular weight of the plasticizer is preferably 200 to 2,000.

[0137] The plasticizer is not particularly limited as long as it is a compound that is compatible with the thermoplastic resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and is more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer is more preferably a polyethyleneoxy structure or a polypropyleneoxy structure.

[0138] Furthermore, the plasticizer preferably contains a (meth)acrylate compound, and from the viewpoints of compatibility, resolution, and adhesion to a substrate, it is more preferred that the thermoplastic resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0139] In the present specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0140] As the (meth)acrylate compound used as the above-mentioned plasticizer, preferably there can be mentioned the (meth)acrylate compound contained in the polymerizable compound in the photosensitive resin layer described later, and polyfunctional (meth)acrylate compounds, (meth)acrylate compounds having an acid group, urethane (meth)acrylate compounds, etc. can also be appropriately used.

[0141] In particular, from the viewpoint of storage stability, it is preferred that the same (meth)acrylate compound is contained in both the thermoplastic resin layer and the photosensitive resin layer. By containing the same (meth)acrylate compound in both the thermoplastic resin layer and the photosensitive resin layer, diffusion of components between the layers is suppressed, and storage stability is improved.

[0142] When a (meth)acrylate compound is contained as the plasticizer, it is preferred that the (meth)acrylate compound is not polymerized in the thermoplastic resin layer in the exposed portion after exposure from the viewpoint of resolution.

[0143] The thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizers.

[0144] 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 of better lamination properties of the photosensitive transfer member at high speed.

[0145] (Other ingredients)

[0146] In addition to the thermoplastic resin and the plasticizer, the thermoplastic resin layer may also contain other components such as an acid-reactive dye or a base-reactive dye (hereinafter referred to as "dye B"), a photoacid generator or a photobase generator, a surfactant, a sensitizer, a polymerization inhibitor, and a rust inhibitor.

[0147] (Pigment B)

[0148] The thermoplastic resin layer preferably has an acid-reactive dye or an alkali-reactive dye (dye B). Dye B is a dye whose maximum absorption wavelength changes due to acid or alkali. The maximum absorption wavelength of dye B in the wavelength range of 400 nm to 780 nm when developing color is preferably 450 nm or more.

[0149] Here, "the maximum absorption wavelength of a pigment changes due to acid or alkali" may refer to any one of the following: a pigment in a colored state decolorizes due to acid or alkali, a pigment in a decolorized state develops color due to acid or alkali, and a pigment in a colored state changes to a colored state of another hue due to acid or alkali.

[0150] From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye B is preferably a dye whose maximum absorption wavelength changes due to acid, and particularly preferably, the dye B is a dye whose maximum absorption wavelength changes due to acid and a photoacid generator described below is used simultaneously.

[0151] As an example of the coloring mechanism of the pigment B in the present disclosure, there can be cited a method in which a photoacid generator or a photobase generator is added to the thermoplastic resin layer, and an acid-reactive pigment or a base-reactive pigment (such as a colorless pigment) is colored by an acid or base generated from the above-mentioned photoacid generator after exposure.

[0152] The maximum absorption wavelength is determined by measuring the transmission spectrum in the range of 400 nm to 780 nm at 25° C. using a spectrophotometer (device name: UV3100, manufactured by Shimadzu Corporation) under an atmospheric atmosphere, and measuring the wavelength (maximum absorption wavelength) at which the intensity of light becomes minimal.

[0153] Examples of the dye B include colorless compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. From the viewpoint of visibility of the exposed portion and the non-exposed portion, a colorless compound is preferred.

[0154] Preferred embodiments of the dye B include the same embodiments as the specific latent dyes described in paragraphs 0023 to 0039 of International Publication No. 2019 / 022089.

[0155] Specific examples of the pigment B include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, methylazonaphthalene red, rose bengal, metamin 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, Victoria pure blue-alkylnaphthalene sulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Powder #312 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red #308 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spilon Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol violet, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, basic sophora flavescens, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyaniline-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyoctadecylamino-4-pN,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone and the like dyes or colorless compounds such as p,p',p"-hexamethyltriaminotriphenylmethane (colorless crystal violet) and Pergascript Blue SRB (manufactured by Ciba-Geigy).

[0156] The dye B may be used alone or in combination of two or more.

[0157] When the thermoplastic resin layer contains the dye B, the content of the dye B is preferably 0.01% by mass or more, more preferably 0.02% by mass to 6% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of visibility of the exposed and non-exposed areas.

[0158] (Photoacid generator or photobase generator)

[0159] From the perspective of improving the visibility of the exposed and non-exposed areas, the thermoplastic resin layer preferably contains a photoacid generator or a photobase generator together with the dye B. A more preferred embodiment is an embodiment containing an acid-reactive dye and a photoacid generator.

[0160] The photoacid generator or photobase generator used in the present invention is a compound that can generate an acid or a base by irradiation with activating light such as ultraviolet rays, extreme ultraviolet rays, X-rays, electron beams, or the like.

[0161] The photoacid generator or photobase generator used in the present invention is preferably a compound that generates an acid or a base by inducing activating light with a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but the chemical structure thereof is not limited. In addition, a photoacid generator or photobase generator that does not directly induce activating light with a wavelength of 300 nm or more can be preferably used in combination with a sensitizer as long as it is a compound that induces activating light with a wavelength of 300 nm or more and generates an acid or a base by using a sensitizer at the same time.

[0162] Examples of the photoacid generator include ionic photoacid generators and nonionic photoacid generators.

[0163] Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, etc. Among these, onium salt compounds are preferred, and triarylsulfonium salts and diaryliodonium salts are particularly preferred.

[0164] As the ionic photoacid generator, those described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

[0165] Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Specific examples of trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-221494.

[0166] Among these, from the viewpoint of sensitivity, resolution, and adhesion, the photoacid generator is preferably an oxime sulfonate compound.

[0167] As the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 can be preferably used.

[0168] The photoacid generator or the photobase generator may be used alone or in combination of two or more.

[0169] (Surfactant)

[0170] From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant.

[0171] Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants. A preferred surfactant is a nonionic surfactant.

[0172] Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine-based surfactants. Preferably, fluorine-based surfactants can be used.

[0173] As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018 / 179640, paragraph 0017 of Japanese Patent No. 4502784, and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362 can be used.

[0174] Furthermore, as a commercially available product of the surfactant, for example, Megafac F-552 or F-554 (both manufactured by DIC Corporation) can be used.

[0175] When the thermoplastic resin layer contains a surfactant, the content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.

[0176] The thermoplastic resin layer may contain one kind of surfactant alone or two or more kinds of surfactants.

[0177] Furthermore, the thermoplastic resin layer may contain other additives in addition to the above. There are no particular restrictions on other additives, and known additives can be used.

[0178] Furthermore, regarding preferred aspects of the thermoplastic resin layer, reference can be made to paragraphs 0189 to 0193 of JP-A-2014-85643.

[0179] The thickness of the thermoplastic resin layer is preferably 18 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, and particularly preferably 6 μm or less, because the development speed of the photosensitive transfer member is excellent and the resolution change is good. If the thermoplastic resin layer is too thick, it takes time to develop, so residues will remain between the formed patterns, and the resolution may be reduced. Because the lamination property of the photosensitive transfer member at high speed is more excellent, the lower limit is preferably 0.5 μm or more.

[0180] The thickness of the thermoplastic resin layer can be measured by the same method as the thickness of the temporary support body described above.

[0181] The viscosity of the thermoplastic resin layer is preferably lower than the viscosity of the photosensitive resin layer at 70° C. If the viscosity of the thermoplastic resin layer is lower than that of the photosensitive resin layer at 70° C., the photosensitive resin layer does not deform, but the thermoplastic resin layer deforms and can follow the substrate, thereby achieving better resolution and high-speed lamination properties.

[0182] The viscosity of the thermoplastic resin layer at 70° C. and the viscosity of the photosensitive resin layer described later are values ​​measured by the following method using a rheometer.

[0183] First, a thermoplastic resin layer or a photosensitive resin layer is taken out from a photosensitive transfer member as a sample.

[0184] Next, the sample was placed on the Peltier plate, and the Gap between the 20 mm parallel plate and the Peltier plate was set to 0.25 to 0.40 mm. After the sample was dissolved or softened at 90°C ± 5°C, it was cooled to 50°C at a temperature drop rate of 5°C / min, and the sample was heated in a Gap-specified mode at a temperature of 50 to 100°C, a temperature rise rate of 5°C / min, a frequency of 1 Hz, and a strain of 0.5% to measure the viscosity.

[0185] The ratio (viscosity A / viscosity C) of the viscosity of the thermoplastic resin layer (hereinafter, simply referred to as "viscosity C") to the viscosity of the photosensitive resin layer (hereinafter, simply referred to as "viscosity A") is preferably 1 or more, more preferably 1-10, and even more preferably 1-5.

[0186] <Water-soluble resin layer>

[0187] 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 purpose of suppressing mixing of the thermoplastic resin layer and the photosensitive resin layer.

[0188] The water-soluble resin layer preferably contains a water-soluble resin.

[0189] Here, water-soluble means that the solubility in 100 g of water at pH 7.0 at 22°C is 0.1 g or more.

[0190] As the water-soluble resin, for example, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, cellulose resin, acrylamide resin, polyethylene oxide resin, gelatin, vinyl ether resin, polyamide resin, and copolymers thereof can be used.

[0191] When preparing 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 components of the thermoplastic resin layer and the water-soluble resin layer described later.

[0192] Among them, from the viewpoint of oxygen barrier properties and suppression of mixing with components of adjacent layers, it is preferable that the water-soluble resin contains polyvinyl alcohol, and it is particularly preferable that the water-soluble resin contains polyvinyl alcohol and polyvinyl pyrrolidone.

[0193] The water-soluble resin layer may contain one type alone or two or more types of the above-mentioned resins.

[0194] The content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but from the viewpoint of oxygen barrier properties and inhibition of mixing with components of adjacent layers, it is preferably 60% to 100% by mass, more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, relative to the total mass of the water-soluble resin layer.

[0195] Additives such as surfactants may be added to the water-soluble resin layer as needed.

[0196] The thickness of the water-soluble resin layer can 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 of good lamination performance at high speed. There is no particular lower limit, but it is preferably 0.1 μm or more.

[0197] The thickness of the water-soluble resin layer can be measured by the same method as the thickness of the temporary support described above.

[0198] (Photosensitive resin layer)

[0199] The photosensitive transfer member of the present invention has a photosensitive resin layer.

[0200] 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, because the development speed of the photosensitive transfer member is excellent and the resolution change is good. The lower limit is not particularly limited, but may be 0.1 μm or more.

[0201] The photosensitive resin layer is not particularly limited, and a known photosensitive resin layer can be used. However, a negative photosensitive resin layer is preferred from the viewpoint of more excellent lamination properties at high speed.

[0202] Here, the negative photosensitive resin layer refers to a photosensitive resin layer whose solubility in a developer is reduced by exposure.

[0203] From the viewpoint of pattern formation properties, the photosensitive resin layer preferably contains a polymerizable compound, a polymer having an acid group, and a photopolymerization initiator.

[0204] As the photosensitive resin layer, for example, a photosensitive resin layer described in Japanese Patent Application Laid-Open No. 2016-224162 may be used.

[0205] (Polymerizable compound)

[0206] The photosensitive resin layer preferably contains a polymerizable compound.

[0207] The polymerizable compound is a component that contributes to the photosensitivity (ie, photocurability) of the negative photosensitive resin layer and the strength of the cured film.

[0208] As the polymerizable compound, an ethylenically unsaturated compound is preferred, and a difunctional or higher-functional ethylenically unsaturated compound is more preferred.

[0209] Here, the ethylenically unsaturated compound refers to a compound having one or more ethylenically unsaturated groups, and the bifunctional or higher-functional ethylenically unsaturated compound refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0210] As the ethylenically unsaturated group, a (meth)acryloyl group is more preferred.

[0211] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0212] The bifunctional 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.), etc. can be mentioned.

[0213] Furthermore, as the bifunctional ethylenically unsaturated compound, a bifunctional ethylenically unsaturated compound having a bisphenol structure can be preferably used.

[0214] Examples of the bifunctional ethylenically unsaturated compound having a bisphenol structure include compounds described in paragraphs 0072 to 0080 of JP-A-2016-224162.

[0215] Specifically, alkylene oxide-modified bisphenol A di(meth)acrylate and the like can be cited, and preferably, polyethylene glycol dimethacrylate (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.) obtained by adding an average of 5 mol of ethylene oxide to both ends of 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, or bisphenol A can be cited.

[0216] The trifunctional or higher ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds, for example, dipentatriol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, trimethylolpropane tri(meth) acrylate, ditrimethylolpropane tetra(meth) acrylate, isocyanuric acid (meth) acrylate, glycerol tri(meth) acrylate skeleton (meth) acrylate compounds, etc. can be cited.

[0217] 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.

[0218] Examples of the ethylenically unsaturated compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.), ethoxylated glyceryl triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-270 (manufactured by TOAGOSEI CO., LTD.), or ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.), etc.

[0219] As the ethylenically unsaturated compound, a urethane (meth) acrylate compound (preferably a trifunctional or higher-functional urethane (meth) acrylate compound) can also be used, for example, 8UX-015A (manufactured by TAISEI FINECHEMICAL CO,.LTD.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

[0220] Furthermore, as the ethylenically unsaturated compound, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.

[0221] The weight average molecular weight (Mw) of the polymerizable compound used in the present invention is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0222] The polymerizable compound may be used alone or in combination of two or more.

[0223] 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 further preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.

[0224] (Polymer having an acid group)

[0225] The photosensitive resin layer preferably contains a polymer having an acid group.

[0226] Preferred embodiments of the polymer having an acid group contained in the photosensitive resin layer include the same embodiments as those exemplified as the polymer having an acid group contained in the above-mentioned thermoplastic resin layer.

[0227] The photosensitive resin layer may contain one kind alone or two or more kinds of polymers having an acid group.

[0228] When the photosensitive resin layer contains a polymer having an acid group, from the viewpoint of photosensitivity, the content of the polymer having an acid group is preferably 10 mass % or more and 90 mass % or less, more preferably 20 mass % or more and 80 mass % or less, and further preferably 30 mass % or more and 70 mass % or less, relative to the total mass of the photosensitive resin layer.

[0229] (Photopolymerization Initiator)

[0230] The photosensitive resin layer preferably contains a photopolymerization initiator.

[0231] The photopolymerization initiator receives activating light such as ultraviolet light and visible light to start polymerization of the polymerizable compound.

[0232] The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0233] Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0234] Furthermore, as the photopolymerization initiator in the photosensitive resin layer, it is preferred that the photopolymerization initiator contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof from the viewpoint of photosensitivity and resolution.

[0235] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-014783 can be used.

[0236] Examples of commercially available photopolymerization initiators include 1-[4-(phenylthio)]-1,2-octanedione-2-(0-benzoyl oxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(0-acetyl oxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one [trade name: IRGACURE (registered trademark) OXE-03, manufactured by BASF], and 1-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], and 1-[(4-methylphenyl)methyl]-2-morpholinylpropane-1-one [trade name: IRGACURE (registered trademark) OXE-04, manufactured by BASF]. BASF registered trademark) 907, BASF Corporation], 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one [trade name: IRGACURE (registered trademark) 127, BASF Corporation], 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: IRGACURE (registered trademark) 369, BASF Corporation], 2-Hydroxy-2-methyl-1-phenylpropane-1-one [trade name: IRGACURE (registered trademark) 1173, BASF Corporation], 1-Hydroxycyclohexylphenylketone [trade name: IRGACURE (registered trademark) 184, BASF Corporation], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: IRGACURE (registered trademark) CURE 651, manufactured by BASF Corporation] and the like, and oxime ester series [trade name: Lunar (registered trademark) 6, manufactured by DKSH Management Ltd.] and the like.

[0237] The photosensitive resin layer may contain one type alone or two or more types of photopolymerization initiators.

[0238] 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.

[0239] Furthermore, 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.

[0240] (Other additives)

[0241] The photosensitive resin layer may contain known additives in addition to the above-mentioned components as needed.

[0242] 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 decolorizer, and a solvent.

[0243] 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.

[0244] When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 3 mass %, more preferably 0.01 to 1 mass %, and further preferably 0.01 to 0.8 mass % based on the total mass of the photosensitive resin layer.

[0245] Examples of the sensitizer include known sensitizers, dyes, pigments, and the like.

[0246] Examples of the plasticizer and the heterocyclic compound include the plasticizer and the heterocyclic compound described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018 / 179640.

[0247] As the color developer, for example, the color developers described in paragraph 0417 of JP-A-2007-178459 can be used, and more preferably, leuco crystal violet, crystal violet lactone, Victoria pure blue-naphthalenesulfonate, or the like can be used.

[0248] When the photosensitive resin layer contains a color developer, the content of the color developer is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass relative to the total mass of the photosensitive resin layer, from the viewpoint of visual recognition and resolution of the exposed portion and the non-exposed portion.

[0249] Furthermore, the photosensitive resin layer of the present invention may also contain known additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal free radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-precipitation agents.

[0250] Preferred embodiments of other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, the contents of which are incorporated herein.

[0251] <Cover film>

[0252] 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 on the side opposite to the intermediate layer.

[0253] Examples of the cover film include resin films and paper, and resin films are particularly preferred from the viewpoints of strength and flexibility. Examples of the resin film include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among them, polyethylene films, polypropylene films, and polyethylene terephthalate films are preferred.

[0254] The thickness of the cover film is not particularly limited, but a thickness of 1 μm to 2 mm is preferred, for example.

[0255] 〔Other layers〕

[0256] The photosensitive transfer member according to the present invention may have layers other than those described above (hereinafter, simply referred to as "other layers"). Examples of other layers include a contrast enhancement layer, an easily peelable layer, and a BARC layer (base antireflection film).

[0257] The preferred method of the contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018 / 179640, and its content is incorporated into this specification.

[0258] Here, reference Figure 1 , schematically shows an example of the layer structure of the photosensitive transfer member involved in the present invention.

[0259] Figure 1 The photosensitive transfer member 100 shown is composed of 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 stacked in this order.

[0260] Figure 1 In the embodiment, the intermediate layer 15 is a layer composed of the thermoplastic resin layer 12 and the water-soluble resin layer 14 .

[0261] [Method for producing photosensitive transfer member]

[0262] The method for producing the photosensitive transfer member of the present invention is not particularly limited, and a known production method can be used.

[0263] Specifically, a composition such as a thermoplastic resin composition is prepared by mixing the structural components of the above-mentioned layers and a solvent, and the above-mentioned composition is applied on a temporary support or a cover film, thereby obtaining a photosensitive transfer component having a temporary support, an intermediate layer having at least a thermoplastic resin layer, and a photosensitive resin layer in sequence.

[0264] Among them, as a method for manufacturing the photosensitive transfer member involved in the present disclosure, a method including the following steps can be preferably mentioned: a step of applying a thermoplastic resin composition on a temporary support and drying it to form a thermoplastic resin layer; a step of applying a water-soluble resin composition on the thermoplastic resin layer and drying it to form a water-soluble resin layer; and a step of applying a photosensitive resin composition on the water-soluble resin layer and drying it to form a photosensitive resin layer.

[0265] Furthermore, the method for producing a photosensitive transfer member according to the present invention preferably further comprises a step of providing a cover film on the photosensitive resin layer after the step of forming the photosensitive resin layer.

[0266] [Method for producing resin pattern]

[0267] The method for manufacturing a resin pattern of the present invention is not particularly limited as long as it is a method for manufacturing a resin pattern using the photosensitive transfer component involved in the present disclosure, but preferably includes the following steps in sequence: a step of bonding the surface of the photosensitive resin layer on the side opposite to the intermediate layer of the photosensitive transfer component to a substrate having a conductive layer (hereinafter referred to as the "bonding step"), a step of exposing the above-mentioned photosensitive resin layer to a pattern (hereinafter referred to as the "exposure step"), and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter referred to as the "development step").

[0268] When the photosensitive transfer member has a cover film, the surface of the photosensitive resin layer on the side opposite to the intermediate layer refers to the surface of the photosensitive resin layer exposed when the cover film is peeled off. Also, for example, when there is a BARC layer between the photosensitive resin layer and the cover film, the surface of the photosensitive resin layer on the side opposite to the intermediate layer refers to the surface of the BARC layer exposed when the cover film is peeled off.

[0269] [Method for manufacturing circuit wiring]

[0270] The manufacturing method of the circuit wiring of the present invention can be any method using the photosensitive transfer component involved in the present disclosure, but preferably includes the following steps in sequence: a step of bonding the surface of the photosensitive resin layer on the side opposite to the intermediate layer of the photosensitive transfer component to a substrate having a conductive layer; a step of pattern-exposing the photosensitive resin layer in the bonded photosensitive transfer component; a step of developing the pattern-exposed photosensitive resin layer to form a resin pattern; and a step of etching the substrate in an area where the resin pattern is not configured (hereinafter referred to as "etching step" for brevity).

[0271] 〔Lamination process〕

[0272] The method for producing a resin pattern or the method for producing a circuit wiring according to the present disclosure preferably includes a step of bringing a surface of a photosensitive resin layer of a photosensitive transfer member opposite to the intermediate layer into contact with and laminating the substrate having a conductive layer (laminating step).

[0273] In the laminating step, the conductive layer is preferably pressed against the surface of the photosensitive resin layer of the photosensitive transfer member opposite to the intermediate layer in such a manner that the conductive layer is in contact with the surface of the photosensitive resin layer of the photosensitive transfer member. In such a manner, the photosensitive resin layer having a pattern formed thereon after exposure and development can be preferably used as an etching resist when etching the conductive layer.

[0274] There is no particular limitation on the method for pressure-bonding the substrate and the photosensitive transfer member, and a known transfer method and lamination method can be used.

[0275] The lamination of the photosensitive transfer member to the substrate is preferably performed in the following manner: the surface of the photosensitive resin layer of the photosensitive transfer member on the side opposite to the intermediate layer is overlapped with the substrate, and pressurized and heated by a roller, etc. For lamination, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used.

[0276] The method for producing the circuit wiring according to the present invention is preferably carried out by a roll-to-roll method. Therefore, the base material constituting the substrate is preferably a resin film.

[0277] The roll-to-roll method is described below.

[0278] The roll-to-roll method refers to the following method: a substrate that can be rolled up and unrolled is used as a substrate, including a step of unrolling the substrate or a structure containing the substrate before any step contained in the circuit wiring manufacturing method (also referred to as a "rolling-up step") and a step of rolling up the substrate or the structure containing 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 containing the substrate.

[0279] The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method may be used in a production method to which a roll-to-roll system is applied.

[0280] 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.

[0281] The substrate may have a conductive layer on a base material such as glass, silicon, or a film, and any layer may be formed as necessary.

[0282] A preferred embodiment of the substrate is described in, for example, paragraph 0140 of International Publication No. 2018 / 155193, and the content is incorporated into this specification.

[0283] From the viewpoint of performing the lamination process in a roll-to-roll method, the substrate having a conductive layer on the substrate is preferably a film substrate. In the method for producing a circuit wiring according to the present invention, in the case of a circuit wiring for a touch panel, the substrate is particularly preferably a sheet-like resin composition.

[0284] As the conductive layer possessed by the substrate, from the viewpoint of conductivity and fine line formability, it is preferably at least one 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.

[0285] Furthermore, the substrate may have one conductive layer or two or more conductive layers. When there are two or more conductive layers, the conductive layers are preferably made of different materials.

[0286] A preferred embodiment of the conductive layer is described in, for example, paragraph 0141 of International Publication No. 2018 / 155193, and the content is incorporated into this specification.

[0287] [Exposure process]

[0288] The method for producing a resin pattern or the method for producing a circuit wiring according to the present invention preferably includes, after the laminating step, a step of pattern-exposing the photosensitive resin layer (exposure step).

[0289] In the present invention, the detailed configuration and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (such as a touch panel) having an input device having a circuit wiring manufactured by the manufacturing method of the circuit wiring involved in the present invention, and to minimize the area occupied by the lead wiring, at least a portion of the pattern (especially the electrode pattern of the touch panel and the lead wiring portion) is preferably a thin line of less than 20 μm, and more preferably a thin line of less than 10 μm.

[0290] Preferred aspects of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs 0146 to 0147 of International Publication No. 2018 / 155193, and these contents are incorporated into this specification.

[0291] 〔Development process〕

[0292] The method for producing a resin pattern or the method for producing a circuit wiring according to the present invention preferably includes, after the exposure step, a step of developing the exposed photosensitive resin layer to form a resin pattern (development step).

[0293] Furthermore, when the photosensitive transfer member has a water-soluble resin layer, the thermoplastic resin layer and the water-soluble resin layer in the non-exposed area are also removed together with the photosensitive resin layer in the non-exposed area in the development step. Furthermore, in the development step, the thermoplastic resin layer and the water-soluble resin layer in the exposed area can also be removed in the form of being dissolved or dispersed in the developer.

[0294] The development of the exposed photosensitive resin layer in the development step can be performed using a developer.

[0295] As for the developer and the developing method, there is no particular limitation as long as the non-image portion of the photosensitive resin layer can be removed, and a known developer and developing method can be used. As a developer that can be appropriately used in the present disclosure, for example, the developer described in paragraph 0194 of International Publication No. 2015 / 093271 can be cited, and as a developing method that can be appropriately used, for example, the developing method described in paragraph 0195 of International Publication No. 2015 / 093271 can be cited.

[0296] 〔Etching process〕

[0297] The method for manufacturing a circuit wiring according to the present invention preferably includes a step of etching the substrate in a region where the resin pattern is not disposed (etching step).

[0298] 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.

[0299] As the etching treatment method, a known method such as the method described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, or a dry etching method such as known plasma etching can be applied.

[0300] 〔Removal process〕

[0301] The method for manufacturing a circuit wiring according to the present invention preferably includes a step of removing the resin pattern (hereinafter, simply referred to as a "removal step").

[0302] The removal step is not particularly limited and can be performed as necessary, but is preferably performed after the etching step.

[0303] The method of removing the remaining photosensitive resin layer is not particularly limited, and a method of removing by chemical treatment can be mentioned, and a method of using a removing liquid is particularly preferred.

[0304] Examples of a method for removing the photosensitive resin layer include a method of immersing the substrate having the photosensitive resin layer and the like in a removing liquid being stirred at preferably 30° C. to 80° C., more preferably 50° C. to 80° C. for 1 minute to 30 minutes.

[0305] Examples of the removing liquid include inorganic base components such as sodium hydroxide and potassium hydroxide or organic base components such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.

[0306] Alternatively, the removal may be performed by using a removal liquid, such as a spraying method, a shower method, or a spin immersion method.

[0307] 〔Other processes〕

[0308] The manufacturing method of the circuit wiring involved in the present invention may include any process (other process) other than the above. For example, in the case where the photosensitive transfer member has a covering film, the process of peeling off the covering film of the photosensitive transfer member, the process of reducing the visible light reflectivity described in paragraph 0172 of International Publication No. 2019 / 22089, and the process of forming a new conductive layer on the insulating film described in paragraph 0172 of International Publication No. 2019 / 22089 can be cited, but it is not limited to these processes.

[0309] Furthermore, as examples of the exposure step, the development step, and other steps in the present invention, the method described in paragraphs 0035 to 0051 of Japanese Patent Application Laid-Open No. 2006-23696 can be preferably used in the present invention.

[0310] The circuit wiring manufactured by the manufacturing method of the circuit wiring involved in the present invention can be applied to various devices. As a device having the circuit wiring manufactured by the manufacturing method of the circuit wiring involved in the present invention, for example, an input device can be cited, preferably a touch panel, and more preferably an electrostatic capacitive touch panel. In addition, the above-mentioned input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

[0311] [Method for manufacturing touch panel]

[0312] The manufacturing method of the touch panel of the present invention only needs to be a method using the photosensitive transfer component involved in the present disclosure, but preferably includes the following steps in sequence: a bonding step (bonding step) of bringing the surface of the photosensitive resin layer on the side opposite to the intermediate layer of the photosensitive transfer component into contact with a substrate having a conductive layer for bonding, a step of exposing the above-mentioned photosensitive resin layer to a pattern (exposure step), a step of developing the exposed photosensitive resin layer to form a resin pattern (development step), and a step of etching the above-mentioned substrate in an area where the above-mentioned resin pattern is not arranged (etching step).

[0313] The specific aspects of each step and the order of performing each step in the method for manufacturing a touch panel according to the present invention are as described in the above-mentioned section “Method for manufacturing circuit wiring”, and the preferred aspects are also the same.

[0314] The method for manufacturing the touch panel according to the present invention can refer to known methods for manufacturing touch panels other than those described above.

[0315] Furthermore, the method for manufacturing a touch panel according to the present invention may include any steps (other steps) other than those described above.

[0316] exist Figure 2 and Figure 3 1 shows an example of a pattern of a mask used in the method for manufacturing a touch panel according to the present invention.

[0317] exist Figure 2 The pattern A and Figure 3 In the pattern B shown in FIG. 1 , SL and G are image portions (openings), and DL virtually represents an alignment frame. In the method for manufacturing a touch panel according to the present invention, for example, Figure 2 By exposing the photosensitive resin layer using a mask of pattern A shown in , a touch panel having circuit wiring having pattern A corresponding to SL and G can be manufactured.

[0318] The touch panel of the present invention is a touch panel having at least a circuit wiring manufactured by the method for manufacturing a circuit wiring of the present invention. In addition, the touch panel of the present invention preferably has at least a transparent substrate, an electrode, an insulating layer or a protective layer.

[0319] The detection method in the touch panel according to the present invention may be any of known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance method is preferred.

[0320] Examples of the touch panel type include so-called in-cell type (for example, as described in FIGS. 5, 6, 7, and 8 of JP-A-2012-517051), so-called out-cell type (for example, as described in FIG. 19 of JP-A-2013-168125, as described in FIG. 2012-89102), and so-called touch panel type (for example, as described in FIG. 19 of JP-A-2013-168125). Figure 1 or as shown in FIG. 5 ), OGS (One Glass Solution: single-piece glass touch technology) type, TOL (Touch-on-Lens) type (for example, Japanese Patent Publication No. 2013-54727) Figure 2 ), other structures (for example, described in FIG. 6 of Japanese Patent Publication No. 2013-164871), various plug-in types (so-called GG, G1·G2, GFF, GF2, GF1, G1F, etc.), etc.

[0321] As an example of the touch panel involved in the present invention, the touch panel described in paragraph 0229 of Japanese Patent Application Laid-Open No. 2017-120345 can be cited.

[0322] Example

[0323] Below, give embodiment and the present invention is described in more detail.As long as the material, usage amount, ratio, processing content, processing step etc. shown in the following examples do not depart from the purpose of the present invention, then can be changed appropriately.Therefore, the scope of the present invention should not be interpreted restrictively by the embodiment shown below.

[0324] <Preparation of temporary support body>

[0325] (Production Example 1)

[0326] The temporary support body was produced by the following method.

[0327] [Preparation of particle-containing layer-forming composition 1]

[0328] The components were mixed in the following formula to obtain a particle-containing layer-forming composition 1. After the particle-containing layer-forming composition 1 was prepared, it was filtered using a 6 μm filter (F20, manufactured by MAHLE Japan Ltd.), and then membrane degassing was performed using 2x6 Radial Flow SuperPhobic (manufactured by Polypore International, Inc.).

[0329] Propylene polymer (AS-563A, manufactured by DAICEL FINECHEM LTD., solid content 27.5 mass %) 167 parts

[0330] Nonionic surfactant (NAROACTY CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 0.7 parts

[0331] · Anionic surfactant (RAPISOL A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1% by mass) 114.4 parts

[0332] 7 parts of carnauba wax dispersion (Cellosol 524, manufactured by CHUKYO YUSHI CO., LTD., solid content 30% by mass)

[0333] · Carbodiimide compound (CARBODILITE V-02-L2, manufactured by Nisshinbo Co., Ltd., diluted with water to a solid content of 10% by mass) 20.9 parts

[0334] Matting agent (Snowtex XL, manufactured by Nissan Chemical Corporation, solid content 40% by mass, average particle size 50 nm) 2.8 parts

[0335] · Water 690.2 parts

[0336] 〔Extrusion molding〕

[0337] Polyethylene terephthalate pellets using the citric acid chelate organic titanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst were dried to a moisture content of 50 ppm or less, and were placed in the hopper of a single-screw kneading extruder with a diameter of 30 mm, and were melted and extruded at 280° C. After passing the melt through a filter (pore size 3 μm), it was extruded from a die onto a cooling roll at 25° C. to obtain an unstretched film. In addition, the extruded melt was brought into close contact with the cooling roll using an electrostatic application method.

[0338] 〔Stretching, coating〕

[0339] The unstretched film solidified by being pressed on a cooling roll in the above method was subjected to biaxial stretching in sequence 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.

[0340] (a) Longitudinal stretching

[0341] The unstretched film was stretched in the longitudinal direction (carrying direction) by passing it between two pairs of nip rolls having different peripheral speeds. The conditions were preheating temperature of 75°C, stretching temperature of 90°C, stretching ratio of 3.4 times, and stretching speed of 1300% / sec.

[0342] (b) Coating

[0343] The particle-containing layer-forming composition 1 was applied to one surface of the longitudinally stretched film using a bar coater so as to have a thickness of 40 nm after film formation.

[0344] (c) Transverse stretching

[0345] The film subjected to the longitudinal stretching and coating was then stretched in the transverse direction using a tenter under the following conditions.

[0346] -Transverse stretching conditions-

[0347] Preheating temperature: 110℃

[0348] Stretching temperature: 120℃

[0349] Stretching ratio: 4.2 times

[0350] Stretching speed: 50% / sec

[0351] [Heat fixation, heat relaxation]

[0352] Next, the biaxially stretched film after the longitudinal stretching and the transverse stretching was heat-set under the following conditions. After the heat-set, the width of the tenter was reduced, and heat relaxation was performed under the following conditions.

[0353] -Heat Fixation Conditions-

[0354] Heat fixation temperature: 227℃

[0355] Thermal fixation time: 6 seconds

[0356] -Thermal relaxation conditions-

[0357] Heat relaxation temperature: 190℃

[0358] Thermal relaxation rate: 4%

[0359] 〔Coiling〕

[0360] After heat fixing and heat relaxation, the two ends were trimmed, and the ends were extruded (knurled) with a width of 10 mm, and then rolled up with a tension of 40 kg / m. In addition, the width was 1.5 m and the roll length was 6300 m. The obtained film roll was used as a temporary support body for Manufacturing Example 1.

[0361] The haze of the obtained temporary support was 0.2. The haze was measured as total light haze using a haze meter (NDH2000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).

[0362] The heat shrinkage rate due to heating at 150° C. for 30 minutes was 1.0% on the MD (machine direction) side and 0.2% on the TD (a direction perpendicular to the machine direction on the film surface) side.

[0363] The film thickness of the particle-containing layer was measured from the cross-sectional TEM photograph to be 40 nm. The average particle size of the particles contained in the particle-containing layer was measured by the above method using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation to be 50 nm.

[0364] (Production Example 2)

[0365] 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.

[0366] (Production Example 3)

[0367] A temporary support body of Manufacturing Example 3 was obtained in the same manner as Manufacturing Example 1, except that the amount of the matting agent in the particle-containing layer-forming composition 1 was increased and the rod used when coating the particle-containing layer-forming composition 1 was adjusted to change the thickness of the particle-containing layer after film formation from 40 nm to 50 nm.

[0368] (Production Example 4)

[0369] 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.

[0370] (Production Example 5)

[0371] 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.

[0372] (Production Example 6)

[0373] 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.

[0374] <Production of polymers>

[0375] In the following synthesis examples, the following abbreviations represent the following compounds, respectively.

[0376] St: Styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0377] MAA: Methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0378] MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0379] BzMA: benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0380] AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0381] PGMEA: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO KK)

[0382] MEK: Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

[0383] V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0384] <Synthesis of Polymer A-1>

[0385] PGMEA (116.5 parts) was added to a three-necked flask, and the temperature was raised to 90°C 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 to the solution in the three-necked flask maintained at 90°C±2°C over 2 hours. After the addition was completed, the mixture was stirred at 90°C±2°C for 2 hours, thereby obtaining a polymer A-1 (solid content concentration 30.0%).

[0386] <Synthesis of Polymer A-2>

[0387] The polymer A-2 was synthesized in the same manner as the polymer A-1 with respect to other conditions except that the types of monomers and the like were changed as shown in the following Table 1. The solid content concentration of the polymer A-2 was set to 30% by mass.

[0388] In addition, the unit of the amount of monomers in Table 1 is mass %.

[0389] [Table 1]

[0390] Polymer A-1 Polymer A-2 St 52 BYZGR 75 MAA 29 10 AA 15 MMA 19 Weight average molecular weight (Mw) 60,000 30,000 Tg 122 75 Acid value 189 186

[0391] <Preparation of Photosensitive Resin Composition 1>

[0392] The following components were mixed to prepare a photosensitive resin composition 1. In addition, the unit of the amount of each component is part by mass.

[0393] Polymer A-1 (solid content concentration 30.0%): 21.87 parts

[0394] B-2: LCV (colorless crystal violet, manufactured by YAMADA CHEMICAL CO., LTD., a pigment that develops color due to free radicals): 0.053 parts

[0395] C-2: B-CIM (photoradical polymerization initiator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Hampford): 0.89 parts

[0396] C-3: EAB-F (photoradical polymerization initiator (sensitizer), 4,4'-bis(diethylamino)benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.05 parts

[0397] D-1: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.85 parts

[0398] D-2: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.): 0.51 parts

[0399] Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.025 parts

[0400] 1-Phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.001 part

[0401] E-1 (Megafac F552 (manufactured by DIC Corporation)): 0.02 parts

[0402] Methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.): 30.87 parts

[0403] PGMEA (manufactured by SHOWA DENKO KK): 33.92 parts

[0404] Tetrahydrofuran (manufactured by Mitsubishi Chemical Corporation): 6.93 parts

[0405] The prepared photosensitive resin composition 1 was applied to the temporary support prepared in Manufacturing Example 1 using a slit nozzle in a manner such that the width was 1.0 m and the thickness was 3.0 μm, and the temporary support was passed through a drying zone at 80° C. for 40 seconds to obtain a photosensitive resin layer. The viscosity of the obtained photosensitive resin layer was measured at 70° C. and the result was 36000 Pa·s. The viscosity was measured by the method described above. As an apparatus, a rheometer DHR-2 manufactured by TA Instruments was used.

[0406] <Preparation of Photosensitive Resin Composition 2>

[0407] The following components were mixed to prepare a photosensitive resin composition 1. In addition, the unit of the amount of each component is part by mass.

[0408] Polymer A-1 (solid content concentration 30.0%): 25.2 parts

[0409] B-2: LCV (colorless crystal violet, manufactured by YAMADA CHEMICAL CO., LTD., a pigment that develops color due to free radicals): 0.06 parts

[0410] C-2: B-CIM (photoradical generator, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by Hampford): 1.03 parts

[0411] C-3: EAB-F (photoradical polymerization initiator (sensitizer), 4,4'-bis(diethylamino)benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.045 parts

[0412] C-4 (N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)): 0.02 parts

[0413] D-1: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.): 5.61 parts

[0414] D-2: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.): 0.58 parts

[0415] F-1 (phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation)): 0.040 parts

[0416] F-2 (CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD.): 0.015 parts

[0417] 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.002 parts

[0418] E-1 (Megafac F552 (manufactured by DIC Corporation)): 0.048 parts

[0419] Methyl ethyl ketone (MEK, manufactured by SANKYO CHEMICAL Co., Ltd.): 43.8 parts

[0420] PGMEA (manufactured by SHOWA DENKO KK): 19.7 parts

[0421] MFG (manufactured by Nippon Nyukazai Co., Ltd.): 3.89 parts

[0422] The prepared photosensitive resin composition 2 was applied to the temporary support prepared in Production Example 1 using a slit nozzle so as to have a width of 1.0 m and a thickness of 2.0 μm, and passed through a drying zone at 80° C. for 40 seconds to obtain a photosensitive resin layer. The viscosity of the obtained photosensitive resin layer was measured at 70° C. and found to be 37,000 Pa·s.

[0423] <Preparation of Water-Soluble Resin Composition 1>

[0424] The following components were mixed to prepare a water-soluble resin composition. The unit of the amount of each component is part by mass.

[0425] Ion exchange water: 38.12 parts

[0426] Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts

[0427] Kuraray Poval PVA-205 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.): 3.22 parts

[0428] Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts

[0429] Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0015 parts

[0430] <Preparation of Water-Soluble Resin Composition 2>

[0431] The following components were mixed to prepare a water-soluble resin composition. The unit of the amount of each component is part by mass.

[0432] Ion exchange water: 38.12 parts

[0433] Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts

[0434] Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by KURARAY CO., LTD.): 3.22 parts

[0435] Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts

[0436] Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 parts

[0437] <Preparation of Thermoplastic Resin Compositions 1 to 7>

[0438] The following components were mixed in the mass parts shown in the following Table 2 to prepare a thermoplastic resin composition.

[0439] [Table 2]

[0440]

[0441] In Table 2, the abbreviations represent the following compounds, respectively.

[0442] B-1: Compound with the following structure (a dye that develops color when exposed to acid)

[0443] [Chemical formula 1]

[0444]

[0445] C-1: A compound having the structure shown below (a photoacid generator, a compound described in paragraph 0227 of JP-A-2013-47765, synthesized according to the method described in paragraph 0227.)

[0446] [Chemical formula 2]

[0447]

[0448] C-2: A compound having the structure shown below (the photoacid generator was synthesized according to the method described in paragraph 0210 of JP-A-2014-197155).

[0449] [Chemical formula 3]

[0450]

[0451] D-3: NK ester A-DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0452] D-4: 8UX-015A (multifunctional urethane acrylate compound, manufactured by TAISEI FINE CHEMICAL CO,.LTD.)

[0453] D-5: ARONIX TO-2349 (polyfunctional acrylate compound having a carboxyl group, manufactured by TOAGOSEI CO., LTD.)

[0454] E-1: Megafac F552 (manufactured by DIC Corporation)

[0455] The prepared thermoplastic resin composition 1 was applied to the temporary support prepared in Production Example 1 using a slit nozzle in a manner such that the width was 1.0 m and the thickness was 3.0 μm, and passed through a drying zone at 80° C. for 40 seconds to obtain 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 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 the above-mentioned photosensitive resin layer. The melt viscosity was measured by the method described above.

[0456] (Example 1)

[0457] <Production of Photosensitive Transfer Member>

[0458] The temporary support body produced in Production Example 1 was prepared.

[0459] Next, the thermoplastic composition 1 was applied to the surface of the temporary support opposite to the particle-containing layer using a slit nozzle to a coating width of 1.0 m and a thickness of 4 μm, and passed through a drying zone at 80° C. for 40 seconds to form a thermoplastic resin layer.

[0460] Then, a water-soluble resin composition was applied on the thermoplastic resin layer using a slit nozzle to a coating width of 1.0 m and a thickness of 1.1 μm, and passed through a drying zone at 80° C. for 40 seconds to form a water-soluble resin layer.

[0461] Furthermore, the photosensitive resin composition 1 was applied on the water-soluble resin layer using a slit nozzle to a coating width of 1.0 m and a thickness of 3.0 μm, and passed through a drying zone at 80° C. for 40 seconds to form a negative photosensitive resin layer.

[0462] Next, a PET film (manufactured by Toray Industries Inc., LUMIRROR 16KS40) was bonded to the negative photosensitive resin layer as a cover film to prepare a photosensitive transfer member, which was then wound up into a roll shape.

[0463] <Resolution Evaluation>

[0464] A PET substrate with a copper layer was prepared by providing a 200 nm thick copper layer on a 100 μm thick polyethylene terephthalate (PET) film by a sputtering method.

[0465] After the produced photosensitive transfer member was unwound, it was laminated on the above-mentioned PET substrate with a copper layer under the lamination conditions of a roller temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. Without peeling off the temporary support, it was exposed by 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 change every 1 μm), and then the temporary support was peeled off and developed. For development, a 1.0% sodium carbonate aqueous solution at 25°C was used for 30 seconds by spray development.

[0466] When a 20 μm line and space pattern is formed by the above method, the residue in the space portion is observed using a scanning electron microscope (SEM), and when the resist line width is exposed to an exposure amount of 20 μm, the minimum line width at which the resist pattern can be resolved without peeling and residue is evaluated as the resolution. A higher score indicates a better resolution, preferably 3 or more.

[0467] 5: Resolution less than 5μm

[0468] 4: Resolution is 5μm or more and less than 7μm

[0469] 3: Resolution is 7μm or more and less than 9μm

[0470] 2: Resolution is 9μm or more and less than 11μm

[0471] 1: Resolution is 11μm or more

[0472] <Development Speed ​​Evaluation>

[0473] After the prepared photosensitive transfer member was unwound, it was laminated on the above-mentioned PET substrate with a copper layer under lamination conditions of a roller temperature of 100°C, a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min. The temporary support was peeled off and spray development was performed using a 1.0% sodium carbonate aqueous solution at 25°C. The time for the photosensitive transfer member to completely dissolve was measured and evaluated. A higher score indicates a better development speed, preferably 3 or more.

[0474] 5: Completely dissolved within 10 seconds

[0475] 4: The time to completely dissolve exceeds 10 seconds, but completely dissolves within 15 seconds

[0476] 3: The time to completely dissolve exceeds 15 seconds, but completely dissolves within 20 seconds

[0477] 2: The time to completely dissolve exceeds 20 seconds, but completely dissolves within 30 seconds

[0478] 1: Cannot be completely dissolved within 30 seconds

[0479] <Evaluation of lamination properties at high speed>

[0480] The produced photosensitive transfer member was unwound and laminated on the above-mentioned PET substrate with a copper layer under lamination conditions of a roll temperature of 90° C., a linear pressure of 1.0 MPa, and a linear speed of 4.0 m / min.

[0481] The substrate was observed visually and under an optical microscope and evaluated as follows: A higher score indicates better lamination properties, and a score of 3 or more is preferred.

[0482] [Evaluation Criteria]

[0483] 5: No lamination bubbles were observed on the PET substrate, and the visually observed flatness was also in a state of no problem.

[0484] 4: Slight lamination bubbles were observed on the PET substrate, but the bubbles disappeared when the substrate was autoclaved under condition I (30° C., 0.5 MPa, 2 hours), so there was no problem.

[0485] 3: Slight lamination bubbles were observed on the PET substrate. The bubbles did not disappear even when the substrate was autoclaved in the above-mentioned treatment I. However, the bubbles disappeared when the substrate was autoclaved in the condition II (50°C, 0.5 MPa, 2 hours). Therefore, there was no problem.

[0486] 2: Lamination bubbles were observed on the PET substrate, and the bubbles did not disappear even when the autoclave was treated under the above-mentioned conditions II (50° C., 0.5 MPa, 2 hours).

[0487] 1: Lamination bubbles were observed on the entire surface of the PET substrate, and the bubbles did not disappear even when the autoclave was treated under the above-mentioned conditions II (50° C., 0.5 MPa, 2 hours).

[0488] The lamination bubbles refer to the mixing of bubbles between the photosensitive transfer member and the PET substrate with a copper layer.

[0489] (Example 2 to Example 14 and Comparative Example 1 to Comparative Example 6)

[0490] Photosensitive transfer members of Examples 2 to 14 and Comparative Examples 1 to 6 were prepared and evaluated in the same manner as in Example 1, except that the temporary support, the thermoplastic resin composition, the water-soluble resin composition, the photosensitive resin composition, and the thickness of each layer were changed as shown in Table 3. The evaluation results are summarized and shown in Table 3.

[0491]

[0492] As shown in Table 3, it was confirmed that the photosensitive transfer member having no thermoplastic resin layer was inferior in resolution and lamination properties at high speed (Comparative Examples 1 and 6).

[0493] Furthermore, it was confirmed that the photosensitive transfer member having a photosensitive resin layer thickness of 5 μm or more had poor resolution (Comparative Examples 2 and 5).

[0494] Furthermore, it was confirmed that the photosensitive transfer member having a total thickness of the temporary support and the intermediate layer exceeding 35 μm had poor resolution (Comparative Examples 3 and 4).

[0495] It was confirmed that, in contrast, a photosensitive transfer component having, in sequence, a temporary support, an intermediate layer comprising at least a thermoplastic resin layer, and a photosensitive resin layer, the thickness of the photosensitive resin layer being less than 5 μm, and the total thickness of the temporary support and the intermediate layer being less than 35 μm, had excellent resolution and lamination properties at high speed (Examples 1 to 14).

[0496] 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° C. or lower had better resolution (Example 1 and Examples 5 and 6).

[0497] Furthermore, it was confirmed that the photosensitive transfer member in which the viscosity of the thermoplastic resin layer at 70° C. was lower than the viscosity of the photosensitive resin layer had more excellent lamination properties at high speed (Example 1 and Examples 5 and 6).

[0498] Furthermore, it was confirmed that the resolution of the photosensitive transfer member in which the haze of the temporary support was set to 0.5 or less was further improved (Examples 1, 4, and 9).

[0499] (Example 101)

[0500] On a 100 μm thick PET substrate, ITO was formed as a second conductive layer with a thickness of 150 nm by sputtering, and thereon, copper was formed as a first conductive layer with a thickness of 200 nm by vacuum deposition to prepare a circuit forming substrate.

[0501] On the copper layer, the photosensitive transfer member obtained in Example 1 was peeled off from the cover film, and the laminate was bonded to a substrate under the following lamination conditions to obtain a laminate.

[0502] Use the following settings: Figure 2 The obtained laminate was subjected to contact pattern exposure using a photomask of pattern A shown in FIG. 1 , which has a structure in which the temporary support is not peeled off and the conductive layer pads are connected in one direction. For exposure, a high-pressure mercury lamp with i-ray (365 nm) as the main exposure wavelength was used.

[0503] Thereafter, the temporary support was peeled off, and development and water washing were performed, whereby a pattern A was obtained.

[0504] Next, the copper layer was etched using a copper etchant (Cu-02 manufactured by KANTO CHEMICAL CO., INC.), and then the ITO layer was etched using an ITO etchant (ITO-02 manufactured by KANTO CHEMICAL CO., INC.), thereby obtaining a substrate on which both copper and ITO were drawn with pattern A.

[0505] Next, the cover film of the photosensitive transfer member obtained in Example 1 was peeled off and again laminated on the remaining resist (cured negative photosensitive layer) under the following lamination conditions.

[0506] In the aligned state, the temporary support is not peeled off and the Figure 3 The pattern B is obtained by pattern exposure using a photomask having the pattern B shown, peeling off the temporary support, performing development and washing with water.

[0507] Next, the copper wiring was etched using Cu-02, and the remaining cured negative photosensitive layer was peeled off using a stripping solution (KP-301 manufactured by KANTO CHEMICAL CO., INC.) to obtain a circuit wiring board.

[0508] The obtained circuit wiring board was observed under a microscope, and it was found that there was no peeling or defect, and the pattern was perfect.

[0509] <Lamination Conditions>

[0510] Lamination roller temperature: 100°C

[0511] Line pressure: 0.8MPa

[0512] Line speed: 3.0m / min

[0513] Explanation of symbols

[0514] 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 portion (exposure portion), G-image portion (exposure portion), DL-alignment frame.

Claims

1. A photosensitive transfer member comprising a temporary support, an intermediate layer, a photosensitive resin layer and a cover film in this order, wherein: The intermediate layer has a thermoplastic resin layer, 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 34 μm or less. At 70° C., the viscosity of the thermoplastic resin layer is lower than the viscosity of the photosensitive resin layer. The ratio of the viscosity of the photosensitive resin layer, namely, the viscosity A, to the viscosity of the thermoplastic resin layer, namely, the viscosity C, namely, the viscosity A / viscosity C, is 1 to 5, The thickness of the temporary support is 25 μm or less. The haze of the temporary support is 0.5 or less, The photosensitive resin layer is directly laminated on the cover film.

2. The photosensitive transfer member according to claim 1, wherein The intermediate layer also 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 claim 1 or 2, wherein The thermoplastic resin layer has a thickness of 10 μm or less.

4. The photosensitive transfer member according to claim 1 or 2, 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 claim 1 or 2, wherein The thermoplastic resin contained in the thermoplastic resin layer has a glass transition temperature of 100° C. or less.

6. The photosensitive transfer member according to claim 1 or 2, wherein: The thermoplastic resin layer has a plasticizer.

7. The photosensitive transfer member according to claim 1 or 2, wherein: The temporary support has a layer containing particles on a surface opposite to the intermediate layer. The average particle size of the particles contained in the particle-containing layer is 30 nm to 600 nm.

8. The photosensitive transfer member according to claim 1 or 2, wherein The photosensitive resin layer is a negative photosensitive resin layer.

9. A method for 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 claims 1 to 8, which is opposite to the intermediate layer, into contact with a substrate having a conductive layer for bonding; A step of exposing the photosensitive resin layer to a pattern; and A step of developing the exposed photosensitive resin layer to form a resin pattern.

10. A method for 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 claims 1 to 8, which is opposite to the intermediate layer, into contact with a substrate having a conductive layer for bonding; A step of exposing the photosensitive resin layer to a pattern; A step of developing the exposed photosensitive resin layer to form a resin pattern; and A step of etching the substrate in a region where the resin pattern is not arranged.

11. A method for 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 claims 1 to 8, which is opposite to the intermediate layer, into contact with a substrate having a conductive layer for bonding; A step of exposing the photosensitive resin layer to a pattern; A step of developing the exposed photosensitive resin layer to form a resin pattern; and A step of etching the substrate in a region where the resin pattern is not arranged.

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