CN116888535A - Photosensitive composition, transfer film, pattern forming method, circuit wiring manufacturing method, and touch panel manufacturing method - Google Patents

Photosensitive composition, transfer film, pattern forming method, circuit wiring manufacturing method, and touch panel manufacturing method Download PDF

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Publication number
CN116888535A
CN116888535A CN202280014728.2A CN202280014728A CN116888535A CN 116888535 A CN116888535 A CN 116888535A CN 202280014728 A CN202280014728 A CN 202280014728A CN 116888535 A CN116888535 A CN 116888535A
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China
Prior art keywords
compound
photosensitive composition
photosensitive
photosensitive layer
exposure
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Inventor
山口圭吾
儿玉邦彦
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Human Computer Interaction (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

The first object of the present invention is to provide a photosensitive composition capable of forming a pattern excellent in corrosion resistance in a hot and humid environment. A second object of the present invention is to provide a transfer film formed using the photosensitive composition. A third object of the present invention is to provide a pattern forming method, a circuit wiring manufacturing method, and a touch panel manufacturing method. The photosensitive composition of the present invention satisfies the requirement A1 and the requirement B1. Condition A1: the glass transition temperature of the photosensitive layer after exposure obtained in the step X is 65 ℃ or higher. Requirement B1: the water content of the photosensitive layer after exposure obtained in the step X at 40 ℃ and 90% RH is less than 2.0 mass%.

Description

Photosensitive composition, transfer film, pattern forming method, circuit wiring manufacturing method, and touch panel manufacturing method
Technical Field
The invention relates to a photosensitive composition, a transfer film, a pattern forming method, a circuit wiring manufacturing method and a touch panel manufacturing method.
Background
In a display device (specifically, an organic Electroluminescence (EL) display device, a liquid crystal display device, or the like) including a touch panel such as a capacitive input device, a conductive pattern such as an electrode pattern of a sensor corresponding to a visual recognition portion, a peripheral wiring portion, and a wiring of a lead-out wiring portion is provided inside the touch panel.
In general, in order to prevent corrosion of metal, an increase in resistance between an electrode and a driving circuit, disconnection, and other defects, a pattern made of a resin may be disposed as a protective film (permanent film) on the conductive pattern.
In general, a photosensitive composition is used for patterning, and particularly, a method of using a transfer film (having a temporary support and a photosensitive layer formed using the photosensitive composition) is widely used because of the small number of steps for obtaining a desired pattern shape. As a method of forming a pattern using a transfer film, there is a method of exposing and developing a photosensitive layer transferred from the transfer film to an arbitrary substrate through a mask having a predetermined pattern shape. For example, in the case where the photosensitive layer is a negative photosensitive layer, since the exposed region is cured, there is a possibility that a dissolution contrast may occur between the exposed region and the unexposed region. As a result, only the unexposed region is removed at the time of the development treatment, whereby a pattern can be formed.
As a photosensitive composition and a transfer film, for example, patent document 1 discloses the following: a photosensitive resin composition comprising, on a substrate: a binder polymer having a carboxyl group with an acid value of 75mgKOH/g or more, a photopolymerizable compound, and a photopolymerization initiator, and a photosensitive element comprising: a support film and a photosensitive layer formed of the photosensitive resin composition and provided on the support film.
Technical literature of the prior art
Patent literature
Patent document 1: international publication No. 2013/084886
Disclosure of Invention
Technical problem to be solved by the invention
As a pattern used as a protective film of a conductive pattern formed of a metal material, a property capable of suppressing corrosion of a metal (hereinafter also referred to as "corrosion resistance") is also required.
As a result of conducting studies by using the photosensitive composition described in patent document 1 to form a pattern, the inventors have found that there is room for improvement in corrosion resistance particularly in a hot and humid environment.
Accordingly, an object of the present invention is to provide a photosensitive composition capable of forming a pattern excellent in corrosion resistance under a hot and humid environment.
The present invention also provides a transfer film formed using the photosensitive composition.
The present invention also provides a method for forming a pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.
Means for solving the technical problems
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.
[ 1 ] A photosensitive composition satisfying the following requirements A1 and B1.
Condition A1: the glass transition temperature of the photosensitive layer after exposure obtained by the following step X is 65 ℃ or higher.
Requirement B1: the water content of the photosensitive layer after exposure obtained by the following step X at 40 ℃ 90% rh is less than 2.0 mass%.
Step X: a laminate having a glass substrate, a photosensitive layer formed of the photosensitive composition, and a resin film in this order was obtained. Next, from the opposite side of the laminate to the glass substrate side, an ultra-high pressure mercury lamp was used so that the cumulative exposure at 365nm wavelength became 80mJ/cm 2 In the above-described mode (a) for the above-described laminated bodyThe photosensitive layer is exposed. After exposure, the laminate was left in an atmosphere of 50% RH at 25℃for 30 minutes, and then the resin film was peeled off. Next, from the side of the surface from which the resin film was peeled, a high-pressure mercury lamp was used so that the cumulative exposure at 365nm in wavelength became 1000mJ/cm 2 The photosensitive layer is exposed again to obtain a post-exposure photosensitive layer.
[ 2 ] the photosensitive composition according to [ 1 ], which further satisfies the following condition A2.
Condition A2: the glass transition temperature of the photosensitive layer after exposure obtained in the step X is 165 ℃ or lower.
The photosensitive composition according to [ 3 ], wherein,
the glass transition temperature in the element A2 is 120 ℃ or lower.
The photosensitive composition according to any one of [ 1 ] to [ 3 ], wherein,
the glass transition temperature in the element A1 is 85 ℃ or higher.
The photosensitive composition according to any one of [ 1 ] to [ 4 ], which further satisfies the following condition B2.
Requirement B2: the water content of the photosensitive layer after exposure obtained by the above step X at 40 ℃ 90% rh is more than 0 mass%.
The photosensitive composition according to [ 6 ], wherein,
the water content in the element B2 is 0.5 mass% or more.
The photosensitive composition according to any one of [ 1 ] to [ 6 ], wherein,
the glass transition temperature in the element A1 is 100 ℃ or higher.
The photosensitive composition according to any one of [ 1 ] to [ 7 ], wherein,
the photosensitive composition contains a compound A having an acid group,
the content of the acid groups in the photosensitive composition is reduced by irradiation with actinic rays or radiation.
The photosensitive composition according to any one of [ 1 ] to [ 8 ], wherein,
The photosensitive composition satisfies the following element (V01) and any of the following elements (W01).
Requirement (V01)
The photosensitive composition includes a compound a having an acid group and a compound β having a structure in which the amount of the acid group included in the compound a is reduced by exposure.
Requirement (W01)
The photosensitive composition includes a compound a having an acid group, and the compound a further includes a structure in which the amount of the acid group is reduced by exposure.
The photosensitive composition according to [ 9 ], wherein,
in the above requirement (V01), the compound β is a compound B having a structure capable of accepting electrons from the acid group contained in the compound A in a photoexcited state,
in the above element (W01), the structure is a structure capable of receiving electrons from the acid group in a photoexcited state.
The photosensitive composition according to [ 9 ] or [ 10 ], which satisfies the above requirement (V01), wherein the compound (β) is a compound (B) having a structure capable of accepting electrons from the acid group contained in the compound (A) in a photoexcited state,
in the photosensitive composition, the total number of the electron-accepting structures included in the compound B is 1 mol% or more based on the total number of the acid groups included in the compound a.
The photosensitive composition according to any one of [ 1 ] to [ 11 ], wherein,
the above compound a contains a polymer having an acid group.
The photosensitive composition according to [ 12 ], wherein,
the polymer has a polymerizable group.
The photosensitive composition according to any one of [ 1 ] to [ 13 ], wherein,
the photosensitive composition further comprises a polymerizable compound.
The photosensitive composition according to any one of [ 1 ] to [ 14 ], wherein,
the photosensitive composition further comprises a photopolymerization initiator.
[ 16 ] A transfer film comprising: a temporary support; and a photosensitive layer formed from the photosensitive composition of any one of [ 1 ] to [ 15 ].
[ 17 ] A pattern forming method: which comprises the following steps in turn:
a step of bringing the surface of the photosensitive layer on the opposite side of the temporary support side of the transfer film described in [ 16 ] into contact with a substrate to bond the transfer film to the substrate;
exposing the photosensitive layer in a pattern; a kind of electronic device with high-pressure air-conditioning system
And developing the exposed photosensitive layer with an alkaline developer to form a pattern.
[ 18 ] A method for manufacturing a circuit wiring, comprising, in order:
a step of bringing the surface of the photosensitive layer on the opposite side of the temporary support side of the transfer film described in [ 16 ] into contact with the conductive layer of the substrate having a conductive layer, thereby bonding the transfer film to the substrate having a conductive layer;
exposing the photosensitive layer in a pattern;
developing the exposed photosensitive layer with an alkaline developer to form a patterned etching resist film; a kind of electronic device with high-pressure air-conditioning system
And etching the conductive layer in a region where the etching resist film is not disposed.
[ 19 ] A method for manufacturing a touch panel: which comprises the following steps in turn:
a step of bringing the surface of the photosensitive layer on the opposite side of the temporary support side of the transfer film described in [ 16 ] into contact with the conductive layer of the substrate having a conductive layer, thereby bonding the transfer film to the substrate having a conductive layer;
exposing the photosensitive layer in a pattern; a kind of electronic device with high-pressure air-conditioning system
And developing the exposed photosensitive layer with an alkaline developer to form a patterned protective film or insulating film of the conductive layer.
Effects of the invention
Therefore, according to the present invention, a photosensitive composition capable of forming a pattern excellent in corrosion resistance in a hot and humid environment can be provided.
Further, according to the present invention, a transfer film formed using the photosensitive composition can be provided.
Drawings
Fig. 1 is a schematic diagram showing an example of a layer structure of a transfer film according to the embodiment.
Detailed Description
The present invention will be described in detail below.
In the present specification, the numerical range indicated by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.
In the numerical ranges described in the present specification, the upper limit or the lower limit of a certain numerical range may be replaced with the upper limit or the lower limit of another numerical range described in a stepwise manner. In addition, in the numerical ranges described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the embodiment.
The term "process" in the present specification includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.
In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700nm is 80% or more, preferably 90% or more. Thus, for example, the term "transparent resin layer" refers to a resin layer having an average transmittance of 80% or more for visible light having a wavelength of 400 to 700 nm.
The average transmittance of visible light is a value measured by a spectrophotometer, and can be measured by using, for example, a spectrophotometer U-3310 manufactured by Hitachi, ltd.
In the present specification, the term "actinic rays" or "radiation" refers to, for example, an open spectrum of a mercury lamp such as g-rays, h-rays, and i-rays, extreme ultraviolet rays (EUV light) typified by excimer laser light, X-rays, and Electron Beams (EB), and the like. In the present invention, light means actinic rays or radiation.
In the present specification, unless otherwise specified, "exposure" includes not only exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, and the like typified by mercury lamps and excimer lasers, but also drawing by particle beams such as electron beams and ion beams. In the present specification, "irradiation with actinic rays or radiation" and "exposure" are used in the same sense.
In the present specification, unless otherwise specified, the content ratio of each structural unit of the polymer is a molar ratio.
In the present specification, the refractive index is a value measured at a wavelength of 550nm by an ellipsometer unless otherwise specified.
In the present specification, unless otherwise specified, the molecular weight when having a molecular weight distribution is a weight average molecular weight.
In the present specification, the weight average molecular weight of the resin is a weight average molecular weight obtained by conversion of polystyrene by Gel Permeation Chromatography (GPC).
In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth) acryl" is a concept including both acryl and methacryl.
In the present specification, the term "alkali-soluble" as used in the compound, the layer constituting the transfer film, and the like means that the dissolution rate obtained by the following method is 0.01 μm/sec or more.
A propylene glycol monomethyl ether acetate solution having a concentration of 25 mass% of an object (for example, a resin) was applied onto a glass substrate, and then heated in an oven at 100 ℃ for 3 minutes, whereby a coating film (thickness 2.0 μm) of the object was formed. The dissolution rate (μm/sec) of the coating film was determined by immersing the coating film in a 1 mass% aqueous solution of sodium carbonate (liquid temperature: 30 ℃).
In addition, when the object is insoluble in propylene glycol monomethyl ether acetate, the object is dissolved in an organic solvent (for example, tetrahydrofuran, toluene, or ethanol) having a boiling point of less than 200 ℃ other than propylene glycol monomethyl ether acetate.
In the present specification, "water-soluble" means that 100g of water at pH7.0 at a liquid temperature of 22℃has a solubility of 0.1g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the above solubility conditions.
The "solid component" of the composition refers to a component forming a composition layer (for example, a photosensitive layer) formed using the composition, and when the composition contains a solvent (for example, an organic solvent, water, or the like), it refers to all components except the solvent. In addition, if the composition layer is formed of a component, the liquid component is also regarded as a solid component.
In the present specification, unless otherwise specified, the thickness (film thickness) of the layer is an average thickness measured using a Scanning Electron Microscope (SEM) for a thickness of 0.5 μm or more, and is an average thickness measured using a Transmission Electron Microscope (TEM) for a thickness of less than 0.5 μm. The average thickness is an average thickness obtained by forming a slice of a measurement object using an ultra-thin microtome, measuring the thickness of any 5 points, and arithmetically averaging them.
[ photosensitive composition ]
The photosensitive composition of the present invention satisfies both the requirement A1 and the requirement B1 described below.
Condition A1: the glass transition temperature of the photosensitive layer after exposure obtained in step X described later is 65 ℃ or higher.
Requirement B1: the water content of the photosensitive layer after exposure obtained by the step X described later at 40 ℃ 90% rh is less than 2.0 mass%.
The pattern obtained from the photosensitive composition having the above structure is excellent in corrosion resistance under a hot and humid environment. The details thereof are not clear, but the present inventors speculate as follows. It is assumed that the pattern formed of the post-exposure photosensitive layer obtained from the photosensitive composition of the present invention has a small molecular motion because the glass transition temperature of the post-exposure photosensitive layer is equal to or higher than a predetermined temperature, and has significantly low hygroscopicity because the water content is equal to or lower than a predetermined value. As a result, the pattern obtained from the photosensitive composition of the present invention is considered to have excellent corrosion resistance in a hot and humid environment.
In the following, the pattern formed from the photosensitive composition of the present invention may be more excellent in corrosion resistance under a hot and humid environment, and the effect of the present invention may be more excellent.
Hereinafter, the characteristics of the photosensitive composition of the present invention will be described in detail.
[ requirement A1 ]
The photosensitive composition of the present invention satisfies the following requirement A1. The photosensitive composition of the present invention also preferably satisfies the following requirement A2.
Condition A1:
the glass transition temperature of the photosensitive layer after exposure obtained in step X described later is 65 ℃ or higher.
Condition A2:
the glass transition temperature of the photosensitive layer after exposure obtained in step X described later is 165 ℃ or lower.
Among these, the glass transition temperature in the element A1 is preferably 85 ℃ or higher, more preferably 100 ℃ or higher, from the viewpoint of further excellent effects of the present invention. Further, from the viewpoint of further excellent effects of the present invention, the glass transition temperature in the element A2 is preferably 120 ℃ or lower. Step X will be described first, and a method for measuring the glass transition temperature will be described next.
< step X >
Step X:a laminate having a glass substrate, a photosensitive layer formed of the photosensitive composition, and a resin film in this order was obtained. Next, the photosensitive layer in the laminate was exposed to light from the opposite side of the laminate to the glass substrate side using an ultra-high pressure mercury lamp so that the cumulative exposure at 365nm wavelength became 80mJ/cm 2 . After exposure, the laminate was left in an atmosphere of 50% RH at 25℃for 30 minutes, and then the resin film was peeled off. Next, the photosensitive layer was again exposed to light from the side from which the resin film was peeled off using a high-pressure mercury lamp so that the cumulative exposure at 365nm in wavelength became 1000mJ/cm 2 To obtain a post-exposure photosensitive layer.
In step X, a high-pressure mercury lamp was used to perform cumulative exposure at a wavelength of 365nm to 1000mJ/cm 2 Exposure processing of (a). When the irradiation conditions are applied, it can be said that the respective reactions of the photosensitive layer (for example, the curing reaction, the decarboxylation reaction of carboxylic acid described later, and the like) are generally substantially completed. Further, as will be described later, the laminate includes a case where another layer is interposed between the photosensitive layer and the resin film, but for example, if the laminate is a layer laminated on a transfer film, the cumulative exposure at 365nm wavelength using a high-pressure mercury lamp becomes 1000mJ/cm 2 In the case of the exposure treatment of (a), it is difficult to inhibit the curing reaction of the photosensitive layer and the decarboxylation reaction of carboxylic acid described later. In other words, even if another layer is interposed between the photosensitive layer and the resin film in the laminate, for example, if the laminate is a layer laminated on a transfer film, the cumulative exposure at 365nm wavelength using a high-pressure mercury lamp becomes 1000mJ/cm 2 In the case of the exposure treatment of (a), each reaction of the photosensitive layer is substantially completed.
In the step X, the illuminance at the time of exposure with an ultra-high pressure mercury lamp is preferably 5 to 100mW/cm 2 More preferably 10 to 50 mW/cm 2 。
Further, the illuminance at the time of exposure with a high-pressure mercury lamp is preferably 10 to 200mW/cm 2 More preferably 15 to]00mW/cm 2 。
In step X, the thickness of the photosensitive layer in the laminate is preferably 0.1 to 20. Mu.m, more preferably 1 to 9. Mu.m.
The photosensitive composition may be a coating composition or a layer form.
The case where the photosensitive composition is in the form of a layer refers to, for example, a case where the photosensitive composition is formed into a photosensitive layer by drying a coating film of the photosensitive composition. Specifically, the photosensitive composition in the form of a layer is a photosensitive layer or the like included in a transfer film.
In the case of performing step X on the photosensitive layer included in the transfer film, other layers may be included between the glass and the photosensitive layer and between the photosensitive layer and the temporary support (resin film) in the laminate.
Hereinafter, step X will be specifically described, with the photosensitive composition being in the form of a coating composition and the photosensitive composition being in the form of a layer.
< step X > in the case where the photosensitive composition is in the form of a coating composition
An example of step X in the case where the photosensitive composition is in the form of a coating composition will be described below.
On a glass substrate (for example, corning Incorporated co., ltd. Manufactured "EAGLE XG"), the photosensitive composition was spin-coated and then dried (for example, at 80 ℃ for 2 minutes) using a hot plate to obtain a film (photosensitive layer: film thickness of, for example, 2 μm).
Next, a resin film (for example, a polyethylene terephthalate film (PET film, for example, manufactured by tolay INDUSTRIES, INC., 16KS40, or the like)) is pressure-bonded from the upper surface of the obtained film (photosensitive layer), and a laminate in which a glass substrate, a photosensitive layer, and a resin film are laminated in this order is produced. As the pressure bonding condition of the resin film and the photosensitive layer, for example, the lamination temperature is set as: 25 ℃, pressure: 0.6Pa, line pressure: 3N/cm, transfer speed: 4 m/min.
Next, the photosensitive layer in the laminate is exposed to light from the side (opposite to the glass substrate side) of the laminate (via a resin film) using an ultra-High pressure mercury lamp (for example, a proximity type exposure machine (Hitachi High-Tech corporation) having an ultra-High pressure mercury lamp) so that the cumulative exposure amount at a wavelength of 365nm becomes 80mJ/cm 2 . In addition, the exposure was 80mJ/cm 2 The cumulative exposure amount of 365nm wavelength light reaching the photosensitive layer through the resin film. In the case where the resin film is a resin film other than a PET film (for example, a polypropylene film (PP film) or a polyethylene film (PE film)), it is preferable to expose the resin film through a filter having a wavelength of 350nm or less, in other words, it is preferable to expose the resin film through a filter having a wavelength of 350nm or less, and the cumulative exposure amount measured by a photometer of 365nm is 80mJ/cm 2 Is a single-layer exposure.
After exposure, the laminate was left in an atmosphere of 50% RH at 25℃for 30 minutes, and then the resin film was peeled off.
Next, the photosensitive layer is exposed from the surface side exposed by peeling of the resin film using a high-pressure mercury lamp (for example, an ultraviolet radiation transmitting device (EYE GRAPHICS CO., LTD.)) having a high-pressure mercury lamp so that the cumulative exposure amount at 365nm is 1000mJ/cm 2 。
In addition, the cumulative exposure at 365nm wavelength was 1000mJ/cm 2 The exposure of (C) means that the cumulative exposure amount measured by a photometer of 365nm becomes 1000mJ/cm 2 Is a single-layer exposure.
Then, the post-exposure photosensitive layer on the glass substrate was shaved off, and 100mg of a powdery test sample (hereinafter, sample X) was prepared. In addition, when the cut post-exposure photosensitive layer is not in a powder form, it is pulverized and used.
< step X > in the case where the photosensitive composition is in the form of a layer
An example of step X when the photosensitive composition is in a layer form will be described below.
The case where the photosensitive composition is in the form of a layer means the case where the photosensitive composition constitutes a photosensitive layer. Hereinafter, a method of obtaining a predetermined post-exposure photosensitive layer (sample X) from a photosensitive layer in a transfer film will be described by taking a transfer film including at least a temporary support (resin film) and a photosensitive layer composed of a photosensitive composition as an example.
First, the transfer film is pressure-bonded (laminated) on a glass substrate (for example, corning Incorporated co., ltd. Manufactured "EAGLE XG"). When laminating the transfer film, the surface of the photosensitive layer on the side opposite to the temporary support (resin film) side of the transfer film is brought into contact with the base material, and the transfer film is bonded to the glass substrate. In the case where the transfer film has a cover film, lamination is performed after the cover film is peeled off from the transfer film. As the lamination conditions, for example, the lamination temperature is set as: 100 ℃, line pressure: 3N/cm, transfer speed: 1 m/min. Thus, a laminate was obtained.
In addition, when the transfer film has other layers in addition to the cover film, photosensitive layer, and temporary support, the transfer film including the other layers is laminated on glass according to a usual use method of the transfer film. In this case, the laminate may have the other layer between the temporary support and the photosensitive layer and/or on the opposite side of the photosensitive layer from the temporary support.
Next, the photosensitive layer in the laminate is exposed from the side of the laminate opposite to the glass substrate side using an ultra-High pressure mercury lamp (for example, a proximity type exposure machine (Hitachi High-Tech corporation) having an ultra-High pressure mercury lamp) so that the cumulative exposure amount at a wavelength of 365nm becomes 80mJ/cm 2 . In addition, the exposure was 80mJ/cm 2 The cumulative exposure amount of 365nm wavelength light reaching the photosensitive layer through the resin film. In the case where the resin film is a resin film other than a PET film (for example, a polypropylene film (PP film) or a polyethylene film (PE film)), it is preferable to expose the resin film through a filter having a wavelength of 350nm or less, in other words, it is preferable to expose the resin film through a filter having a wavelength of 350nm or less, and the cumulative exposure amount measured by a photometer of 365nm is 80mJ/cm 2 Is a single-layer exposure.
After exposure, the laminate was left in an atmosphere of 50% RH at 25℃for 30 minutes, and then the temporary support (resin film) was peeled off.
Next, the photosensitive layer is exposed from the surface side exposed by the peeling of the temporary support (resin film) using a high-pressure mercury lamp (for example, an ultraviolet radiation transmitting device (EYE GRAPHICS co., ltd.) having a high-pressure mercury lamp) so that the cumulative exposure amount at 365nm wavelength becomes 100 0mJ/cm 2 。
In addition, the cumulative exposure at 365nm wavelength was 1000mJ/cm 2 The exposure of (C) means that the cumulative exposure amount measured by a photometer of 365nm becomes 1000mJ/cm 2 Is a single-layer exposure.
In the laminate obtained by laminating the transfer film on the glass substrate, when the other layer (for example, the thermoplastic resin layer, the intermediate layer, and the like) is present between the temporary support and the photosensitive layer, the cumulative exposure at the wavelength 365nm is preferably 1000mJ/cm 2 The other layers are removed after exposure. The removal method is not particularly limited, and for example, the other layers can be removed from the laminate by an alkali development treatment, a solvent cleaning treatment, a tape stripping treatment, or the like. The photosensitive layer is exposed to the outermost layer by the above-mentioned removal treatment.
Among these, in the above-described treatment, it is preferable that the laminate is not subjected to a heat treatment.
The photosensitive layer is not deteriorated as much as possible when the above-mentioned treatment is performed.
Then, the post-exposure photosensitive layer on the glass substrate was shaved off, and 100mg of a powdery test sample (hereinafter, sample X) was prepared. In addition, when the cut post-exposure photosensitive layer is not in a powder form, it is pulverized and used.
Measurement of glass transition temperature of post-exposure photosensitive layer formed by step X
Using 5 to 6mg of the sample X prepared in the step X, a temperature-modulated differential scanning calorimeter measurement was performed under the following conditions. The measurement conditions using temperature-modulated differential scanning calorimetric measurement are preferably the following conditions.
The device comprises: DSC2500 manufactured by TA Instruments (Tzero aluminum crucible was used when the sample was enclosed)
Measurement conditions: under nitrogen atmosphere, temperature range-70-200 ℃ (5 ℃/min), temperature modulation condition + -1 ℃/min (n=2))
Next, the temperature (midpoint) of the baseline shift in the reversible heat Flow (rev. Heat Flow) was taken as the glass transition temperature (average value of n 2).
[ requirement B1 ]
The photosensitive composition of the present invention satisfies the following requirement B1. The photosensitive composition of the present invention also preferably satisfies the following requirement B2.
Requirement B1:
the water content of the photosensitive layer after exposure formed by step X described later is less than 2.0 mass% at 40 ℃ 90% rh.
Requirement B2:
the water content of the photosensitive layer after exposure formed by step X described later is more than 0 mass% at 40 ℃ and 90% rh.
Among these, the water content at 40 ℃ 90% rh in the element B2 is preferably 0.5 mass% or more from the viewpoint of further excellent effects of the present invention.
Hereinafter, the method for measuring the water content in step X will be described. The method for measuring the water content includes steps (1) to (9) described below.
< step X >
The step X is the same as < < step X > > in the explanation of the element A.
Measurement of moisture content of the photosensitive layer after exposure formed by step X at 40 ℃ 90% RH
(1) In a laboratory at 23℃with 50% RH, 11 to 12mg of sample X prepared in step X was weighed. The mass of the sample X weighed here was a [ mg ].
(2) Next, the weighed sample X was charged into a furnace of a heated discharge device heated to 150 ℃, and the moisture content was measured using a karl fischer moisture meter for 15 minutes.
As the karl fischer moisture meter, for example, "AQ-2100" manufactured by hicamoma co., ltd. As the heating discharge device, "EV-2000" manufactured by HIRANUMA co., ltd.
(3) Then, the water content x [ mass% ] at 23 ℃ 50% rh was determined from the measured water content by the following formula.
(moisture amount/a) ×100=x [ mass% ]
(4) In a laboratory at 23℃with 50% RH, 11 to 12mg of sample X prepared in step X was weighed. The mass of the sample X weighed here was b [ mg ].
(5) Then, the weighed sample X was stored in a constant temperature and humidity tank at 40℃and 90% RH for 24 hours.
(6) Immediately after the sample X was taken out of the constant temperature and humidity tank, it was put into a furnace of a heated discharge device heated to 150 ℃, and the moisture content was measured for 15 minutes using a karl fischer moisture meter.
As the karl fischer moisture meter, for example, "AQ-2100" manufactured by hicamoma co., ltd. As the heating discharge device, "EV-2000" manufactured by HIRANUMA co., ltd.
(7) Then, the water content y [ mass% ] at 40 ℃ and 90% rh (apparent) was determined from the measured water content by the following formula.
(moisture amount/b) ×100=y [ mass% ]
(8) The water content at 40℃and 90% RH was determined by the following formula using the values of x and y determined in (3) and (7).
{ moisture amount/(dry mass+moisture amount) } ×100[ mass% ] = [ (b×y/100)/{ b× (100-x)/100+b×y/100} ] ×100[ mass% ] = { y/(100-x+y) } ×100[ mass% ]
(9) The water content was measured 5 times in a series of steps (1) to (8) above, and the arithmetic average was taken as the water content (mass%) at 40℃and 90% RH.
[ photosensitive composition ]
Hereinafter, specific embodiments of the photosensitive composition satisfying both the above-described requirements A1 and B1 will be described.
The photosensitive composition preferably contains the compound a having an acid group, and the content of the acid group in the photosensitive composition is reduced by irradiation with actinic rays or radiation.
The photosensitive layer formed by using the photosensitive composition having such a structure is reduced in content of the acid group by exposure. That is, the polarity in the photosensitive layer changes before and after exposure, and thus the solubility in the developer (alkaline developer and organic solvent-based developer) changes. Therefore, when such a photosensitive layer is subjected to pattern exposure, a dissolution contrast with respect to a developer is generated in the exposed portion and the non-exposed portion, and thus a pattern can be formed.
As an example of the photosensitive composition having a mechanism of reducing the content of the acid group, a photosensitive composition containing a compound a having a carboxyl group and having a mechanism of reducing the content of the carboxyl group in the photosensitive composition by causing the decarboxylation reaction of the carboxyl group by exposure to light can be given.
The photosensitive layer formed using the photosensitive composition having such a structure exhibits excellent pattern formability in a developer (an alkaline developer and an organic solvent-based developer). Further, since the amount of the acid groups in the photosensitive layer is reduced by exposure, the moisture permeability due to the presence of the acid groups is reduced, and as a result, the corrosion resistance in a hot and humid environment is more excellent. Therefore, the pattern formed by the photosensitive layer can be preferably used as a protective film (permanent film) for a conductive pattern or the like.
The photosensitive composition preferably contains a polymerizable compound as described later.
For example, when the acid group (for example, carboxyl group or the like) is released (for example, decarboxylation reaction) in the photosensitive layer formed using the photosensitive composition having such a structure, radicals can be generated in the portion of the compound a from which the acid group is released. By radical polymerization of such a radical-initiated polymerizable compound, the compound a in the exposed portion can be crosslinked.
The photosensitive composition preferably contains a polymerizable compound and a photopolymerization initiator, as will be described later.
The photosensitive layer formed using the photosensitive composition having such a structure can cause the detachment of the acid group (carboxyl group or the like) and the polymerization initiation reaction at different times. For example, a photosensitive layer formed using the photosensitive composition having the above-described structure may be first subjected to a first exposure at a wavelength or an exposure amount at which the detachment of an acid group hardly occurs, and polymerized by a photopolymerization initiator to be cured. Then, the cured photosensitive layer may be subjected to a second exposure to cause the release of the acid groups. The first exposure may be a pattern-like exposure, and the second exposure may be performed after a development step for removing the unexposed portion or the exposed portion is performed before the second exposure, to obtain a pattern.
Condition (V01), condition (W01)
The photosensitive composition is preferably one satisfying any of the following requirements (V01) and (W01). The photosensitive composition may satisfy both the requirement (V01) and the requirement (W01).
Requirement (V01)
The photosensitive composition contains a compound a having an acid group and a compound β having a structure (hereinafter, also referred to as "specific structure S0") in which the amount of the acid group contained in the compound a is reduced by exposure to light.
Requirement (W01)
The photosensitive composition contains a compound a having an acid group, and the compound a further contains a structure (specific structure S0) in which the amount of the acid group is reduced by exposure.
The specific structure S0 is a structure that, when exposed to light, exhibits an effect of reducing the amount of acid groups contained in the compound a. As the specific structure S0, a structure that is converted from a base state to an excited state by exposure and shows an effect of reducing an acid group in the compound a in the excited state is preferable. The specific structure S0 may be, for example, a structure (specific structure S1 described below) which is exposed to light and is in a photoexcited state and which can accept electrons from an acid group included in the compound a.
The above-described element (V01) is preferably the element (V1) shown below, and the above-described element (W01) is preferably the element (W1) shown below. That is, in the above requirement (V01), the compound β is preferably a compound B having a structure capable of receiving electrons from an acid group included in the compound a in a photoexcited state. In the above requirement (W01), the structure is preferably a structure capable of receiving electrons from the acid group included in the compound a in the photoexcited state.
Requirement (V1): the photosensitive composition contains a compound a having an acid group and a compound B having a structure (specific structure S1) capable of accepting electrons from the acid group contained in the compound a in a photoexcited state.
Element (W1): the photosensitive composition contains a compound a having an acid group, and the compound a further contains a structure (specific structure S1) capable of accepting electrons from the acid group in a photoexcited state.
The photosensitive composition may be one satisfying both the requirement (V1) and the requirement (W1).
Among these, a photosensitive composition satisfying any of the requirements (V1-C) and the requirements (W1-C) is more preferable. The element (V1-C) corresponds to the way in which the acid group in the element (V1) is a carboxyl group, and the element (W1-C) corresponds to the way in which the acid group in the element (W1) is a carboxyl group.
Essential element (V1-C)
The photosensitive composition X includes a compound a having a carboxyl group and a compound B having a structure capable of accepting electrons from the carboxyl group in the compound a in a photoexcited state (hereinafter also referred to as "specific structure S1").
Essential element (W1-C)
The photosensitive composition X contains a compound a having a carboxyl group, and the above compound a further contains a structure (specific structure S1) capable of accepting electrons from the carboxyl group in the compound a in a photoexcited state.
The photosensitive composition may be one satisfying both the requirement (V1-C) and the requirement (W1-C).
Hereinafter, a mechanism for estimating the reduction in the content of an acid group (carboxyl group) derived from the compound a by exposure will be described in detail, taking as an example a case where the photosensitive composition contains polyacrylic acid as the compound a and quinoline as the compound β (compound B).
As shown in the following figures, carboxyl groups of polyacrylic acid and nitrogen atoms of quinoline form hydrogen bonds in a coexisting state. When quinoline is exposed to light, the electron acceptance increases, and electrons are transferred from the carboxyl group of polyacrylic acid (step 1: photoexcitation). If the carboxyl group of polyacrylic acid transfers electrons to quinoline, it becomes unstable and becomes carbon dioxide to be released (step 2: decarboxylation). When the decarboxylation reaction is performed, radicals are generated at the residue of polyacrylic acid, and the radical reaction proceeds. Radical reaction (step 3: polarity inversion, crosslinking, polymerization reaction) can occur between the residues of polyacrylic acid and each other, between the residues of polyacrylic acid and the polymerizable compound (monomer (M)) optionally contained, and between hydrogen atoms in the atmosphere. After the radical reaction is completed, the compound β is regenerated to be able to contribute again to the decarboxylation process of the compound a (step 4: compound β (catalyst) regeneration).
[ chemical formula 1]
The means for reducing the content of the acid group derived from the compound a by exposure is not limited to the method based on decarboxylation as described above, and a known method capable of reducing the content of the acid group derived from the compound a can be appropriately selected.
From the viewpoint of the photosensitive composition having more excellent patterning ability particularly for an alkaline developer, the content of the acid group (preferably carboxyl group) derived from the compound a is preferably reduced at a reduction rate of 5 mol% or more, more preferably at a reduction rate of 10 mol% or more, still more preferably at a reduction rate of 20 mol% or more, still more preferably at a reduction rate of 31 mol% or more, particularly preferably at a reduction rate of 40 mol% or more, even more preferably at a reduction rate of 51 mol% or more, and most preferably at a reduction rate of 71 mol% or more. The upper limit is not particularly limited, and is, for example, 100 mol% or less.
The reduction in the content of the acid group (preferably carboxyl group) derived from the compound a by exposure of the photosensitive composition can be quantified by the same method as the reduction rate of the content of the carboxyl group derived from the compound a in the photosensitive layer in the transfer film described later.
Example of embodiment of photosensitive composition
An example of an embodiment of the photosensitive composition is shown below.
Photosensitive composition of embodiment X-1-a1
The photosensitive composition is a photosensitive composition which satisfies at least one of the requirements (V01) and (W01) and contains substantially no polymerizable compound and photopolymerization initiator.
Photosensitive composition of embodiment X-1-a2
The photosensitive composition is a photosensitive composition which satisfies at least one of the requirements (V01) and (W01) and contains substantially no photopolymerization initiator.
Photosensitive layer of embodiment X-1-a3
The photosensitive composition satisfies at least one of the requirements (V01) and (W01) and contains a polymerizable compound and a photopolymerization initiator.
In the photosensitive composition of embodiment X-1-a1, the phrase "the photosensitive composition contains substantially no polymerizable compound" means that the content of the polymerizable compound is preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, relative to the total solid content of the photosensitive composition, as long as the content is less than 3% by mass.
In the photosensitive compositions of embodiments X-1-a1 and X-1-a2, the phrase "the photosensitive composition contains substantially no photopolymerization initiator" means that the content of the photopolymerization initiator is preferably 0 to 0.05 mass%, more preferably 0 to 0.01 mass% relative to the total solid content of the photosensitive composition.
The photosensitive compositions of embodiments X-1-a1 and X-1-a2 are preferably applied to the pattern forming method of embodiment 1 described below. The photosensitive composition of embodiment X-1 to a3 is preferably applied to the pattern forming method of embodiment 2 described below.
Further, as an embodiment of the photosensitive composition, the photosensitive compositions of embodiments X-1-a1-C to X-1-a3-C are more preferable. Further, embodiments X-1-a1-C to X-1-a3-C correspond to the manner in which the element (V01) and the element (W01) in embodiments X-1-a1 to X-1-a3 are the element (V1-C) and the element (W1-C), respectively.
< various Components >
< Compound A having an acid group >
The photosensitive composition contains a compound a (compound a) having an acid group.
The acid group included in the compound a is preferably a proton dissociable group having a pKa of 12 or less. Specific examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group, and the like, and a carboxyl group is preferable.
The compound a may be a low-molecular compound or a high-molecular compound (hereinafter also referred to as "polymer"), but preferably contains a polymer (a polymer having an acid group), and more preferably contains a polymer having a polymerizable group.
Examples of the polymerizable group include an ethylenically unsaturated group (for example, (meth) acryl, vinyl, styryl, etc.), a cyclic ether group (for example, epoxy, oxetanyl, etc.), etc., preferably an ethylenically unsaturated group, more preferably a (meth) acryl.
In the case where the compound a is a low-molecular compound, the molecular weight of the compound a is preferably less than 5,000, more preferably 2,000 or less, further preferably 1,000 or less, particularly preferably 500 or less, and most preferably 400 or less.
In the case where the compound a is a polymer, the lower limit value of the weight average molecular weight of the compound a is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more, from the viewpoint of excellent formability of the photosensitive layer (in other words, excellent film forming performance for forming the photosensitive layer). The upper limit is not particularly limited, but is preferably 50,000 or less from the viewpoint of further excellent adhesion (lamination adhesion) when the adhesive is bonded to an arbitrary substrate (at the time of transfer).
In the case where the compound A is a polymer, the acid value of the compound A as a polymer is preferably 60 to 300mgKOH/g, more preferably 60 to 275mgKOH/g, and even more preferably 75 to 250mgKOH/g from the viewpoint of developability.
In the present specification, the acid value of the resin is a value measured by a titration method specified in JIS K0070 (1992).
The compound a also preferably contains a structure (specific structure S0) in which the amount of acid groups contained in the compound a is reduced by exposure. In the following, the compound a not including the specific structure S0 is also referred to as "compound Aa", and the compound a including the specific structure S0 is referred to as "compound Ab". In addition, the compound Ab is preferably a polymer.
The fact that compound a does not include specific structure S0 means that compound a does not substantially include specific structure S0, and for example, the content of specific structure S0 in compound Aa may be less than 1% by mass, preferably 0 to 0.5% by mass, and more preferably 0 to 0.05% by mass, relative to the total mass of compound Aa.
The content of the specific structure S0 in the compound Ab is preferably 1% by mass or more, more preferably 1 to 50% by mass, still more preferably 5 to 40% by mass, relative to the total mass of the compound Ab.
In the case where compound a contains compound Ab, the content of compound Ab is preferably 5 to 100 mass% relative to the total mass of compound a.
As described above, the specific structure S0 is a structure that, when exposed to light, exhibits an effect of reducing the amount of acid groups contained in the compound a. As the specific structure S0, a structure that is converted from a base state to an excited state by exposure and shows an effect of reducing an acid group in the compound a in the excited state is preferable.
The specific structure S0 of the compound a includes a structure (specific structure S1) capable of accepting electrons from an acid group included in the compound a in a photoexcited state.
The specific structure S1 includes a heteroaromatic ring.
The heteroaromatic ring may be a single ring or multiple rings, and is preferably multiple rings. Polycyclic heteroaromatic rings are fused by a plurality (e.g., 2 to 5) of aromatic ring structures, and at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom.
The heteroaromatic ring has 1 or more heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as a ring member atom, preferably 1 to 4 heteroatoms. The heteroaromatic ring preferably has 1 or more (for example, 1 to 4) nitrogen atoms as the ring member atoms.
The number of ring members of the heteroaromatic ring is preferably 5 to 15.
Examples of the heteroaromatic ring include: monocyclic heteroaromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring and triazine ring; heteroaromatic rings obtained by fusing 2 rings such as quinoline ring, isoquinoline ring, quinoxaline ring and quinazoline ring; heteroaromatic rings obtained by fusing 3 rings such as an acridine ring, a phenanthridine ring, a phenanthroline ring, and a phenazine ring.
The heteroaromatic ring may have 1 or more (for example, 1 to 5) substituents, and examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, and a nitro group. In the case where the aromatic ring has 2 or more substituents, a plurality of substituents may be bonded to each other to form a non-aromatic ring.
Further, the heteroaromatic ring is also preferably directly bonded to the carbonyl group.
It is also preferable that the heteroaromatic ring is bonded to an imide group to form a heteroaromatic imide group. In addition, the imide group in the heteroaromatic imide group may or may not form an imide ring together with the heteroaromatic ring.
In the compound a, a series of aromatic ring structures bonded by a structure selected from the group consisting of a single bond, a carbonyl group, and multiple bonds (e.g., vinylidene groups which may have substituents, -c≡c-, -n=n-, etc.) are formed in a plurality of aromatic rings (e.g., 2 to 5 aromatic rings), and when 1 or more of the plurality of aromatic rings constituting the series of aromatic ring structures are the above-mentioned heteroaromatic rings, the whole series of aromatic ring structures is regarded as 1 specific structure S1.
In addition, some or all of the acid groups of the compound a may be anionic or non-anionic in the photosensitive composition, and both the anionic acid groups and the non-anionic acid groups are included and referred to as acid groups. That is, the compound a may be anionic or non-anionic in the photosensitive composition.
Among these, the compound having a carboxyl group is preferable from the viewpoint of more excellent patterning ability of the photosensitive composition and the viewpoint of more excellent film forming property.
The compound having a carboxyl group is preferably a monomer containing a carboxyl group (hereinafter, also referred to as "carboxyl group-containing monomer") or a polymer containing a carboxyl group (hereinafter, also referred to as "carboxyl group-containing polymer"), and is more preferably a polymer containing a carboxyl group from the viewpoint of more excellent patterning ability and more excellent film forming property of the photosensitive composition.
In addition, a part or all of carboxyl groups (-COOH) contained in the carboxyl group-containing monomer and the carboxyl group-containing polymer may be anionic or non-anionic in the photosensitive composition, and the anionic carboxyl groups (-COO) - ) Both the carboxyl groups and the non-anionic carboxyl groups are included and are referred to as carboxyl groups.
That is, the carboxyl group-containing monomer may be anionic or non-anionic in the photosensitive composition, and both the anionic carboxyl group-containing monomer and the non-anionic carboxyl group-containing monomer are included and referred to as carboxyl group-containing monomers.
That is, the carboxyl group-containing polymer may be anionized or not anionized in the photosensitive composition, and both the anionized carboxyl group-containing polymer and the non-anionized carboxyl group-containing polymer are included and referred to as carboxyl group-containing polymers.
As described above, the compound a containing a carboxyl group may contain a specific structure S0 (preferably a specific structure S1). In other words, the carboxyl group-containing monomer and the carboxyl group-containing polymer may contain a specific structure S0 (preferably a specific structure S1). In the case where the compound a containing a carboxyl group contains a specific structure S0 (preferably a specific structure S1), among them, a carboxyl group-containing polymer containing a specific structure S0 (preferably a specific structure S1) is preferable, and a carboxyl group-containing polymer containing a specific structure S1 is more preferable.
In the photosensitive composition, the lower limit of the content of the compound a is preferably 1% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, still more preferably 45% by mass or more, and particularly preferably 50% by mass or more, relative to the total solid content of the photosensitive composition. The upper limit of the content of the compound a is preferably 100% by mass or less, more preferably 99% by mass or less, further preferably 97% by mass or less, particularly preferably 93% by mass or less, more particularly preferably 85% by mass or less, and most preferably 75% by mass or less, based on the total solid content of the photosensitive composition. When the photosensitive composition satisfies the requirement W01, the upper limit of the content of the compound a is preferably 99 mass% or less with respect to the total solid content of the photosensitive composition.
The compound A may be used singly or in combination of two or more.
(carboxyl group-containing monomer)
Examples of the carboxyl group-containing monomer include polymerizable compounds containing a carboxyl group and containing 1 or more (for example, 1 to 15) ethylenically unsaturated groups.
Examples of the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, and a styryl group, and a (meth) acryloyl group is preferable.
The monomer having a carboxyl group is preferably a monomer having 2 or more functions including a carboxyl group, from the viewpoint of more excellent film forming property. The monomer having 2 or more functions means a polymerizable compound having 2 or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.
The carboxyl group-containing monomer may further have an acid group other than the carboxyl group as an acid group. Examples of the acid group other than the carboxyl group include phenolic hydroxyl group, phosphate group and sulfonate group.
The monomer having 2 or more functions including a carboxyl group is not particularly limited, and may be appropriately selected from known compounds.
Examples of the monomer having a carboxyl group of 2 or more functions include ARONIX (registered trademark) TO-2349 (toakosie co., ltd. Manufactured), ARONIX M-520 (toakosie co., ltd. Manufactured), ARONIX M-510 (toakosie co., ltd. Manufactured), and the like.
Examples of the monomer having 2 or more functions including a carboxyl group include a polymerizable compound having 3 to 4 functions including a carboxyl group (a compound having a carboxyl group introduced into pentaerythritol tri-and tetra-acrylate [ PETA ] skeleton (acid value=80 to 120 mgKOH/g)), a polymerizable compound having 5 to 6 functions including a carboxyl group (a compound having a carboxyl group introduced into dipentaerythritol penta-and hexaacrylate [ DPHA ] skeleton (acid value=25 to 70 mgKOH/g)), and the like. In the case of using a monomer having 3 or more functions including the carboxyl group, it is preferable to use a monomer having 2 or more functions including the carboxyl group at the same time, from the viewpoint of further excellent film forming property.
Examples of the monomer having 2 or more functions including a carboxyl group include polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The content of this publication is incorporated into the present specification.
(carboxyl group-containing Polymer)
Typically, the carboxyl group-containing polymer is an alkali-soluble resin. In addition, the definition and measurement method of alkali solubility are as already described.
The polymer containing a carboxyl group may further have an acid group other than the carboxyl group as an acid group. Examples of the acid group other than the carboxyl group include phenolic hydroxyl group, phosphate group and sulfonate group.
From the viewpoint of developability, the acid value of the carboxyl group-containing polymer is preferably 60 to 300mgKOH/g, more preferably 60 to 275mgKOH/g, still more preferably 75 to 250mgKOH/g.
Repeating units having carboxyl groups
The polymer having a carboxyl group preferably has a repeating unit having a carboxyl group.
Examples of the repeating unit having a carboxyl group include repeating units represented by the following general formula (a).
[ chemical formula 2]
In the general formula (A), R A1 Represents a hydrogen atom, a halogen atom or an alkyl group.
The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1.
In the general formula (A), A 1 Represents a single bond or a divalent linking group.
As the above divalent linking group, for example, can be exemplified by-CO-, -O-; -S-, -SO 2 -、-NR N -(R N An alkyl group having 1 to 5 carbon atoms), a hydrocarbon group (e.g., an arylene group such as an alkylene group, a cycloalkylene group, an alkenylene group, or a phenylene group), and a linking group formed by linking a plurality of these groups.
Examples of the monomer that is a source of the repeating unit having a carboxyl group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among them, (meth) acrylic acid is preferable from the viewpoint of more excellent patterning properties. That is, the repeating unit having a carboxyl group is preferably derived from a repeating unit of (meth) acrylic acid.
In the carboxyl group-containing polymer, the content of the repeating unit having a carboxyl group is preferably 5 to 100 mol%, more preferably 10 to 65 mol%, and even more preferably 15 to 45 mol% with respect to all the repeating units of the carboxyl group-containing polymer.
In the carboxyl group-containing polymer, the content of the repeating unit having a carboxyl group is preferably 1 to 100% by mass, more preferably 5 to 70% by mass, and still more preferably 12 to 50% by mass, based on all the repeating units of the carboxyl group-containing polymer.
The repeating unit having a carboxyl group may be used singly or in combination of two or more.
Repeating units having polymerizable groups
In addition to the above-mentioned repeating units, the carboxyl group-containing polymer preferably contains a repeating unit having a polymerizable group.
Examples of the polymerizable group include an ethylenically unsaturated group (for example, (meth) acryl, vinyl, styryl, etc.), a cyclic ether group (for example, epoxy, oxetanyl, etc.), etc., preferably an ethylenically unsaturated group, more preferably a (meth) acryl.
Examples of the repeating unit having a polymerizable group include repeating units represented by the following general formula (B).
[ chemical formula 3]
In the general formula (B), X B1 X is X B2 Each independently represents-O-or-NR N -。
R N Represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and preferably has 1 to 5 carbon atoms.
L represents an alkylene group or an arylene group. The alkylene group may be linear or branched, and preferably has 1 to 5 carbon atoms. The arylene group may be a single ring or multiple rings, and the number of carbon atoms is preferably 6 to 15. The alkylene group and the arylene group may have a substituent, and for example, a hydroxyl group is preferable as the substituent.
R B1 R is R B2 Each independently represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1.
The content of the repeating unit having a polymerizable group in the polymer having a carboxyl group is preferably 3 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 30 mol% based on all the repeating units of the polymer having a carboxyl group.
In the carboxyl group-containing polymer, the content of the repeating unit having a polymerizable group is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, and still more preferably 12 to 45% by mass, relative to all the repeating units of the carboxyl group-containing polymer.
The repeating unit having a polymerizable group may be used singly or in combination of two or more.
Repeating units having the specific structure S0
In addition to the above-mentioned repeating units, the carboxyl group-containing polymer preferably also contains a repeating unit having a specific structure S0 (preferably a specific structure S1).
The specific structure S0 and the specific structure S1 are as described above.
Among the repeating units having the specific structure S0 (preferably the specific structure S1), the specific structure S0 (preferably the specific structure S1) may be present in the main chain or in the side chain, preferably in the side chain. In the case where the specific structure S0 (preferably the specific structure S1) is present in the side chain, the specific structure S0 (preferably the specific structure S1) is bonded to the polymer main chain via a single bond or a linking group.
The repeating unit having the specific structure S0 (preferably the specific structure S1) is, for example, a repeating unit based on a monomer having a heteroaromatic ring (specifically, a (meth) acrylate monomer having a vinyl heteroaromatic ring and a heteroaromatic ring such as vinyl pyridine and vinyl (iso) quinoline).
Specific examples of the repeating unit having the specific structure S0 (preferably the specific structure S1) are shown below, but the present invention is not limited thereto.
[ chemical formula 4]
In the case where the carboxyl group-containing polymer contains a repeating unit having a specific structure S0 (preferably a specific structure S1), the content thereof is preferably 3 to 75 mol%, more preferably 5 to 60 mol%, and still more preferably 10 to 50 mol% with respect to all the repeating units of the carboxyl group-containing polymer.
In the case where the carboxyl group-containing polymer contains a repeating unit having a specific structure S0 (preferably a specific structure S1), the content thereof is preferably 1 to 75% by mass, more preferably 3 to 60% by mass, and even more preferably 5 to 30% by mass, relative to all the repeating units of the carboxyl group-containing polymer.
The repeating units having the specific structure S0 (preferably the specific structure S1) may be used singly or in combination of two or more.
Repeating units having aromatic rings
The polymer containing a carboxyl group preferably contains a repeating unit having an aromatic ring (preferably an aromatic hydrocarbon ring) in addition to the repeating unit. For example, a repeating unit based on a (meth) acrylate having an aromatic ring, and a repeating unit based on styrene and a polymerizable styrene derivative are given.
Examples of the (meth) acrylate having an aromatic ring include benzyl (meth) acrylate, phenethyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
Examples of styrene and polymerizable styrene derivatives include methyl styrene, vinyl toluene, t-butoxy styrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, and styrene trimer.
As the repeating unit having an aromatic ring, for example, a repeating unit represented by the following general formula (C) is also preferable.
[ chemical formula 5]
In the general formula (C), R C1 Represents a hydrogen atom, a halogen atom or an alkyl group. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1.
Ar C Represents phenyl or naphthyl. The phenyl group and the naphthyl group may have 1 or more substituents, and examples of the substituents include an alkyl group, an alkoxy group, an aryl group, a halogen atom, and a hydroxyl group.
Hereinafter, a repeating unit having an aromatic ring is exemplified.
[ chemical formula 6]
Among them, the following structure is preferable as the repeating unit having an aromatic ring.
[ chemical formula 7]
In the carboxyl group-containing polymer, the content of the repeating unit having an aromatic ring is preferably 5 to 80 mol%, more preferably 15 to 75 mol%, and still more preferably 30 to 70 mol% with respect to all the repeating units of the carboxyl group-containing polymer.
In the carboxyl group-containing polymer, the content of the repeating unit having an aromatic ring is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 30 to 70% by mass, relative to all the repeating units of the carboxyl group-containing polymer.
The repeating unit having an aromatic ring may be used singly or in combination of two or more.
Repeating units having an alicyclic structure
In addition to the above-mentioned repeating units, the carboxyl group-containing polymer preferably contains repeating units having an alicyclic structure. The alicyclic structure may be a single ring or multiple rings.
Examples of the alicyclic structure include a dicyclopentyl ring structure, a dicyclopentenyl ring structure, an isobornyl ring structure, an adamantane ring structure, and a cyclohexyl ring structure.
Examples of the monomer derived from a repeating unit having an alicyclic structure include dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and cyclohexyl (meth) acrylate.
In the carboxyl group-containing polymer, the content of the repeating unit having an alicyclic structure is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, and still more preferably 10 to 55 mol% based on all the repeating units of the carboxyl group-containing polymer.
In the carboxyl group-containing polymer, the content of the repeating unit having an alicyclic structure is preferably 3 to 90% by mass, more preferably 5 to 70% by mass, and even more preferably 25 to 60% by mass, relative to all the repeating units of the carboxyl group-containing polymer.
The repeating unit having an alicyclic structure may be used singly or in combination of two or more.
Other repeating units
The carboxyl group-containing polymer may have other repeating units in addition to the above-mentioned repeating units.
The monomer that is a source of the other repeating unit includes an alkyl (meth) acrylate, and the alkyl group includes an alkyl group having a chain structure. The chain structure may be a straight chain structure or a branched structure. Substituents such as hydroxyl groups may be present in the alkyl group. The number of carbon atoms of the alkyl group is 1 to 50, more preferably 1 to 10. Specific examples thereof include methyl (meth) acrylate.
In the carboxyl group-containing polymer, the content of the other repeating units is preferably 1 to 70 mol%, more preferably 2 to 50 mol%, and still more preferably 3 to 20 mol% based on all the repeating units of the carboxyl group-containing polymer.
In the carboxyl group-containing polymer, the content of the other repeating units is preferably 1 to 70% by mass, more preferably 2 to 50% by mass, and even more preferably 5 to 35% by mass, relative to all the repeating units of the carboxyl group-containing polymer.
The other repeating units may be used singly or in combination of two or more.
The weight average molecular weight of the carboxyl group-containing polymer is preferably 5000 to 200000, more preferably 10000 to 100000, most preferably 11000 to 49000.
The content of the polymer (preferably a polymer containing a carboxyl group) in the compound a is preferably 75 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, relative to the total content of the compound a.
The content of the monomer (preferably a carboxyl group-containing monomer) in the compound a is preferably 0 to 25% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 5% by mass, relative to the total content of the compound a.
The content of the compound a is preferably 25 to 100% by mass based on the total solid content of the photosensitive composition. When the photosensitive composition satisfies the requirement (V01) and/or the requirement (V1) (that is, when the photosensitive composition contains the compound β and/or the compound B), the content of the compound a is preferably 25 to 99 mass% with respect to the total solid content of the photosensitive composition.
In the photosensitive composition of embodiment X-1-a1, the content of the compound A is preferably 40 to 98% by mass, more preferably 50 to 96% by mass, and still more preferably 60 to 93% by mass, based on the total solid content of the photosensitive composition.
In the photosensitive composition of embodiment X-1-a2, the content of the compound A is preferably 30 to 85% by mass, more preferably 45 to 75% by mass, based on the total solid content of the photosensitive composition.
In the photosensitive composition of embodiment X-1-a3, the content of the compound A is preferably 30 to 85% by mass, more preferably 45 to 75% by mass, based on the total solid content of the photosensitive composition.
< Compound beta >
The photosensitive composition preferably contains a compound β.
The compound β is a compound having a structure (specific structure S0) in which the amount of acid groups contained in the compound a is reduced by exposure. In addition, the description has been made regarding the specific structure S0.
The specific structure S0 of the compound β may be an integral structure constituting the whole of the compound β or may be a partial structure constituting a part of the compound β.
The compound β may be a high molecular compound, or may be a low molecular compound, and is preferably a low molecular compound.
The molecular weight of the compound β as a low molecular compound is preferably less than 5,000, more preferably less than 1,000, further preferably 65 to 300, particularly preferably 75 to 250.
Among these specific structures S0, a structure capable of accepting electrons from the acid group included in the compound a in the photoexcited state (specific structure S1) is preferable. That is, the compound β is preferably a compound B having a structure (specific structure S1) capable of accepting electrons from the acid group included in the compound a in a photoexcited state.
Hereinafter, the compound β (preferably the compound B) will be described.
From the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern, the compound β (preferably the compound B) is preferably an aromatic compound.
The aromatic compound is a compound having 1 or more aromatic rings.
The aromatic ring may be present in the compound β (preferably the compound B) in an amount of only 1 or in an amount of more than one. When there are a plurality of aromatic rings, for example, the aromatic rings may be present in the side chain of the resin.
In the compound β (preferably the compound B), an aromatic ring can be used as a structure (specific structure S1) capable of accepting electrons from an acid group included in the compound a in the above-described photoexcited state. The aromatic ring may have an overall structure constituting the whole of the compound β (preferably the compound B), or may have a partial structure constituting a part of the compound β (preferably the compound B).
The aromatic ring may be a single ring or multiple rings, and is preferably multiple rings. The polycyclic aromatic ring is, for example, an aromatic ring in which a plurality of (for example, 2 to 5) aromatic ring structures are condensed, and at least one of the plurality of aromatic ring structures preferably has a heteroatom as a ring member atom.
The aromatic ring may be a heteroaromatic ring, and preferably has 1 or more (for example, 1 to 4) heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as a ring member atom, and more preferably has 1 or more (for example, 1 to 4) nitrogen atoms as a ring member atom.
The number of ring members of the aromatic ring is preferably 5 to 15.
Examples of the aromatic ring include monocyclic aromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; an aromatic ring formed by fusing 2 rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; an aromatic ring formed by fusing 3 rings such as an acridine ring, a phenanthridine ring, a phenanthroline ring and a phenazine ring.
The aromatic ring may have 1 or more (for example, 1 to 5) substituents, and examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, an amino group, and a nitro group. In the case where the aromatic ring has 2 or more substituents, a plurality of substituents may be bonded to each other to form a non-aromatic ring.
It is also preferable that the aromatic ring is directly bonded to the carbonyl group to form an aromatic carbonyl group in the compound β (preferably the compound B). The plurality of aromatic rings are also preferably bonded via a carbonyl group.
It is also preferable that the aromatic ring is bonded to an imide group to form an aromatic imide group in the compound β (preferably the compound B). The imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring.
In addition, when a series of aromatic ring structures are formed by bonding a plurality of aromatic rings (for example, 2 to 5 aromatic rings) through a structure selected from the group consisting of a single bond, a carbonyl group, and multiple bonds (for example, vinylidene groups which may have substituents, -c≡c-, -n=n-, etc.), the whole of the series of aromatic ring structures is regarded as 1 specific structure S1.
Further, it is preferable that 1 or more of the plurality of aromatic rings constituting the series of aromatic ring structures are the heteroaromatic rings.
From the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern, the compound β (preferably the compound B) is preferably a compound satisfying 1 or more (for example, 1 to 4) of the following requirements (1) to (4). Among them, at least the requirement (2) is preferably satisfied, and the heteroatom of the heteroaromatic ring preferably has at least a nitrogen atom.
(1) Having a polycyclic aromatic ring.
(2) Has a heteroaromatic ring.
(3) Has an aromatic carbonyl group.
(4) Has an aromatic imide group.
Specific examples of the compound β (preferably the compound B) include monocyclic aromatic compounds such as pyridine and pyridine derivatives, pyrazine and pyrazine derivatives, pyrimidine and pyrimidine derivatives, and triazine derivatives; compounds in which 2 rings such as quinoline and quinoline derivatives, isoquinoline and isoquinoline derivatives, quinoxaline and quinoxaline derivatives, and quinazoline derivatives are condensed to form an aromatic ring; such compounds are compounds in which 3 or more rings such as acridine and acridine derivatives, phenanthridine and phenanthridine derivatives, phenanthroline and phenanthroline derivatives, and phenazine derivatives are condensed to form aromatic rings.
Among them, the compound β (preferably the compound B) is preferably 1 or more selected from the group consisting of pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline derivatives, more preferably 1 or more selected from the group consisting of quinoline and quinoline derivatives, and isoquinoline derivatives, and still more preferably 1 or more selected from the group consisting of isoquinoline and isoquinoline derivatives.
These compounds and derivatives thereof may further have a substituent, and as the substituent, an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group, an amino group or a nitro group is preferable, an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group or a nitro group is more preferable, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxyl group, a cyano group or a nitro group is more preferable, and an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms) is particularly preferable.
Further, from the viewpoint of more excellent patterning ability and/or the lower moisture permeability of the formed pattern, the compound β (preferably the compound B) is preferably an aromatic compound having a substituent (a compound having a substituent at a constituent atom of an aromatic ring contained in the compound β (preferably the compound B)), and more preferably a compound satisfying 1 or more (for example, 1 to 4) of the above-described requirements (1) to (4) and further having a substituent.
For example, in the case where the compound β (preferably the compound B) is quinoline or a quinoline derivative, the substituent is preferably at least at the 2-and 4-positions on the quinoline ring from the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern. Further, for example, in the case where the compound β (preferably the compound B) is isoquinoline or an isoquinoline derivative, it is preferable to have a substituent at least at the 1-position on the isoquinoline ring from the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern. Further, as the substituent, an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms) is preferable.
In the case where compound β (preferably compound B) is a polymer, specific structure S0 (preferably specific structure S1) may be a polymer bonded to the polymer backbone via a single bond or a linking group.
The compound β (preferably compound B) as a polymer is obtained, for example, by polymerizing a monomer having a heteroaromatic ring (specifically, a (meth) acrylate monomer having a vinyl heteroaromatic ring and/or a specific structure S0 (preferably, a specific structure S1, more preferably, a heteroaromatic ring). Can be copolymerized with other monomers as required.
From the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern, the molar absorption coefficient (molar absorption coefficient ε) of the compound β (preferably the compound B) to light having a wavelength of 365nm is, for example, 1×10 3 (cm·mol/L) -1 Hereinafter, it is preferably 1X 10 3 (cm·mol/L) -1 Hereinafter, more preferably less than 5X 10 2 (cm·mol/L) -1 Further preferably 1X 10 2 (cm·mol/L) -1 The following is given. The lower limit of the molar absorptivity epsilon is not particularly limited, and is, for example, more than 0 (cm. Mol/L) -1 。
The molar absorptivity epsilon of the compound β (preferably the compound B) is within the above range, which is particularly advantageous when exposing the photosensitive layer formed of the photosensitive composition via a temporary support (preferably a PET film).
That is, in the case where the acid group of the compound a having an acid group is a carboxyl group, since the molar absorptivity epsilon is moderately low, even if exposure is performed through the temporary support, the generation of bubbles due to decarboxylation can be controlled, and deterioration of the pattern shape can be prevented.
When the photosensitive composition is used for the purpose of producing a protective film (permanent film), coloring of the film can be suppressed by setting the molar absorption coefficient epsilon of the compound beta (preferably, the compound B) in the above range.
As the compound having such a molar absorptivity epsilon, the above monocyclic aromatic compound or the aromatic compound having 2 rings condensed to form an aromatic ring is preferable, pyridine or a pyridine derivative, quinoline or a quinoline derivative or isoquinoline or an isoquinoline derivative is more preferable, and isoquinoline or an isoquinoline derivative is still more preferable.
Further, from the viewpoint of more excellent patterning ability and/or the lower moisture permeability of the formed pattern, the ratio of the molar absorption coefficient (molar absorption coefficient ε) of the compound β (preferably the compound B) at 365nm to the molar absorption coefficient (molar absorption coefficient ε ') of the compound β (preferably the compound B) at 313nm (i.e., the ratio represented by the molar absorption coefficient ε/the molar absorption coefficient ε') is preferably 3 or less, more preferably 2 or less, and even more preferably less than 1. The lower limit is not particularly limited, and is, for example, 0.01 or more.
The molar absorptivity (molar absorptivity epsilon ') of the compound β (preferably compound B) with respect to light having a wavelength of 365nm and the molar absorptivity (molar absorptivity epsilon') of the compound β (preferably compound B) with respect to light having a wavelength of 313nm are measured by dissolving the compound β (preferably compound B) in acetonitrile. In the case where compound β (preferably compound B) is not dissolved in acetonitrile, a solvent for dissolving compound β (preferably compound B) may be appropriately changed.
Specific examples of the compound β (preferred compound B) include 5,6,7, 8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, 1-phenylisoquinoline, 1-n-butylisoquinoline, 1-n-butyl-4-methylisoquinoline, 1-methylisoquinoline, 2,4,5, 7-tetramethylquinoline, 2-methyl-4-methoxyquinoline, 2, 4-dimethylquinoline, phenanthridine, 9-methylacridine, 9-phenylacridine, pyridine, isoquinoline, quinoline, acridine, 4-aminopyridine, and 2-chloropyridine.
The lower limit value of pKa of the compound β (preferably the compound B) in the base state is preferably 0.50 or more, and more preferably 2.00 or more from the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern. The upper limit of pKa of the compound β (preferably the compound B) in the basal state is preferably 10.00 or less, more preferably 9.00 or less, further preferably 8.00 or less, and particularly preferably 7.00 or less. The pKa of the compound β (preferably compound B) in the basal state refers to the pKa of the compound β (preferably compound B) in the unexcited state, and can be obtained by acid titration. In addition, in the case where the compound β (preferably the compound B) is a nitrogen-containing aromatic compound, the pKa of the compound β (preferably the compound B) in the base state refers to the pKa of the co-conjugated acid of the compound β (preferably the compound B) in the base state.
In the case of forming the photosensitive layer by coating, the molecular weight of the compound β (preferably, the compound B) is more preferably 120 or more, still more preferably 130 or more, still more preferably 150 or more from the viewpoint of being less volatile in the coating process and further excellent in the residual rate in the photosensitive layer (further, from the viewpoint of being more excellent in the patterning ability and/or the moisture permeability of the formed pattern becoming lower). The upper limit of the molecular weight of the compound β (preferably, the compound B) is not particularly limited, and is, for example, 50,000 or less.
In the case where the compound β (preferably the compound B) is a compound (for example, a nitrogen-containing aromatic compound) that shows a cationic state, the energy level of HOMO (highest occupied molecular orbital) of the compound β (preferably the compound B) in the cationic state is preferably-7.50 eV or less, and more preferably-7.80 eV or less from the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern. The lower limit is not particularly limited, but is more preferably-13.60 eV or more.
In this specification, the energy level of HOMO of compound β (preferably compound B) in the cationic state (HOMO in the first electron excited state) is calculated by the quantum chemical calculation program Gaussian09 (Gaussian 09,Revision A.02,M.J.Frisch,G.W.Trucks,H.B.Schlegel,G.E.Scuseria,M.A.Robb,J.R.Cheeseman,G.Scalmani,V.Barone,B.Mennucci,G.A.Petersson,H.Nakatsuji,M.Caricato,X.Li,H.P.Hratchian,A.F.Izmaylov,J.Bloino,G.Zheng,J.L.Sonnenberg,M.Hada,M.Ehara,K.Toyota,R.Fukuda,J.Hasegawa,M.Ishida,T.Nakajima,Y.Honda,O.Kitao,H.Nakai,T.Vreven,J.A.Montgomery,Jr, J.E.Peralta, F.Ogliaro, M.Bearpark, J.J.Heyd, E.Brothers, K.N.Kudin, V.N.Staroverov, R.Kobayashi, J.Normand, K.Raghavachari, A.Rendell, J.C.Burant, S.S.Iyengar, J.Tomasi, M.Cossi, N.Rega, J.M.Millam, M.Klene, J.E.Knox, J.B.Cross, V.Bakken, C.Adamo, J.Jaramillo, R.Gomperts, R.E.Stratmann, O.Yazyev, A.J.Austin, R.Cammi, C.Pomelli, J.W.OchLerski, R.L.Martin, K.Morokuma, V.G.Zakrzewski, G.A.Voth, P.Salvador, J.J.Dannenberg, S.Dapprich, A.D.Daniels, O.Farkas, J.B.Fore sman, J.V.Ortiz, J.Cioslowski, and d.j.fox, gaussian, inc., wallingford CT, 2009).
As a calculation method, a time-density functional method using B3LYP for the functional function and 6-31+G (d, p) for the base function was used. In order to promote the solvent effect, a PCM method based on parameters of chloroform set in Gaussian09 is used. The structure optimization calculation of the first electron excitation state is performed by the present method to find the structure that becomes the smallest energy, and the energy of HOMO in the structure is calculated.
Hereinafter, a representative example of the compound β (preferably compound B) is shown as the HOMO level (eV) in the cationic state. The molecular weights are also indicated.
TABLE 1
In the photosensitive composition, the content of the compound β (preferably, the compound B) is preferably 0.1 to 50% by mass relative to the total solid content of the photosensitive composition.
In the photosensitive composition of embodiment X-1-a1, the content of the compound β (preferably, the compound B) is preferably 2.0 to 40% by mass, more preferably 4 to 35% by mass, and even more preferably 8 to 30% by mass, based on the total solid content of the photosensitive composition.
In the photosensitive composition of embodiment X-1-a2, the content of the compound β (preferably, the compound B) is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive composition.
In the photosensitive composition of embodiment X-1-a3, the content of the compound β (preferably, the compound B) is preferably 0.3 to 20% by mass, more preferably 0.5 to 8% by mass, based on the total solid content of the photosensitive composition.
The compound β (preferably compound B) may be used singly or in combination of two or more.
In the case where the compound β is the compound B, the total number of the structures capable of accepting electrons (specific structure S1) of the compound B is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, particularly preferably 10 mol% or more, and most preferably 20 mol% or more, with respect to the total number of the acid groups (preferably carboxyl groups) of the compound a in the photosensitive composition, from the viewpoint of further excellent effects of the present invention.
The upper limit of the total number of structures (specific structures S1) capable of accepting electrons of the compound B is not particularly limited, but is preferably 200 mol% or less, more preferably 100 mol% or less, and still more preferably 80 mol% or less, with respect to the total number of acid groups (preferably carboxyl groups) of the compound a, from the viewpoint of the film quality of the obtained film.
< polymerizable Compound >
The photosensitive composition also preferably contains a polymerizable compound. The polymerizable compound is a component different from the compound a having an acid group, and preferably does not contain an acid group.
The polymerizable compound is preferably a component different from the compound a, for example, a compound having a molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of less than 5,000, and is also preferably a polymerizable monomer.
The polymerizable compound is a polymerizable compound having 1 or more (for example, 1 to 15) ethylenically unsaturated groups in one molecule.
The polymerizable compound preferably contains a polymerizable compound having 2 or more functions.
The polymerizable compound having 2 or more functions is a polymerizable compound having 2 or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.
Examples of the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, and a styryl group, and a (meth) acryloyl group is preferable.
As the polymerizable compound, (meth) acrylic acid esters are preferable.
The photosensitive composition preferably contains a 2-functional polymerizable compound (preferably a 2-functional (meth) acrylate) and/or a 3-functional or more polymerizable compound (preferably a 3-functional or more (meth) acrylate).
The 2-functional polymerizable compound is not particularly limited, and may be appropriately selected from known compounds.
Examples of the 2-functional polymerizable compound include tricyclodecane dimethanol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate and 1, 6-hexanediol di (meth) acrylate.
More specifically, examples of the 2-functional polymerizable compound include tricyclodecane dimethanol diacrylate (A-DCP Shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP Shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (A-NOD-N Shin-Nakamura Chemical Co., ltd.), and 1, 6-hexanediol diacrylate (A-HD-N Shin-Nakamura Chemical Co., ltd.).
The polymerizable compound having 3 or more functions is not particularly limited, and may be appropriately selected from known compounds.
Examples of the polymerizable compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compounds having a glycerol tri (meth) acrylate skeleton.
Here, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
Examples of the polymerizable compound include caprolactone-modified compounds (Nippon Kayaku Co., ltd., manufactured KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical Co., ltd., manufactured A-9300-1CL, etc.), alkylene oxide-modified compounds (Nippon Kayaku Co., ltd., manufactured KAYARADRP-1040, shin-Nakamura Chemical Co., ltd., manufactured ATM-35E, A-9300, manufactured EBRYLEL-ALLNEX LTD., manufactured EBRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., manufactured A-GLY-9E, etc.), etc. of the (meth) acrylate compound.
The polymerizable compound may be urethane (meth) acrylate (preferably 3-functional or more urethane (meth) acrylate). The lower limit of the number of functional groups is more preferably 6 or more functions, and still more preferably 8 or more functions. The upper limit of the number of functional groups is, for example, 20 or less.
Examples of the urethane (meth) acrylate having 3 or more functions include 8UX-015A (TAISEI FINE CHEMICAL CO,. Ltd.): UA-32P, U-15HA and UA-1100H (both Shin-Nakamura Chemical Co., manufactured by L td.): KYOEISHA CHEMICAL Co., LTD. Manufactured AH-600 (trade name): UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (both of Nippon Kayaku Co., ltd.) and the like.
The weight average molecular weight (Mw) of the polymerizable compound that can be contained in the photosensitive composition is preferably 200 to 3000, more preferably 250 to 2600, and even more preferably 280 to 2200.
When the photosensitive composition contains a polymerizable compound, the molecular weight of the polymerizable compound having the smallest molecular weight among all the polymerizable compounds contained in the photosensitive composition is preferably 250 or more, more preferably 280 or more.
When the photosensitive composition contains a polymerizable compound, the content thereof is preferably 3 to 70% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 55% by mass, relative to the total solid content of the photosensitive composition.
When the photosensitive composition contains a polymerizable compound, the mass ratio of the polymerizable compound to the compound a (mass of the polymerizable compound/mass of the compound a) is preferably 0.2 to 2.0, more preferably 0.4 to 0.9.
The polymerizable compound may be used alone or in combination of two or more.
When the photosensitive composition contains a 2-functional polymerizable compound and a 3-functional or more polymerizable compound, the content of the 2-functional polymerizable compound is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and still more preferably 30 to 80% by mass, relative to all the polymerizable compounds contained in the photosensitive composition.
The content of the polymerizable compound having 3 or more functions is preferably 10 to 100% by mass, more preferably 15 to 100% by mass, and even more preferably 20 to 100% by mass, based on the total amount of the polymerizable compounds contained in the photosensitive composition. Particularly preferably 70 to 100% by mass.
In the case where the photosensitive composition contains a polymerizable compound having 2 or more functions, the photosensitive composition may further contain a monofunctional polymerizable compound.
Among them, when the photosensitive composition contains a polymerizable compound having 2 or more functions, among the polymerizable compounds that the photosensitive composition can contain, the polymerizable compound having 2 or more functions is preferable as a main component.
Specifically, when the photosensitive composition contains a 2-functional or higher polymerizable compound, the content of the 2-functional or higher polymerizable compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total content of the polymerizable compounds contained in the photosensitive composition.
< photopolymerization initiator >
The photosensitive composition also preferably contains a photopolymerization initiator.
The photopolymerization initiator may be a photo radical polymerization initiator, a photo cation polymerization initiator, a photo anion polymerization initiator, or preferably a photo radical polymerization initiator.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
The photopolymerization initiator is preferably an oxime ester compound (photopolymerization initiator having an oxime ester structure) or an alkylbenzene ketone compound (photopolymerization initiator having an alkylbenzene ketone structure), and may contain at least one of these compounds or may contain two of these compounds. In the case of containing the above two compounds, the content of the oxime ester compound is preferably 5 to 90% by mass, more preferably 15 to 50% by mass, relative to the total content of the two compounds. The alkylbenzene ketone compound is also preferably an aminoacetophenone compound (photopolymerization initiator having an aminoacetophenone structure).
The photopolymerization initiator may be used together with other photopolymerization initiators, and examples thereof include hydroxyacetophenone compounds, acylphosphine oxide compounds, and ditritylimidazole compounds.
Further, as the photopolymerization initiator, for example, those described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-095716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-014783 can be used.
As specific examples of the photopolymerization initiator, the following photopolymerization initiator can be exemplified.
Examples of the oxime ester compound include 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -2- (O-benzoyl oxime) ] (trade name: IRGACURE OXE-01, IRGACURE series BASF corporation), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyl oxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), [8- [5- (2, 4, 6-trimethylphenyl) -11- (2-ethylhexyl) -11H-benzo [ a ] carbazole ] [2- (2, 3-tetrafluoropropoxy) phenyl ] methanone- (0-acetyl oxime) (trade name: IRGACURE OXE-03, manufactured by BASF corporation), 1- [4- [4- (2-benzofuranylcarbonyl) phenyl ] thio ] phenyl ] -4-methylpentanone-1- (0-acetyl oxime) (trade name: IRGACURE OXE-04, manufactured by BASF corporation: lunar6, manufactured by DKSH Japan K.K.), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (0-benzoyl oxime) (trade name: TR-PBG-305, changzhou Tronly New Electronic Materials Co., ltd. manufactured), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (trade name: TR-PBG-326, changzhou Tronly New Electronic Materials co., ltd., manufactured), 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (trade name: TR-PBG-391, changzhou Tronly New Flectronic Materials co., ltd.).
Examples of the aminoacetophenone compound include 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omnirad 379, manufactured by Omnirad series IGM Resins b.v. company), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: omnirad 907), APi-307 (manufactured by 1- (biphenyl-4-yl) -2-methyl-2-morpholinopropan-1-one, and Shenzhen UV-ChemTech ltd.).
Examples of the other photopolymerization initiator include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one (trade name: omnirad 127), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: omnifad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: omnirad 1173), 1-hydroxy-cyclohexyl-phenyl ketone (trade name: omnirad 184), 2-dimethoxy-1, 2-diphenylethane-1-one (trade name: omnirad 651), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad H), and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819).
When the photosensitive composition contains a photopolymerization initiator, the content thereof is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass, relative to the total solid content of the photosensitive composition.
The photopolymerization initiator may be used singly or in combination of two or more.
< surfactant >
The photosensitive composition may contain a surfactant.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (Nonionic) surfactants, and amphoteric surfactants, and Nonionic surfactants are preferable.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyethylene glycol, silicone surfactants, and fluorine surfactants.
As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of International publication No. 2018/179640 can also be used.
The surfactant described in paragraphs 0017 and 0060 to 0071 of JP-A2009-237362 can also be used.
As a commercial product of the fluorine-based surfactant, for example, examples of the catalyst include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation) F ] Uorad FC 430, FC431, FC171 (manufactured above as Sumitomo3 MLimited), surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured above as AGC Inc.), poly Fox PF636, PF656, PF6320, PF6520, PF7002 (manufactured above as OMNOVA Solutions Inc.), FTERGENT710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured as ENEOS Corporation above), and the like.
As the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and a functional group portion containing a fluorine atom is preferably used, and the fluorine atom is preferably volatilized by cleavage of the functional group portion containing a fluorine atom when heat is applied. Examples of the fluorine-based surfactant include MEGAFACE DS series (chemical industry journal of date (2016, 2, 22 days) and daily industrial news (2016, 2, 23 days)) manufactured by DIC Corporation, and MEGAFACE DS-21.
As the fluorine-based surfactant, a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound, which have a fluorinated alkyl group or a fluorinated alkylene ether group, is also preferably used.
Also, as the fluorine-based surfactant, a block polymer can be used.
As the fluorine-based surfactant, a fluorine-containing polymer compound containing: repeat units derived from a (meth) acrylate compound having a fluorine atom and repeat units derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups).
As the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain can be used. Examples thereof include MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation).
From the viewpoint of improving the environmental suitability, the fluorine-based surfactant is preferably a surfactant derived from a substitute material of a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS).
Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF corporation), solsperse 20000 (manufactured by Japan Lubrizol Corporation) and the like, NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation) and the like, pin D-6112, D-6112-W, D-6315 (manufactured by tamotol & Fat Co, manufactured by oltdco), ne1010, ltd.440, ltd.400, and the like.
The silicone surfactant includes a linear polymer composed of siloxane bonds, and a modified siloxane polymer obtained by introducing an organic group into a side chain or a terminal.
Specific examples of the surfactant include DOWSIL8032ADDITIVE, toray Silicone DC PA, toray Silicone SH7PA, toray Silicone DC1 1PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by Ltd. Above Dow Corning Toray Co.), and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., above), F-40, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by MatalsC. Above Momentive Performance), matalsK 307, and BYK.323, BYH.sub.330.
The content of the surfactant is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and even more preferably 0.005 to 3% by mass, based on the total solid content of the photosensitive composition.
The surfactant may be used singly or in combination of two or more.
< solvent >
As the solvent, a commonly used solvent can be used without particular limitation.
As the solvent, an organic solvent is preferable.
Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, 2-propanol, and a mixed solvent thereof.
The solvent is preferably a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
When the photosensitive composition contains a solvent, the content of the solvent is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, and further preferably 70 to 95% by mass, relative to the total mass of the photosensitive composition.
The solvent may be used singly or in combination of two or more.
When the photosensitive composition contains a solvent, the viscosity (25 ℃) of the photosensitive composition is preferably 1 to 50mpa·s, more preferably 2 to 40mpa·s, and even more preferably 3 to 30mpa·s, from the viewpoint of coatability.
Viscosity is measured, for example, using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
When the photosensitive composition contains a solvent, the surface tension (25 ℃) of the photosensitive composition is preferably 5 to 100mN/m, more preferably 10 to 80mN/m, and even more preferably 15 to 40mN/m from the viewpoint of coatability.
Surface tension is for example Automatic Surface Tensiometer
CBVP-Z (Kyowa Interface Science co., ltd.) was measured.
As the Solvent, solvent described in 0054 and 0055 of U.S. application publication 2005/282073, the contents of which are incorporated herein by reference, can also be used.
As the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250 ℃ can be used as needed.
In the case where the photosensitive composition of the present invention is used to form a photosensitive layer in a transfer film or the like described later, the photosensitive layer preferably contains substantially no solvent. Substantially free of the solvent means that the content of the solvent is preferably 0 to 0.5 mass%, more preferably 0 to 0.001 mass% relative to the total mass of the photosensitive composition (photosensitive layer) as long as the content is less than 1 mass%.
< other additives >
The photosensitive composition may contain other additives as required.
Examples of the other additives include plasticizers, sensitizers, heterocyclic compounds, and alkoxysilane compounds.
Examples of plasticizers, sensitizers, heterocyclic compounds and alkoxysilane compounds include those described in paragraphs 0097 to 0119 of International publication No. 2018/179640.
The photosensitive composition may further contain, as other additives, known additives such as rust inhibitors, metal oxide particles, antioxidants, dispersants, acid breeder agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents.
A preferred embodiment of these components is described in paragraphs 0165 to 0184 of japanese unexamined patent publication No. 2014-085643, the contents of which are incorporated herein by reference.
The photosensitive composition may contain impurities.
Examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, the following contents are particularly preferred because halide ions, sodium ions, and potassium ions are easily mixed as impurities.
The content of impurities in the photosensitive composition is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less, relative to the total solid content of the photosensitive composition. The content of impurities in the photosensitive composition may be 1 ppb by mass or 0.1 ppm by mass or more based on the total solid content of the photosensitive composition.
As a method for setting the impurity in the above range, for example, there can be mentioned: a method of selecting a material having a small impurity content as a raw material of a photosensitive composition, a method of preventing contamination of impurities during formation of the photosensitive composition, and a method of removing impurities by cleaning. The impurity amount can be set within the above range by this method.
The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma: inductively coupled plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.
Further, the photosensitive composition preferably contains a small amount of a compound such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, hexane, and the like. The content of these compounds in the photosensitive composition is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and still more preferably 4 mass ppm or less, respectively, based on the total solid content of the photosensitive composition.
The lower limit of the content may be 10 ppb by mass or more, or 100 ppb by mass or more, respectively, relative to the total solid content of the photosensitive composition. The content of these compounds can be suppressed by the same method as the impurities of the above metals. Further, the amount can be determined by a known measurement method.
From the viewpoint of improving the patterning property, the content of water in the photosensitive composition is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass% with respect to the total solid content of the photosensitive composition.
[ transfer film ]
The transfer film of the present invention has a temporary support and a photosensitive layer (hereinafter, also simply referred to as "photosensitive layer") formed using the photosensitive composition of the present invention.
Hereinafter, the transfer film of the present invention will be described in detail.
Fig. 1 is a schematic cross-sectional view showing an example of the transfer film according to the embodiment of the present invention.
The transfer film 100 shown in fig. 1 has a structure in which a temporary support 12, a photosensitive layer (a photosensitive layer formed using the photosensitive composition of the present invention) 14, and a cover film 16 are laminated in this order.
The cover film 16 may be omitted.
< temporary support >
The temporary support is a support that supports the photosensitive layer and can be peeled off from the photosensitive layer.
The temporary support preferably has light transmittance from the viewpoint that the photosensitive layer can be exposed through the temporary support when the photosensitive layer is subjected to pattern exposure.
Here, "light-transmitting" means that the transmittance of the dominant wavelength of light used for exposure (pattern exposure or full-face exposure) is 50% or more. From the viewpoint of more excellent exposure sensitivity, the transmittance of the dominant wavelength of light used for exposure is preferably 60% or more, more preferably 70% or more. As a method of measuring transmittance, a method using MCPD Series manufactured by Otsuka Electronics co., ltd.
The transmittance of the temporary support is more specifically, the transmittance at 313nm, 365nm, 313nm, 405nm and 436nm is more preferably 70% or more, still more preferably 80% or more, particularly preferably 90% or more. Preferred values of the transmittance include, for example, 87%, 92% and 98%.
The temporary support is specifically a glass substrate, a resin film, paper, or the like, and the resin film is preferable from the viewpoint of further excellent strength, flexibility, or the like. Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among them, biaxially stretched polyethylene terephthalate film is preferable.
From the viewpoints of the patterning property at the time of pattern exposure via the temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matters, and defects contained in the temporary support be small. The number of particles and foreign matter defects having a diameter of 2 μm or more is preferably 50/10 mm 2 Hereinafter, more preferably 10 pieces/10 mm 2 Hereinafter, it is more preferably 3/10 mm 2 The following is given. The lower limit is not particularly limited and can be set to 1/10 mm 2 The above.
From the viewpoint of further improving the handleability, the temporary support preferably has 1 particle/mm of particles having a diameter of 0.5 to 5 μm on the surface opposite to the side on which the photosensitive layer is formed 2 The above layers are more preferably present in an amount of 1 to 50 per mm 2 。
The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 150 μm, from the viewpoint of easy handling and excellent versatility.
The thickness of the temporary support can be appropriately selected depending on the material from the viewpoints of the strength as the support, the flexibility required for adhesion to the circuit wiring forming substrate, the light transmittance required in the initial exposure step, and the like.
The temporary support may be a recycled product. As the recovered product, a product obtained by washing and cutting a used film or the like into pieces and producing a film is exemplified. Specific examples of the recovered product include the Ecouse series of TORAY INDUSTRIES, INC..
Preferable modes of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-085643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-027363, paragraphs 0041 to 0057 of WO2012/081680A1 and paragraphs 0029 to 0040 of WO2018/179370A1, the contents of which are incorporated herein by reference.
As the temporary support, for example, cosmo Shine (registered trademark) a4100, cosmo Shine (registered trademark) a4160, and Cosmo Shine (registered trademark) a4360 (both of which are TOYOBO co., ltd. Manufactured above), lumirror (registered trademark) 16FB40, lumirror (registered trademark) 16QS62 (16 KS 40), lumirror (registered trademark) #38-U48, lumirror (registered trademark) #75-U34, and Lumirror (registered trademark) #25-T60 (both of which are TORAY INDUSTRIES, manufactured above) [ NC. ] can be used.
Further, as a particularly preferable mode of the temporary support, there are a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.
< photosensitive layer >
The photosensitive layer in the transfer film is a layer formed using the photosensitive composition of the present invention, and for example, the photosensitive layer is preferably a layer substantially composed of only the solid component of the photosensitive composition. That is, the photosensitive composition constituting the photosensitive layer preferably contains solid components (components other than the solvent) that can be contained in the photosensitive composition in the above-described content.
In the case of forming a photosensitive layer by applying and drying a photosensitive composition containing a solvent, the photosensitive layer may contain a solvent because a solvent remains in the photosensitive layer even after drying.
From the viewpoint of the photosensitive layer having more excellent patterning ability particularly with respect to an alkaline developer, the content of the acid group (preferably carboxyl group) derived from the compound a is preferably reduced at a reduction rate of 5 mol% or more, more preferably at a reduction rate of 10 mol% or more, still more preferably at a reduction rate of 20 mol% or more, still more preferably at a reduction rate of 31 mol% or more, particularly preferably at a reduction rate of 40 mol% or more, particularly more preferably at a reduction rate of 51 mol% or more, and most preferably at a reduction rate of 71 mol% or more. The upper limit is not particularly limited, and is, for example, 100 mol% or less.
In addition, in the case where the acid group derived from the compound a is a carboxyl group, the reduction rate of the content of the carboxyl group derived from the compound a in the photosensitive layer can be calculated by measuring the amount of the carboxyl group of the photosensitive layer before and after exposure. In measuring the amount of carboxyl groups in the photosensitive layer before exposure, for example, analysis and quantification can be performed by potentiometric titration. When measuring the amount of carboxyl groups in the photosensitive layer after exposure, the hydrogen atoms in the carboxyl groups can be replaced with metal ions such as lithium, and the amount of the metal ions can be calculated by analysis and quantification by ICP-OES (Inductivity coupled plasma optical emission spectrometer: inductively coupled plasma emission spectrometer).
Further, the reduction rate of the content of the acid group derived from the compound a in the photosensitive layer can also be obtained by measuring the IR (infrared) spectrum of the photosensitive layer before and after exposure and calculating the reduction rate of the peak derived from the acid group.
< average thickness of photosensitive layer >
The average thickness of the photosensitive layer is preferably 0.5 to 20. Mu.m. The resolution of the pattern is more excellent when the average thickness of the photosensitive layer is 20 μm or less, and it is preferable from the viewpoint of the linearity of the pattern when the average thickness of the photosensitive layer is 0.5 μm or more. The average thickness of the photosensitive layer is more preferably 0.8 to 15. Mu.m, and still more preferably 1.0 to 10. Mu.m. Specific examples of the average thickness of the photosensitive layer include 3.0 μm, 5.0 μm and 8.0 μm.
< method for Forming photosensitive layer >
The photosensitive layer can be formed by applying the photosensitive composition of the present invention and drying. In the case of forming a photosensitive layer from the photosensitive composition of the present invention, it is preferable to filter the photosensitive composition before it is formed, for example, by using a filter having a pore diameter of 0.2 to 30 μm.
The photosensitive layer can be formed by applying the photosensitive composition onto a temporary support or a cover film and drying it.
The coating method is not particularly limited, and may be any known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In the case where another layer to be described later is formed on the temporary support or the cover film, the photosensitive layer may be formed on the other layer.
The transmittance of the photosensitive layer at 365nm is preferably 20% or more, more preferably 65% or more, and even more preferably 90% or more, from the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern. The upper limit is not particularly limited, but is 100% or less.
The ratio of the transmittance at 365nm of the photosensitive layer to the transmittance at 313nm of the photosensitive layer (the ratio represented by the transmittance at 365nm of the photosensitive layer/the transmittance at 313nm of the photosensitive layer) is preferably 1 or more, more preferably 1.5 or more from the viewpoint of more excellent patterning ability and/or the viewpoint of lower moisture permeability of the formed pattern. The upper limit is not particularly limited, and is, for example, 1000 or less.
In the photosensitive layer, the acid group of the compound a is preferably a carboxyl group. The photosensitive layer is preferably irradiated with actinic rays or radiation to reduce the content of carboxyl groups in the photosensitive layer by a reduction rate of 5 mol% or more. More preferably, the photosensitive layer satisfies any one of the above-mentioned requirements (V1-C) and requirements (W1-C).
Further, among these, the photosensitive layers of the above embodiments X-1-a1-C to X-1-a3-C are more preferable as embodiments of the photosensitive layer.
The visible light transmittance of the photosensitive layer per 1.0 μm film thickness is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.
As the visible light transmittance, it is preferable that the average transmittance at a wavelength of 400 to 800nm, the minimum value of the transmittance at a wavelength of 400 to 800nm, and the transmittance at a wavelength of 400nm satisfy the above conditions.
Preferable values of visible light transmittance per 1.0 μm film thickness of the photosensitive layer include, for example, 87%, 92%, 98%, and the like.
From the viewpoint of suppressing residues during development, the dissolution rate of the photosensitive layer in a 1.0 mass% aqueous solution of sodium carbonate is preferably 0.01 μm/sec or more, more preferably 0.10 μm/sec or more, and still more preferably 0.20 μm/sec or more. Further, from the viewpoint of the edge shape of the pattern, it is preferably 5.0 μm/sec or less. Specific preferable values include, for example, 1.8 μm/sec, 1.0 μm/sec, and 0.7 μm/sec.
The dissolution rate of the photosensitive layer per unit time in a 1.0 mass% sodium carbonate aqueous solution was measured as follows.
For the photosensitive layer (film thickness in the range of 1.0 to 10 μm) formed on the glass substrate, from which the solvent was sufficiently removed, spray development was performed at 25 ℃ using 1.0 mass% sodium carbonate aqueous solution until the photosensitive layer was completely dissolved (among them, up to 2 minutes).
The dissolution rate was determined by dividing the film thickness of the photosensitive layer by the time required for the photosensitive layer to dissolve completely. If the film is not completely dissolved within 2 minutes, the film thickness change amount up to this point is calculated in the same manner.
For development, a spray nozzle of 1/4MINJJX030PP manufactured by ltd. Was used, and the spray pressure of the spray was set to 0.08MPa. In the case of the above conditions, the shower flow rate per unit time was set to 1, 800 mL/min.
From the viewpoint of patterning properties, the number of foreign matters having a diameter of 1.0 μm or more in the photosensitive layer is preferably 10 pieces/mm 2 Hereinafter, more preferably 5 pieces/mm 2 The following is given.
The amount of foreign matter was measured as follows.
The number of foreign matters having a diameter of 1.0 μm or more in each region was measured by observing arbitrary 5 regions (1 mm×1 mm) on the surface of the photosensitive layer with naked eyes from the normal direction of the surface of the photosensitive layer using an optical microscope, and these were arithmetically averaged to calculate the number of foreign matters.
As a specific preferable value, for example, 0 pieces/mm can be mentioned 2 1/mm 2 4/mm 2 8 pieces/mm 2 Etc.
From the viewpoint of suppressing the generation of aggregates during development, 1.0cm was used 3 The haze of a solution obtained by dissolving 1.0 mass% of sodium carbonate in 1.0 liter of a 30 ℃ aqueous solution is preferably 60% or less, more preferably 30% or less, still more preferably 10% or less, and most preferably 1% or less.
Haze was measured as follows.
First, a 1.0 mass% aqueous sodium carbonate solution was prepared, and the liquid temperature was adjusted to 30 ℃. Will be 1.0cm 3 Is put into 1.0L of sodium carbonate aqueous solution. While taking care not to mix in bubbles, the mixture was stirred at 30℃for 4 hours. After stirring, the haze of the solution in which the photosensitive resin layer was dissolved was measured. The haze was measured using a haze meter (product names "NDH4000", NIPPON DENSHOKU INDUSTRIES co., LTD) and using a liquid measuring cell and a liquid measuring cell having an optical path length of 20 mm.
Specific preferable values include, for example, 0.4%, 1.0%, 9%, 24%.
< cover film >
The transfer film of the present invention may further have a cover film on the side opposite to the temporary support when viewed from the photosensitive layer.
In the case where the transfer film of the present invention includes a high refractive index layer described later, the cover film is preferably disposed on the opposite side of the temporary support (i.e., on the opposite side of the photosensitive layer) when viewed from the high refractive index layer. In this case, the transfer film is, for example, a laminate in which a temporary support, a photosensitive layer, a high refractive index layer, and a cover film are laminated in this order.
The number of fish eyes having a diameter of 80 μm or more contained in the cover film is preferably 5/m 2 The following is given. In addition, the "fish eyes" means a substance in which foreign substances, undissolved substances, and/or oxidized degradation substances of a material are incorporated into a film when the film is manufactured by a method such as hot melting, kneading, extruding, and/or biaxial stretching and casting of the material.
The number of particles having a diameter of 3 μm or more contained in the cover film is preferably 30 particles/mm 2 Hereinafter, more preferably 10 pieces/mm 2 Hereinafter, more preferably 5 pieces/mm 2 The following is given. This can suppress defects caused by transfer of irregularities due to particles contained in the cover film to the photosensitive resin layer.
The arithmetic average roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. When Ra is within such a range, for example, in the case where the transfer film is long, the winding property at the time of winding up the transfer film can be improved.
Further, from the viewpoint of suppressing defects at the time of transfer, ra is preferably less than 0.50. Mu.m, more preferably 0.40. Mu.m, and still more preferably 0.30. Mu.m.
Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film.
As the cover film, for example, the films described in paragraphs 0083 to 0087 and 0093 of Japanese patent application laid-open No. 2006-259138 can be used.
As the cover film, for example, alfan (registered trademark) FG-201 manufactured by Oji F-Tex co., ltd. Or A1fan (registered trademark) E-201F, TORAY ADVANCED FILM co manufactured by Oji F-Tex co., ltd. Or carapel (registered trademark) 25WZ manufactured by ltd. Or luraror (registered trademark) 16QS62 (16 KS 40) manufactured by TORAY INDUSTRIES, INC. can be used.
< other layers >
The transfer film may have other layers than the above.
Examples of the other layer include a high refractive index layer.
In the case of forming a high refractive index layer on the temporary support or the cover film, a photosensitive layer may be formed on the high refractive index layer.
< high refractive index layer >
The high refractive index layer is preferably disposed adjacent to the photosensitive layer, and is also preferably disposed on the side opposite to the temporary support when viewed from the photosensitive layer.
The high refractive index layer is not particularly limited except for a layer having a refractive index of 1.50 or more at a wavelength of 550 nm.
The refractive index of the high refractive index layer is preferably 1.55 or more, more preferably 1.60 or more.
The upper limit of the refractive index of the high refractive index layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.
The refractive index of the high refractive index layer is preferably higher than that of the photosensitive layer.
The high refractive index layer may have photo-curability (i.e., photosensitivity), may have thermosetting property, or may have both photo-curability and thermosetting property.
The manner in which the high refractive index layer has photosensitivity has the following advantages: after transfer, the photosensitive layer and the high refractive index layer transferred onto the substrate can be patterned together by one-time photolithography.
The high refractive index layer preferably has alkali solubility (e.g., solubility in a weakly alkaline aqueous solution).
The high refractive index layer is preferably a transparent layer.
The film thickness of the high refractive index layer is preferably 500nm or less, more preferably 110nm or less, and further preferably 100nm or less.
The film thickness of the high refractive index layer is preferably 20nm or more, more preferably 55nm or more, still more preferably 60nm or more, and particularly preferably 70nm or more.
The high refractive index layer may be sandwiched between a transparent electrode pattern (preferably an ITO pattern) and a photosensitive layer after transfer to form a laminate together with the transparent electrode pattern and the photosensitive layer. At this time, by reducing the refractive index difference between the transparent electrode pattern and the high refractive index layer and the refractive index difference between the high refractive index layer and the photosensitive layer, the light reflection is further reduced. Thus, the concealment of the transparent electrode pattern is further improved.
For example, when a transparent electrode pattern, a high refractive index layer, and a photosensitive layer are laminated in this order, the transparent electrode pattern is not easily recognized when viewed from the transparent electrode pattern side.
The refractive index of the high refractive index layer is preferably adjusted according to the refractive index of the transparent electrode pattern.
For example, in the case where the refractive index of the transparent electrode pattern is In the range of 1.8 to 2.0 as In the case of formation using oxides of In and Sn (ITO), the refractive index of the high refractive index layer is preferably 1.60 or more. The upper limit of the refractive index of the high refractive index layer in this case is not particularly limited, but is preferably 2.1 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.
For example, in the case where the refractive index of the transparent electrode pattern exceeds 2.0 as In the case of using In and Zn oxide (IZO; indium Zinc Oxide (indium zinc oxide)), the refractive index of the high refractive index layer is preferably 1.70 or more and 1.85 or less.
The method of controlling the refractive index of the high refractive index layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, and a method of using a complex of a metal salt and a resin.
The metal oxide particles or the types of metal particles are not particularly limited, and known metal oxide particles or metal particles can be used. The metal in the metal oxide particles or the metal particles further includes semi-metals such as B, si, ge, as, sb and Te.
For example, from the viewpoint of transparency, the average primary particle diameter of the particles (metal oxide particles or metal particles) is preferably 1 to 200nm, more preferably 3 to 80nm.
The average primary particle diameter of the particles was calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. In addition, when the particle shape is non-spherical, the longest side is defined as the particle diameter.
The metal oxide particles are preferably selected from the group consisting of zirconium oxide particles (ZrO 2 Particles, nb 2 O 5 Particles, titanium oxide particles (TiO 2 Particles) and silica particles (SiO 2 Particles) and at least one of the group consisting of composite particles thereof.
Among these, for example, at least one selected from the group consisting of zirconia particles and titania particles is more preferable from the viewpoint of facilitating adjustment of the refractive index of the high refractive index layer to 1.6 or more.
When the high refractive index layer contains metal oxide particles, the high refractive index layer may contain only 1 kind of metal oxide particles, or may contain 2 or more kinds of metal oxide particles.
The content of the particles (metal oxide particles or metal particles) is preferably 1 to 95 mass%, more preferably 20 to 90 mass%, and even more preferably 40 to 85 mass% relative to the total mass of the high refractive index layer, from the viewpoint that the concealment of the concealed object such as the electrode pattern becomes good and the visibility of the concealed object can be effectively improved.
When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass of the high refractive index layer.
Examples of the commercial products of the metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F76), zirconia particles (manufactured by nano OZ-S30M, NISSAN CHEMICAL INDUSTRIES, LTD.), and zirconia particles (manufactured by nano OZ-S30K, NISSAN CHEMICAL INDUSTRIES, LTD.).
The high refractive index layer preferably contains 1 or more selected from the group consisting of inorganic particles (metal oxide particles or metal particles) having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more), a resin having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more), and a polymerizable compound having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more).
In this case, the refractive index of the high refractive index layer is easily adjusted to 1.50 or more (more preferably 1.55 or more, particularly preferably 1.60 or more).
The high refractive index layer preferably contains a binder polymer, a polymerizable monomer, and particles.
The components of the high refractive index layer can be exemplified by the components of the curable transparent resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of JP-A2014-108541, the components of the transparent layer described in paragraphs 0024 to 0035 and 0110 to 0112 of JP-A2014-010814, and the components of the composition having an ammonium salt described in paragraphs 0034 to 0056 of International publication 2016/009980.
Also, the high refractive index layer preferably contains a metal antioxidant.
When the high refractive index layer contains a metal antioxidant, a member (for example, a conductive member formed on a substrate) in direct contact with the high refractive index layer can be subjected to surface treatment when the high refractive index layer is transferred onto the substrate (i.e., transfer target). The surface treatment imparts a metal oxidation inhibition function (protection) to the member in direct contact with the high refractive index layer.
The metal antioxidant is preferably a compound having an aromatic ring containing a nitrogen atom. The compound having an aromatic ring containing a nitrogen atom may have a substituent.
The aromatic ring containing a nitrogen atom is preferably an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, or a condensed ring of any one of them with another aromatic ring, and more preferably an imidazole ring, a triazole ring, a tetrazole ring, or a condensed ring of any one of them with another aromatic ring.
The "other aromatic ring" forming the condensed ring may be a single ring or a heterocyclic ring, but is preferably a single ring, more preferably a benzene ring or a naphthalene ring, and further preferably a benzene ring.
As the metal antioxidant, imidazole, benzimidazole, tetrazole, 5-amino-1H-tetrazole, mercaptothiadiazole, or benzotriazole is preferable, and imidazole, benzimidazole, 5-amino-1H-tetrazole, or benzotriazole is more preferable.
As the metal antioxidant, commercially available products can be used, and as commercially available products, for example, BT120 manufactured by JOHOKU CHEMICAL co., ltd.
When the high refractive index layer contains a metal antioxidant, the content of the metal antioxidant is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 5% by mass, relative to the total solid content of the high refractive index layer.
The high refractive index layer may contain other components than the above components.
The other component that can be contained in the high refractive index layer includes the same component as the other component that can be contained in the photosensitive layer.
The high refractive index layer also preferably contains a surfactant.
The method for forming the high refractive index layer is not particularly limited.
As a method for forming the high refractive index layer, for example, a method of forming the high refractive index layer by applying a composition for forming a high refractive index layer containing an aqueous solvent to the photosensitive layer formed on the temporary support and drying the composition as necessary is given.
The composition for forming a high refractive index layer may contain each component of the high refractive index layer.
The composition for forming a high refractive index layer includes, for example, a binder polymer, a polymerizable monomer, particles, and an aqueous solvent.
Further, as the composition for forming a high refractive index layer, the composition having an ammonium salt described in paragraphs 0034 to 0056 of International publication No. 2016/009980 is also preferable.
The photosensitive layer and the high refractive index layer are preferably colorless. Specifically, CIE1976 (L) at total reflection (incidence angle 8 °, light source: D-65 (2 ° field of view)) * 、a * 、b * ) In color space, L * The value is preferably from 10 to 90, a * The value is preferably from-1.0 to 1.0, b * The value is preferably-1.0 to 1.0.
< other layer >
The transfer film may contain other layers (hereinafter, also referred to as "other layers") than the above layers. Examples of the other layer include an intermediate layer and a thermoplastic resin layer, and a known layer can be suitably used.
Preferred modes of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A2014-085643 and preferred modes of the other layers other than those described above, respectively, in paragraphs 0194 to 0196 of JP-A2014-085643, the contents of which are incorporated herein by reference.
Method for producing transfer film
The method for producing the transfer film is not particularly limited, and a known production method can be applied.
The method for producing the transfer film preferably includes a step of forming a photosensitive layer from the photosensitive composition of the present invention on a temporary support, and more preferably includes a step of disposing a cover film on the photosensitive layer after the step of forming the photosensitive layer.
Further, after the step of forming the photosensitive layer, a step of forming a high refractive index layer by applying a composition for forming a high refractive index layer and drying the composition may be further included. In this case, it is more preferable that the method further includes a step of disposing a cover film on the high refractive layer after the step of forming the high refractive layer.
[ method of Forming Pattern ]
The pattern forming method according to the present invention (also referred to as "the pattern forming method of the present invention") is not particularly limited as long as it is a pattern forming method using the photosensitive composition of the present invention, but preferably includes, in order: a step of forming a photosensitive layer on a substrate using the photosensitive composition of the present invention; a step of exposing the photosensitive layer to a pattern; and developing (particularly, alkali developing) the exposed photosensitive layer. In the case where the development is organic solvent development, the method preferably includes a step of further exposing the obtained pattern.
In addition, when the photosensitive composition of the present invention is used to form a photosensitive layer on a substrate, the photosensitive composition may be used to form the transfer film, and the photosensitive layer may be formed on the substrate by using the transfer film. Specifically, as such a method, there may be mentioned: and a method in which the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support side is brought into contact with a substrate to bond the transfer film to the substrate, and the photosensitive layer in the transfer film is used as the photosensitive layer on the substrate.
Specific embodiments of the pattern forming method of the present invention include the pattern forming methods of embodiments 1 and 2.
The steps of the pattern forming methods according to embodiments 1 and 2 will be described in detail below.
[ Pattern Forming method of embodiment 1 ]
The pattern forming method of embodiment 1 includes steps X1 to X3. The following step X2 corresponds to a step of reducing the content of the acid group derived from the compound a in the photosensitive layer by exposure. Among these, when the developer in step X3 is an organic solvent-based developer, step X4 is preferably further provided after step X3.
Step X1: a step of bonding the transfer film to the substrate by bringing the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support side into contact with the substrate
Step X2: pattern exposure process for photosensitive layer
Step X3: developing the photosensitive layer with a developing solution (for example, an alkaline developing solution or an organic solvent-based developing solution)
Step X4: a step of exposing the pattern formed by the development after the development step of the step X3
When an alkaline developer is used as the developer in step X3, the photosensitive layer is preferably the photosensitive layer of embodiments X-1-a1 and X-1-a 2. When an organic solvent-based developer is used as the developer in step X3, the photosensitive layer is preferably the photosensitive material of embodiment X-1-a 1.
The pattern forming method of embodiment 1 is preferably applied to a transfer film including the photosensitive layers of embodiments X-1 to a1 and embodiments X-1 to a2 described above.
The pattern forming method of embodiment 1 preferably includes a step of peeling off the temporary support between the steps X1 and X2 or between the steps X2 and X3.
< procedure X1>
The pattern forming method according to embodiment 1 includes a step of bonding the transfer film to the substrate by bringing the surface of the photosensitive layer of the transfer film on the side opposite to the temporary support side into contact with the substrate.
Substrate material
The base material is not particularly limited, and examples thereof include a glass substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer. Examples of the substrate included in the substrate having the conductive layer include a glass substrate, a silicon substrate, and a resin substrate.
The substrate is preferably transparent.
The refractive index of the base material is preferably 1.50 to 1.52.
The base material may be a light-transmitting substrate such as a Glass substrate, and for example, a tempered Glass typified by Gorilla Glass, corning Incorporated co., ltd. The material contained in the base material is preferably a material used in japanese patent application laid-open publication nos. 2010-086684, 2010-152809 and 2010-257492.
When the base material includes a resin substrate, a resin film having small optical distortion and/or high transparency is more preferably used as the resin substrate. Specific examples of the material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymer.
As the substrate included in the substrate having the conductive layer, a resin substrate is preferable, and a resin film is more preferable from the viewpoint of roll-to-roll production.
The conductive layer may be any conductive layer used for a normal circuit wiring or a touch panel wiring.
The conductive layer is preferably 1 or more layers selected from the group consisting of a metal layer (metal foil or the like), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and still more preferably a copper layer or a silver layer, from the viewpoints of conductivity and fine line formation property.
The number of conductive layers in the substrate having the conductive layer may be 1 or 2 or more.
When the substrate having the conductive layers includes 2 or more conductive layers, the conductive layers are preferably conductive layers of different materials from each other.
Examples of the material of the conductive layer include a metal monomer and a conductive metal oxide.
Examples of the metal monomer include Al, zn, cu, fe, ni, cr, mo, ag and Au.
Examples of the conductive metal Oxide include ITO (indium tin Oxide), IZO (Indium Zinc Oxide: indium zinc Oxide) and SiO 2 Etc. In addition, "conductivity" means volume resistivity of less than 1X 10 6 Omega cm, preferably volume resistivity less than 1X 10 4 Ωcm。
In the case where the number of conductive layers in the substrate having the conductive layers is 2 or more, at least one of the conductive layers preferably contains a conductive metal oxide.
The conductive layer is preferably a wiring corresponding to an electrode pattern or a peripheral lead-out portion of a sensor of a visual recognition portion (used in a capacitive touch panel).
And, the conductive layer is preferably a transparent layer.
Step of Process X1
The step X1 is preferably a bonding step by pressing with a roller or the like and heating. For lamination, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator can be used.
The step X1 is preferably performed by a roll-to-roll method, and therefore, the substrate to be bonded to the transfer film is preferably a resin film or a resin film having a conductive layer.
Hereinafter, a roll-to-roll system will be described.
The roll-to-roll method is the following: a substrate capable of winding and unwinding is used as the substrate, and includes: a step of unreeling the base material (also referred to as "unreeling step") before any step included in the pattern forming method of the present invention; and a step of winding the base material after any step (also referred to as a "winding step"), and at least any step (preferably all steps or all steps except for a heating step) is performed while conveying the base material.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in the manufacturing method using the roll-to-roll method.
< procedure X2>
The pattern forming method according to embodiment 1 includes a step of exposing the photosensitive layer to a pattern after the step X1 (step X2). The step X2 corresponds to a step of reducing the content of the acid group derived from the compound a in the photosensitive layer by exposure. More specifically, it is preferable to pattern-expose the photosensitive layer by using light having a wavelength at which the specific structure S0 (preferably the specific structure S1) of the compound β (preferably the compound B) in the photosensitive layer (when the element V01 is present) and the specific structure S0 (preferably the specific structure S1) of the compound a (when the element W01 is present) are excited.
In the exposure process, the detailed arrangement and specific size of the pattern are not particularly limited.
For example, when the pattern forming method of embodiment 1 is applied to the manufacture of circuit wiring, at least a part of the pattern (particularly, a part corresponding to the electrode pattern and the lead-out wiring of the touch panel) is preferably a thin line of 100 μm or less, more preferably a thin line of 70 μm or less, from the viewpoint of improving the display quality of a display device (for example, a touch panel) including the input device including the circuit wiring manufactured by the pattern forming method of embodiment 1 and reducing the area occupied by the lead-out wiring as much as possible.
As a light source used for exposure, light having a wavelength which can be excited by light in a wavelength region in which the content of acid groups derived from the compound a in the photosensitive layer is reduced (light in a wavelength region such as 254nm, 313nm, 365nm, 405nm, etc., in the case where the photosensitive layer is the photosensitive layer), the specific structure S0 (preferably the specific structure S1) in the compound β (preferably the compound B) in the photosensitive layer (when the element V01 is provided) and the specific structure S0 (preferably the specific structure S1) in the compound a (when the element W01 is provided) can be appropriately selected. Specifically, an ultra-high pressure mercury lamp, a metal halide lamp, an LED (Light Emitting Diode: light emitting diode), and the like are given.
As the exposure amount, 10 to 10000mJ/cm is preferable 2 More preferably 50 to 3000mJ/cm 2 。
In step X2, the temporary support may be removed from the photosensitive layer and then subjected to pattern exposure, or the temporary support may be removed after pattern exposure with the temporary support interposed therebetween before removal of the temporary support. In order to prevent contamination of the mask due to contact between the photosensitive layer and the mask and to avoid influence on exposure due to foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling off the temporary support. The pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
Before step X3 described later, the temporary support is peeled off from the photosensitive layer.
< procedure X3>
The pattern forming method according to embodiment 1 includes a step (step X3) +of developing the pattern-exposed photosensitive layer with a developing solution (particularly, an alkaline developing solution) after the step X2.
The photosensitive layer subjected to step X2 has a reduced content of acid groups in the photosensitive layer of the exposed portion, and thus a difference in solubility in a developer (dissolution contrast) occurs between the exposed portion and the unexposed portion. The pattern can be formed in step X3 by forming the dissolution contrast in the photosensitive layer. In addition, when the developer in the step X3 is an alkaline developer, the unexposed area is removed to form a negative pattern by performing the step X3. On the other hand, when the developer in the step X3 is an organic solvent-based developer, the exposure portion is removed to form a positive pattern by performing the step X3. The positive pattern thus obtained is subjected to a process in which the content of acid groups derived from the compound a is reduced by the step X4 described later.
(alkaline developer)
The alkali developer is not particularly limited as long as the unexposed portion of the photosensitive resin layer can be removed, and for example, a known developer such as the developer described in japanese patent application laid-open No. 5-072724 can be used.
As the alkali developer, for example, an alkali aqueous developer containing a compound having pka=7 to 13 at a concentration of 0.05 to 5mol/L (liter) is preferable.
The alkaline developer may further contain a water-soluble organic solvent, a surfactant, and the like. As the alkali developer, for example, the developer described in paragraph 0194 of international publication No. 2015/093271 is preferable.
The concentration of water in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. The upper limit is, for example, less than 100 mass%.
(organic solvent developer)
The organic solvent-based developer is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed, and for example, a developer containing an organic solvent such as a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, and a hydrocarbon-based solvent can be used.
The organic solvent-based developer may be mixed with a plurality of organic solvents, or may be mixed with an organic solvent other than the above or water for use. In order to sufficiently exhibit the effects of the present invention, the water content of the entire organic solvent-based developer is preferably less than 10% by mass, and more preferably substantially no water is contained. The concentration of the organic solvent (total in the case of mixing plural types) in the organic solvent-based developer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. The upper limit is, for example, 100 mass% or less.
The development method is not particularly limited, and may be any of spin immersion development, spray development, spin development, dip development, and the like. In the description of the shower development, unnecessary portions can be removed by blowing the developer to the photosensitive resin layer after exposure by the shower. After development, it is also preferable to remove the development residues by spraying and blowing a cleaning agent or the like while wiping with a brush or the like. The liquid temperature of the developer is preferably 20 to 40 ℃.
The pattern forming method of embodiment 1 may further include a post baking step of heat-treating the pattern including the photosensitive layer obtained by development, or may not include a post baking step.
The post baking is preferably performed in an atmosphere of 8.1 to 121.6kPa, more preferably 50.66kPa or more. On the other hand, the operation is more preferably performed under an environment of 111.46kPa or less, and still more preferably performed under an environment of 101.3kPa or less.
The post-baking temperature is preferably 80 to 250 ℃, more preferably 110 to 170 ℃, and even more preferably 130 to 150 ℃.
The post-baking time is preferably 1 to 60 minutes, more preferably 2 to 50 minutes, and still more preferably 5 to 40 minutes.
Post baking may be performed in an air environment or in a nitrogen-substituted environment.
< procedure X4>
When the developer in the step X3 is an organic solvent-based developer, the step X4 is performed on the positive pattern obtained. The step X4 corresponds to a step of exposing the positive pattern obtained in the step X3 to light and reducing the content of the acid group derived from the compound a. More specifically, it is preferable to pattern-expose the photosensitive layer by using light having a wavelength at which the specific structure S0 (preferably the specific structure S1) of the compound β (preferably the compound B) in the photosensitive layer (when the element V01 is present) and the specific structure S0 (preferably the specific structure S1) of the compound a (when the element W01 is present) are excited.
The light source and the exposure amount used for exposure are preferably the same as those described in the step X1.
[ Pattern Forming method of embodiment 2 ]
The pattern forming method according to embodiment 2 includes a step Y1, a step Y2P, and a step Y3 in this order, and further includes a step Y2Q (step of exposing the exposed photosensitive layer in the step Y2P) between the step Y2P and the step Y3 or after the step Y3.
Step Y1: a step of bonding the transfer film to the base material by bringing the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support into contact with the base material
Process Y2P: exposing the photosensitive layer
Step Y3: developing the photosensitive layer
As described above, the pattern formation method according to embodiment 2 corresponds to a mode in which the photosensitive layer can be applied when the photosensitive layer further contains a photopolymerization initiator and a polymerizable compound. Accordingly, the pattern forming method of embodiment 2 is preferably applied to a transfer film including the photosensitive layers of embodiments X-1 to a3 described above.
Hereinafter, the pattern forming method of embodiment 2 will be described, and the steps Y1 and Y3 are the same as the steps X1 and X3, respectively, and therefore, the description thereof will be omitted.
The process Y3 may be performed at least after the process Y2P, and the process Y3 may be performed between the process Y2P and the process Y2Q.
The pattern formation method according to embodiment 2 may further include a post baking step of heat-treating the pattern including the photosensitive layer obtained by development after step Y3, or may not include a post baking step. The post-baking step can be performed by the same method as the post-baking step that can be included in the pattern forming method according to embodiment 1. In the case of performing the step Y3 between the step Y2P and the step Y2Q, the post-baking step may be performed before the step Y2Q or after the step Y2Q as long as the post-baking step is performed after the step Y3.
The pattern forming method of embodiment 2 preferably includes a step of peeling off the temporary support between the step Y1 and the step Y2P or between the step Y2P and the step Y3.
Process Y2P, process Y2Q-
The pattern forming method according to embodiment 2 includes a step of exposing the photosensitive layer having undergone the step Y1 (step Y2P) and a step of further exposing the exposed photosensitive layer (step Y2Q).
The exposure treatment (step Y2P and step Y2Q) mainly corresponds to exposure for reducing the content of the acid groups derived from the compound a by exposure, and the other exposure treatment (step Y2P and step Y2Q) mainly corresponds to exposure for causing polymerization reaction of the polymerizable compound by the photopolymerization initiator. The exposure process (step Y2P and step Y2Q) may be either a full-face exposure or a pattern exposure, but any of the exposure processes may be a pattern exposure.
For example, in the case where the step Y2P is a pattern for reducing the content of the acid groups derived from the compound a by exposure, the developer used in the step Y3 may be an alkaline developer or an organic solvent developer. In the case of development with an organic solvent-based developer, the step Y2Q is usually performed after the step Y3, and the polymerization reaction of the polymerizable compound by the photopolymerization initiator is caused in the photosensitive layer (pattern) to be developed, and the content of the acid group (preferably carboxyl group) derived from the compound a is reduced.
For example, when the step Y2P is a pattern exposure for causing a polymerization reaction of a polymerizable compound by a photopolymerization initiator, the developer used in the step Y3 is usually an alkaline developer. In this case, the process Y2Q may be performed before or after the process Y3, and the process Y2Q performed before the process Y3 is usually pattern exposure.
In the steps Y2P and Y2Q, as a light source used for exposure, light in a wavelength region capable of reducing the content of an acid group derived from the compound a in the photosensitive layer (light in a wavelength region capable of causing a reaction of a polymerizable compound based on a photopolymerization initiator in the photosensitive layer (light in a wavelength region capable of causing a photopolymerization initiator, for example, 254nm, 313nm, 365nm, 405nm, etc.) or light in a wavelength region capable of causing a reaction of a photopolymerization initiator in the photosensitive layer (light in a wavelength region capable of causing a photopolymerization initiator, for example, 254nm, 313nm, 365nm, 405nm, etc.) is preferably selected. Specifically, an ultra-high pressure mercury lamp, a metal halide lamp, an LED (Light Emitting Diode: light emitting diode), and the like are given.
In the exposure for reducing the content of the acid group derived from the compound A in the photosensitive layer, the exposure amount is preferably 10 to 10000mJ/cm 2 More preferably 50 to 3000mJ/cm 2 。
In the exposure for causing the reaction of the polymerizable compound based on the photopolymerization initiator in the photosensitive layer, the exposure amount is preferably 5 to 200mJ/cm 2 More preferably 10 to 150mJ/cm 2 。
In the steps Y2P and Y2Q, the temporary support may be removed from the photosensitive layer and then subjected to pattern exposure, or the temporary support may be removed after pattern exposure with the temporary support interposed therebetween before removal of the temporary support. In order to prevent contamination of the mask due to contact between the photosensitive layer and the mask and to avoid influence on exposure due to foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling off the temporary support. The pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
In the exposure process, the detailed arrangement and specific size of the pattern are not particularly limited.
For example, when the pattern forming method of embodiment 2 is applied to the manufacture of circuit wiring, at least a part of the pattern (particularly, a part corresponding to the electrode pattern and the lead-out wiring of the touch panel) is preferably a thin line of 100 μm or less, more preferably a thin line of 70 μm or less, from the viewpoint of improving the display quality of a display device (for example, a touch panel) including the input device including the circuit wiring manufactured by the pattern forming method of embodiment 2 and reducing the area occupied by the lead-out wiring as much as possible.
Preferred mode-
As the pattern forming method of embodiment 2, it is also preferable to sequentially include a step Y1, a step Y2A, a step Y3, and a step Y2B. It is also preferable that one of the steps Y2A and Y2B is an exposure step for reducing the content of the acid groups derived from the compound a by exposure, and the other is an exposure step for causing polymerization reaction of the polymerizable compound by the photopolymerization initiator.
Step Y1: a step of bonding the transfer film to the base material by bringing the surface of the photosensitive layer in the transfer film on the side opposite to the temporary support into contact with the base material
Step Y2A: pattern exposure process for photosensitive layer
Step Y3: developing the photosensitive layer with an alkaline developer to form a pattern
Step Y2B: exposing the pattern obtained in the step Y3
In the pattern forming method, the step of peeling off the temporary support is preferably performed between the step Y1 and the step Y2A or between the step Y2A and the step Y3.
The step Y2A is preferably an exposure step for causing a polymerization reaction of a polymerizable compound based on a photopolymerization initiator, and the step Y2B is preferably an exposure step for reducing the content of an acid group derived from the compound a by exposure.
[ optional steps that the pattern formation methods of embodiment 1 and embodiment 2 can have ]
The pattern formation methods according to embodiments 1 and 2 may include any process (other process) other than the above. For example, the following steps may be mentioned, but the present invention is not limited to these steps.
Cover film peeling step
In the case where the transfer film has a cover film, the pattern forming method preferably includes a step of peeling off the cover film of the transfer film (hereinafter, also referred to as a "cover film peeling step"). The method of peeling the cover film is not particularly limited, and a known method can be applied.
Process for reducing reflectance of visible rays
In the case where the substrate is a substrate having a conductive layer, the pattern forming method may further include a step of performing a treatment for reducing the visible ray reflectance of the conductive layer. In the case where the substrate is a substrate having a plurality of conductive layers, the treatment for reducing the reflectance of visible light may be performed on a part of the conductive layers or may be performed on all the conductive layers.
As the treatment for reducing the reflectance of visible light, an oxidation treatment is given. For example, the visible ray reflectance of the conductive layer can be reduced by oxidizing copper to form copper oxide to darken it.
A preferred embodiment of the treatment for reducing the reflectance of visible light is described in paragraphs 0017 to 0025 of japanese patent application laid-open publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of japanese patent application laid-open publication No. 2013-206315, the contents of which are incorporated herein by reference.
Etching procedure-
In the case where the substrate is a substrate having a conductive layer, the pattern forming method preferably includes a step (etching step) of using the pattern formed in the steps X3 (or X4) and Y3 as an etching resist film and performing etching treatment on the conductive layer in a region where the etching resist film is not provided.
As a method of etching treatment, a wet etching method described in paragraphs 0048 to 0054 and the like of jp 2010-152155 a, a known dry etching method such as plasma etching, and the like can be applied.
For example, a wet etching method in which a conventional etching treatment is performed by immersing in an etching liquid is given as an example of the etching treatment. The etching liquid used in the wet etching may be an acidic type or an alkaline type etching liquid as appropriate depending on the object to be etched.
Examples of the acidic etching liquid include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid alone, and aqueous solutions of acidic components mixed with salts such as ferric chloride, ammonium fluoride, and potassium permanganate. As the acidic component, a component obtained by combining a plurality of acidic components can be used.
Examples of the alkaline etching liquid include aqueous solutions of alkali components such as salts of organic amines including sodium hydroxide, potassium hydroxide, ammonia, organic amines, and tetramethylammonium hydroxide, and aqueous solutions of mixtures of alkali components and salts of potassium permanganate. As the alkali component, a component obtained by combining a plurality of alkali components can be used.
The temperature of the etching solution is not particularly limited, but is preferably 45 ℃ or lower. In the method for manufacturing a circuit wiring of the present invention, the pattern formed in the step X3 (or the step X4) and the step Y3 (or the step Y2B) used as the etching resist film preferably exhibits particularly excellent resistance to an acidic and alkaline etching solution in a temperature range of 45 ℃ or less. With the above structure, peeling of the etching resist film in the etching process can be prevented, and a portion where the etching resist film does not exist can be selectively etched.
After the etching step, a cleaning step of cleaning the etched substrate and a drying step of drying the cleaned substrate may be performed as necessary in order to prevent contamination of the process line.
< other embodiments >
In the above-described pattern formation method, it is also preferable that a substrate having a plurality of conductive layers is used on each of the two surfaces, and the conductive layers formed on the two surfaces are sequentially or simultaneously patterned.
With this structure, the first conductive pattern can be formed on one surface of the substrate and the second conductive pattern can be formed on the other surface. It is also preferable to form it from both sides of the substrate in a roll-to-roll manner.
[ Pattern ]
The pattern formed by the pattern formation method according to the above-described embodiments 1 and 2 has reduced polarity, moisture permeability, and relative permittivity due to reduced content of acid groups.
The content of the acid groups in the pattern is preferably reduced by 5 mol% or more, more preferably by 10 mol% or more, still more preferably by 20 mol% or more, still more preferably by 31 mol% or more, particularly preferably by 40 mol% or more, particularly preferably by 51 mol% or more, and most preferably by 71 mol% or more, relative to the content of the acid groups in the photosensitive layer formed in the step X1 or the step Y1. The upper limit is not particularly limited, and is, for example, 100 mol% or less.
The moisture permeability of the pattern is preferably reduced by 5% or more, more preferably by 10% or more, and even more preferably by 20% or more, relative to the moisture permeability of the photosensitive layer formed in step X1 or step Y1. The upper limit is not particularly limited, and is, for example, 100% or less.
The relative permittivity of the pattern is preferably reduced by 5% or more, more preferably by 10% or more, and even more preferably by 15% or more, relative permittivity of the photosensitive layer formed in step X1 or step Y1. The upper limit is not particularly limited, and is, for example, 100% or less.
The average thickness of the pattern formed by the pattern forming method is preferably 0.5 to 20. Mu.m. The average thickness of the pattern is more preferably 0.8 to 15. Mu.m, still more preferably 1.0 to 10. Mu.m.
The pattern formed by the above-described pattern forming method is preferably colorless. Specifically, total reflection (incidence angle 8 °, light source: D-65 (2 ° field of view)) is observed in CIE1976 (L) * 、a * 、b * ) In color space, L of pattern * The value is preferably 10 to 90, a of the pattern * The value is preferably-1.0 to 1.0, b of the pattern * The value is preferably-1.0 to 1.0.
The use of the pattern formed by the pattern forming method described above is not particularly limited, and the pattern can be used as various protective films or insulating films.
Specifically, the use of a protective film (permanent film) for protecting conductive patterns, the use of an interlayer insulating film between conductive patterns, the use of an etching resist film in manufacturing circuit wiring, and the like are given. Among them, the use as a protective film (permanent film) for protecting a conductive pattern or an interlayer insulating film between conductive patterns is preferable because the patterns are excellent in low moisture permeability.
In addition, the above pattern can be used, for example, for the following purposes: a protective film (permanent film) for protecting conductive patterns such as electrode patterns, peripheral wiring portions, and wirings leading out from wiring portions of a sensor corresponding to a visual recognition portion provided in a touch panel, or an interlayer insulating film between the conductive patterns.
[ method of manufacturing Circuit Wiring ]
The invention also relates to a method for manufacturing the circuit wiring.
The method for producing a circuit wiring according to the present invention (also referred to as "the method for producing a circuit wiring according to the present invention") is not particularly limited as long as it is a method for producing a circuit wiring using the photosensitive composition, and among them, a method for producing a circuit wiring using the transfer film is preferable.
As a method for manufacturing a circuit wiring using the transfer film, it is preferable to sequentially include: a step (bonding step) of bonding the transfer film to the substrate having the conductive layer by bringing the surface of the photosensitive layer on the side opposite to the temporary support side of the transfer film into contact with the conductive layer of the substrate having the conductive layer; a step of performing pattern exposure (first exposure step) on the photosensitive layer in the bonded transfer film; a step of developing the exposed photosensitive layer with an alkaline developer to form a patterned etching resist film (etching resist film forming step); and a step of etching the conductive layer in a region where the etching resist film is not disposed (etching step). The etching resist film forming step preferably includes the steps of: a step of developing the exposed photosensitive layer obtained through the first exposure step with an alkaline developer to form a pattern (alkaline development step); and a step of exposing the obtained pattern to light to form an etching resist film (second exposure step).
In the method for manufacturing a circuit wiring according to the present invention, the bonding step, the first exposure step, the alkaline development step, and the second exposure step can be performed by the same steps as the steps Y1, Y2A, Y3, and Y2B of the pattern forming method according to embodiment 2 described above. The etching resist film forming step may be performed by the same method as in step Y3. The substrate having a conductive layer used in the method for manufacturing a circuit wiring of the present invention is the same as the substrate having a conductive layer used in the step X1. The method for manufacturing a circuit wiring according to the present invention may have steps other than the above steps. As other steps, the same steps as those which can be provided in the pattern forming method according to the first embodiment and the second embodiment can be mentioned.
In the method for manufacturing a circuit wiring according to the present invention, it is preferable that the bonding step, the first exposure step, the developing step, the second exposure step, and the etching step are repeated 1 set of 4 steps.
The film used as the etching resist film can also be used as a protective film (permanent film) of the formed circuit wiring.
[ method of manufacturing touch Panel ]
The invention also relates to a manufacturing method of the touch panel.
The method for producing a touch panel according to the present invention (also referred to as "the method for producing a touch panel according to the present invention") is not particularly limited as long as it is a method for producing a touch panel using the photosensitive composition, and among them, a method for producing a touch panel using the transfer film is preferable.
As a method for manufacturing a touch panel according to the present invention, it is preferable to sequentially include: a step (bonding step) of bonding the transfer film to the substrate having the conductive layer (preferably, the patterned conductive layer, specifically, the conductive pattern such as the touch panel electrode pattern or the wiring) by bringing the surface of the photosensitive layer on the side opposite to the temporary support side of the transfer film into contact with the conductive layer in the substrate having the conductive layer; a step of performing pattern exposure (first exposure step) on the photosensitive layer in the bonded transfer film; and a step of forming a patterned protective film or insulating film of the conductive layer by developing the exposed photosensitive layer with an alkaline developer (protective film or insulating film forming step). The protective film or insulating film forming step preferably includes the steps of: a step of developing the exposed photosensitive layer obtained through the first exposure step with an alkaline developer to form a pattern (alkaline development step); and a step of exposing the obtained pattern to form a protective film or an insulating film of the conductive layer (second exposure step).
The protective film has a function as a film for protecting the surface of the conductive layer. The insulating film also functions as an interlayer insulating film between the conductive layers. In addition, in the case of forming the insulating film of the conductive layer, the method for manufacturing a touch panel of the present invention preferably further includes a step of forming a conductive layer (preferably a patterned conductive layer, specifically, a conductive pattern such as a touch panel electrode pattern or a wiring) on the insulating film.
In the method for manufacturing a touch panel according to the present invention, the bonding step, the first exposure step, the alkaline development step, and the second exposure step can be performed by the same steps as the steps Y1, Y2A, Y3, and Y2B of the pattern forming method according to embodiment 2. The protective film or insulating film forming step may be performed by the same steps as those in step Y3. The substrate having a conductive layer used in the method for manufacturing a touch panel according to the present invention is the same as the substrate having a conductive layer used in the step X1. As other steps, the same steps as those which can be provided in the pattern forming method according to the first embodiment and the second embodiment can be mentioned.
As a method for manufacturing a touch panel according to the present invention, a known method for manufacturing a touch panel can be referred to for a structure other than the above-described method.
The touch panel manufactured by the method for manufacturing a touch panel of the present invention preferably has a transparent substrate, electrodes, and a protective layer (protective film).
The detection method in the touch panel may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.
Examples of the Touch panel type include a so-called in-line type (for example, a structure described in fig. 5, 6, 7, and 8 of japanese patent application laid-open No. 2012-517051), a so-called out-line type (for example, a structure described in fig. 19 of japanese patent application laid-open No. 2013-168125, a structure described in fig. 1 and 5 of japanese patent application laid-open No. 2012-089102), an OGS (One Glass Solution: one-piece type Touch panel), a TOL (Touch-on-Lens: overlay Touch) type (for example, a structure described in fig. 2 of japanese patent application laid-open No. 2013-054727), and other structures (for example, a structure described in fig. 6 of japanese patent application laid-open No. 2013-164871) and various kinds of out-line types (so-called GG, G1/G2, GFF, GF2, GF1, G1F, and the like).
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, proportions, treatment contents, treatment steps and the like shown in the following examples can be appropriately modified as long as they do not depart from the gist of the present invention. Accordingly, the scope of the present invention should not be limited to the examples shown below for explanation. In addition, "%" is based on mass unless otherwise specifically indicated. In the following examples, the weight average molecular weight of the resin was obtained by conversion of polystyrene by Gel Permeation Chromatography (GPC).
[ preparation of photosensitive composition ]
The components were mixed and stirred to obtain the composition and the formulation shown in Table 2 in the latter stage, thereby preparing a photosensitive composition. The numerical values of the polymer content (parts by mass) in table 2 indicate the amounts of solid components (excluding the solvent).
[ Components of photosensitive composition ]
The various components used in table 2 are shown below.
< Compound having an acid group >
The compounds having an acid group (polymers 1 to 9) were synthesized.
The method for synthesizing the polymer 8 is shown below as an example. Other polymers were synthesized in the same manner by changing the type and amount of the monomer to be charged.
Synthesis of Polymer 8 (copolymer of DCPMA/AA/AA-GMA [ composition ratio (mass ratio): 68/16/16, weight average molecular weight (Mw): 15000) ];
propylene glycol monomethyl ether 77.2g was charged to the flask and heated to 90℃under a nitrogen stream. 89.8g of dicyclopentanyl methacrylate (Showa Denko Materials co., ltd.) was added dropwise to this solution over 2 hours, followed by dissolution of 28.3g of acrylic acid in 30g of propylene glycol monomethyl ether and dissolution of 5.5g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 30g of propylene glycol monomethyl ether. After completion of the dropwise addition, 0.7g of V-601 was added after reacting at 90℃for 1 hour. Then, it was reacted for 3 hours. Then, the mixture was diluted with 60.4g of propylene glycol monomethyl ether acetate and 26.4g of propylene glycol monomethyl ether. The reaction solution was warmed to 100℃under an air flow, and 0.47g of tetraethylammonium bromide and 0.23g of p-methoxyphenol were added. To this, 14.0G of glycidyl methacrylate (BLEMER G manufactured by NOF CORPORATION) was added dropwise over 20 minutes. It was reacted at 100℃for 7 hours to obtain a solution of polymer 8. The solid content concentration of the obtained solution was 36.3 mass%. The weight average molecular weight in terms of standard polystyrene in GPC was 15000, the dispersity was 2.2, and the acid value of the polymer was 125mgKOH/g. The amount of residual monomer measured by gas chromatography was less than 0.1 mass% in any monomer relative to the solid content of the polymer.
In addition, each polymer is synthesized in a state of being contained in a solution, but when the polymer is used as a component of the photosensitive composition, only a solid component (polymer) contained in the solution is added as a component of the photosensitive composition. For example, the photosensitive composition used for the transfer films of examples 1 and 2 contains 100 parts by mass of the polymer 1 itself, instead of 100 parts by mass of the solution.
Polymer 1: copolymers of St/MAA/MMA/MAA-GMA [ composition ratio (mass ratio): st/MAA/MMA/MAA-GMA=47.7/19/1.3/32, weight average molecular weight (Mw): 18,000 ]
Polymer 2: copolymer of CHMA/MAA/MMA/MAA-GMA [ composition ratio (mass ratio): 55.1/14.5/1.3/29.1, weight average molecular weight (Mw): 27,000 ]
Polymer 3: copolymer of IBMA/MAA [ composition ratio (mass ratio): 80/20, weight average molecular weight (Mw): 12000 ]
Polymer 4: copolymer of DCPMA/MAA [ composition ratio (mass ratio): 80/20, weight average molecular weight (Mw): 30000)
Polymer 5: copolymer of DCPMA/AA [ composition ratio (mass ratio): 83/17, weight average molecular weight (Mw): 20000
Polymer 6: copolymer of IBMA/IBA/AA [ composition ratio (mass ratio): 20/63/17, weight average molecular weight (Mw): 33000)
Polymer 7: copolymer of DCPMA/AA/AA-GMA [ composition ratio (mass ratio): 74/16/10, weight average molecular weight (Mw): 24000)
Polymer 8: copolymer of DCPMA/AA/AA-GMA [ composition ratio (mass ratio): 68/16/16, weight average molecular weight (Mw): 15000 ]
Polymer 9: copolymer of DCPMA/AA/AA-GMA [ composition ratio (mass ratio): 52/16/32, weight average molecular weight (Mw): 16000)
Hereinafter, abbreviations in the above polymers are shown.
St: styrene-based repeat units
MAA: methacrylic acid-based repeat units
MMA: methyl methacrylate-based repeat units
MAA-GMA: repeating units obtained by reacting a glycidyl methacrylate with a carboxyl group of a repeating unit based on methacrylic acid
CHMA: cyclohexyl methacrylate-based repeat units
DCPMA: repeat units based on dicyclopentanyl methacrylate
AA: acrylic acid-based repeating units
AA-GMA: repeating units obtained by reacting a carboxyl group of an acrylic acid-based repeating unit with glycidyl methacrylate
IBMA: isobornyl methacrylate-based repeat units
IBA: isobornyl acrylate-based repeat units
< Compound beta >
1-methylisoquinoline (manufactured by FUJIFILM Wako Pure Chemical Corporatio)
2, 4-dimethylquinoline (manufactured by FUJIFILM Wako Pure Chemical Corporatio)
< polymerizable Compound >
TMPTA: trimethylolpropane triacrylate (Shin Nakamura Chemical Industry Co., LTD. Manufactured A-TMPT)
DTMPTA: ditrimethylolpropane tetraacrylate (KAYARAD T-1420 (T) manufactured by Nippon Kayaku co., ltd.)
DPHA: dipentaerythritol hexaacrylate (Shin Nakamura Chemical Industry Co., LTD. Manufactured A-DPH)
a-NOD-N:1, 9-nonanediol diacrylate (Shin Nakamura Chemical Industry Co., LTD. Manufactured A-NOD-N)
< initiator >
Irg379: omnirad 379 (alkyl benzophenone compound, manufactured by IGM Resins B.V.)
Oxe02: irgacure OXE02 (oxime ester Compound manufactured by BASF Co., ltd.) in acetonitrile, molar absorption coefficient 2700 (cm. Mol/L) with respect to light having a wavelength of 365nm -1
Api307:1- (Biphenyl-4-yl) -2-methyl-2-morpholinopropan-1-one (1- (biphen-4-yl) -2-methyl-2-morphol inopropan-1-one) (manufactured by Shenzhen UV-Chem Tech LTD)
< surfactant >
F551A: MEGAFACE F551 (DIC Corporation)
< solvent >
MEK: methyl ethyl ketone
PGMEA: propylene glycol monomethyl ether acetate
MFG: propylene glycol monomethyl ether
[ various measurements ]
[ preparation of test sample (sample X) ]
The prepared photosensitive composition was spin-coated on a glass substrate (Corning Incorporated co., ltd., manufactured "EAGLE XG"), and then dried at 80 ℃ for 2 minutes using a hot plate to obtain a film (photosensitive layer) having a film thickness of 2 μm. Next, a polyethylene terephthalate film (PET film, 16KS40 manufactured by tar INDUSTRIES, INC.) was pressure-bonded from the upper surface of the obtained film (photosensitive layer), and a laminate in which a glass substrate, a photosensitive layer, and a PET film were laminated in this order was produced. The pressure bonding conditions were set to a lamination temperature: 25 ℃, pressure: 0.6Pa, line pressure 3N/cm, and conveying speed 4 m/min. Next, the photosensitive layer in the laminate was exposed to light through a PET film using a proximity exposure machine (mtachi High-Tech corporation) having an ultra-High pressure mercury lamp so that the cumulative exposure amount at 365nm wavelength became 80mJ/cm 2 . After exposure, the laminate was left in an atmosphere of 50% RH at 25℃for 30 minutes, and then the PET film was peeled off. Next, the photosensitive layer exposed by peeling of the PET film was exposed to light using an ultraviolet radiation transfer device (EYE GRAPHICS CO., LTD.) having a high-pressure mercury lamp so that the cumulative exposure at 365nm wavelength became 1000mJ/cm 2 . Then, the post-exposure feel on the glass substrate is shavedThe light-emitting layer was prepared as a 100mg powder test sample (hereinafter, sample X). In addition, when the cut post-exposure photosensitive layer is not in a powder form, it is pulverized and used.
[ measurement of glass transition temperature of photosensitive layer after exposure ]
(1) Using 5 to 6mg of sample X, temperature-modulated differential scanning calorimetric measurement was performed under the following conditions.
The device comprises: DSC2500 from TA Instruments (Tzero aluminum crucible was used to enclose the sample)
Measurement conditions: under nitrogen atmosphere, temperature range-70-200 ℃ (5 ℃/min), temperature modulation condition + -1 ℃/min (n=2))
(2) Next, the temperature (midpoint) of the baseline shift in the reversible heat Flow (rev. Heat Flow) was taken as the glass transition temperature (average value of n 2). The measurement results are shown in table 2.
[ measurement of moisture content of photosensitive layer after exposure at 40 ℃ 90% RH ]
(1) 11-12 mg of sample X (a [ mg ]) was weighed in a laboratory at 23℃and 50% RH.
(2) This was charged into a furnace of a heating and discharging apparatus heated to 150℃and measured for 15 minutes using a Karl Fischer moisture meter (apparatus: karl Fischer moisture meter was used as "AQ-2100" manufactured by HIRANUMA Co., ltd., heating and discharging apparatus was used as "EV-2000" manufactured by HIRANUMACo., ltd.).
(3) From the measured components, the water content x [ mass% ] at 23℃50% RH was determined by the following formula.
(moisture amount/a) ×100=x [ mass% ]
(4) 11-12 mg of sample X (b [ mg ]) was weighed in a laboratory at 23℃and 50% RH.
(5) Sample X was stored in a constant temperature and humidity tank at 40℃and 90% RH for 24 hours.
(6) Immediately after being taken out of the constant temperature and humidity tank, the mixture was charged into a furnace of a heating and discharging device heated to 150℃and measured for 15 minutes by using a Karl Fischer moisture meter (apparatus: karl Fischer moisture meter was used as "AQ-2100" manufactured by HIRANUMACo., ltd., heating and discharging device was used as "EV-2000" manufactured by HIRANUMACo., ltd.).
(7) From the measured moisture content, the (apparent) moisture content y [ mass% ] at 40 ℃ 90% rh was determined by the following formula.
(moisture amount/b) ×100=y [ mass% ]
(8) The water content at 40℃and 90% RH was determined by the following formula using the values of x and y.
{ moisture amount/(dry mass+moisture amount) } ×100[ mass% ] = [ (b×y/100)/{ b× (100-x)/100+b×y/100} ] ×100[ mass% ] = { y/(100-x+y) } ×100[ mass% ]
(9) The measurements (1) to (8) were carried out 5 times, and the arithmetic average was used as the water content. The measurement results are shown in table 2.
[ production of transfer film ]
The photosensitive composition of each example or comparative example was applied to a PET film (manufactured by tolay INDUSTRIES, INC., 16KS40 (16 QS 62)) (temporary support) having a thickness of 16 μm by using a slit nozzle, and the film was dried at 100 ℃ for 2 minutes so that the thickness of the film became the film thickness described in table 2.
The obtained photosensitive layer was pressure-bonded with a PET film (manufactured by tolay INDUSTRIES, INC., 16KS40 (16 QS 62)) (cover film) having a thickness of 16 μm, and transfer films of examples and comparative examples were produced.
[ evaluation: corrosion test ]
< preparation of test sample >
(1) The cover film of the transfer film thus produced was peeled off to expose the photosensitive layer.
Next, a transfer film was laminated on a copper base material (PET film (manufactured by geomotec co., ltd.) in which copper foil was laminated) so that the copper foil was in contact with the exposed photosensitive layer. The lamination conditions were set to lamination temperature: 100 ℃, line thickness: 3N/cm, transfer speed: 1 m/min.
(2) The photosensitive layer was exposed to light through a PET film as a temporary support by using a proximity type exposure machine (Hi tachi high-Tech corporation) having an ultra-high pressure mercury lamp to cause wavesThe cumulative exposure at 365nm length was 80mJ/cm 2 。
(3) After exposure, the film was left to stand in an atmosphere of 50% RH at 25℃for 30 minutes, and then the PET film as a temporary support was peeled off.
(4) Next, the photosensitive layer exposed by peeling the PET film as a temporary support was exposed to light using an ultraviolet radiation transfer device (EYE GRAPHICS CO., LTD.) having a high-pressure mercury lamp so that the cumulative exposure at 365nm wavelength became 1000mJ/cm 2 。
(5) Then, a copper base material having the above-described photosensitive layer after exposure was used as a test sample, and a corrosion test described later was performed.
< Corrosion test >
The test sample was placed in an environment of 83 ℃ and 87% rh, and the change in copper color after a prescribed time was observed visually. The results are shown in Table 2.
(evaluation criterion)
"A": copper does not change color at the time of 1000 hours.
"B": copper does not change color at the time of 800 hours, while copper changes color at the time of 1000 hours.
"C": copper changes color at the time of 800 hours.
Table 2 is shown below.
TABLE 2
From the results of table 2, it is clear that the post-exposure photosensitive layer obtained from the photosensitive composition of example is excellent in corrosion resistance under a hot and humid environment. Therefore, it is found that the photosensitive composition according to the examples can form a pattern excellent in corrosion resistance under a hot and humid environment. It is also clear that even in the case of a transfer film having a photosensitive layer formed from the photosensitive composition of the examples, a pattern excellent in corrosion resistance under a hot and humid environment can be formed.
Further, for example, as is clear from the comparison of examples 1 and 2 and the comparison of examples 3 and 4, the photosensitive composition according to the examples can form a pattern excellent in corrosion resistance under a hot and humid environment irrespective of the film thickness of the photosensitive layer formed of the photosensitive composition.
It is also clear from the comparison of examples 1 to 12 that when the photosensitive composition satisfies the requirements A1 and A2 and the glass transition temperature of the requirement A1 is 100 ℃ or higher and the glass transition temperature of the requirement A2 is 120 ℃ or lower, a pattern excellent in corrosion resistance under a hot and humid environment can be formed.
The photosensitive composition of the comparative example did not exhibit the desired effect.
Example 13
Using the photosensitive compositions of examples 1 to 12, patterning was performed in accordance with the following procedure.
(1) The cover film of the transfer film thus produced was peeled off to expose the photosensitive layer.
Next, a transfer film was laminated on a copper base material (PET film (manufactured by geomotec co., ltd.) in which copper foil was laminated) so that the copper foil was in contact with the exposed photosensitive layer. The lamination conditions were set to lamination temperature: 100 ℃, line thickness: 3N/cm, transfer speed: 1 m/min.
(2) Using a proximity type exposure machine (Hitachi High-Tech corporation) having an ultra-High pressure mercury lamp, the distance between the exposure mask surface having a line-space pattern (line size=150 μm, line: space=1:1) and the surface of the temporary support was set to 125 μm, and the photosensitive layer was subjected to pattern exposure via a PET film as the temporary support so that the cumulative exposure amount at 365nm became 80mJ/em 2 。
(3) After exposure, the film was left to stand in an atmosphere of 50% RH at 25℃for 30 minutes, and then the PET film as a temporary support was peeled off.
(4) The photosensitive layer after exposure was developed with a1 mass% aqueous solution (liquid temperature: 30 ℃) of sodium carbonate as a developing solution for 45 seconds. After development, the pattern was obtained by washing with pure water for 15 seconds and blowing air to remove moisture.
(5) Next, ultraviolet irradiation with high-pressure mercury lamp is usedA feeder (EYE GRAPHICS CO., LTD.) for performing full-face exposure to the pattern so that the cumulative exposure at 365nm becomes 1000mJ/cm 2 。
It was confirmed that the photosensitive compositions of examples 1 to 12 used obtained a line-and-space pattern that was cleaned.
Symbol description
12-temporary support, 14-photosensitive layer, 16-cover film, 100-transfer film.

Claims (19)

1. A photosensitive composition satisfying the following requirements A1 and B1,
condition A1: the glass transition temperature of the photosensitive layer after exposure obtained by the following step X is 65 ℃ or higher,
requirement B1: the water content of the photosensitive layer after exposure obtained by the following step X at 40 ℃ and 90% RH is less than 2.0% by mass,
step X: a laminate comprising a glass substrate, a photosensitive layer formed of the photosensitive composition and a resin film in this order is obtained, and then, from the side of the laminate opposite to the glass substrate side, an ultra-high pressure mercury lamp is used so that the cumulative exposure at a wavelength of 365nm becomes 80mJ/cm 2 The photosensitive layer in the laminate was exposed to light, the laminate was left in an atmosphere of 50% RH at 25℃for 30 minutes after the exposure, the resin film was peeled off, and then a high-pressure mercury lamp was used from the side from which the resin film was peeled off, so that the cumulative exposure at a wavelength of 365nm became 1000mJ/cm 2 The photosensitive layer is exposed again to obtain a photosensitive layer after exposure.
2. The photosensitive composition according to claim 1, which further satisfies the following condition A2,
condition A2: the glass transition temperature of the photosensitive layer after exposure obtained in the step X is 165 ℃ or lower.
3. The photosensitive composition according to claim 2, wherein,
the glass transition temperature in the element A2 is 120 ℃ or lower.
4. The photosensitive composition according to any one of claim 1 to 3, wherein,
the glass transition temperature in the element A1 is 85 ℃ or higher.
5. The photosensitive composition according to any one of claims 1 to 4, which further satisfies the following condition B2,
requirement B2: the water content of the photosensitive layer after exposure obtained by the step X is more than 0 mass percent at 40 ℃ and 90% RH.
6. The photosensitive composition according to claim 5, wherein,
the water content in the element B2 is 0.5 mass% or more.
7. The photosensitive composition according to any one of claims 1 to 6, wherein,
the glass transition temperature in the element A1 is 100 ℃ or higher.
8. The photosensitive composition according to any one of claims 1 to 7, wherein,
the photosensitive composition comprises a compound A having an acid group,
the content of the acid groups in the photosensitive composition is reduced by irradiation with actinic rays or radiation.
9. The photosensitive composition according to any one of claims 1 to 8, wherein,
the photosensitive composition satisfies the following condition (V01) and any condition (W01),
requirement (V01)
The photosensitive composition comprises a compound A having an acid group and a compound beta having a structure in which the amount of the acid group contained in the compound A is reduced by exposure to light,
requirement (W01)
The photosensitive composition includes a compound a having an acid group, and the compound a further includes a structure in which the amount of the acid group is reduced by exposure.
10. The photosensitive composition according to claim 9, wherein,
In the requirement (V01), the compound beta is a compound B having a structure capable of accepting electrons from the acid group contained in the compound A in a photoexcited state,
in the element (W01), the structure is a structure capable of accepting electrons from the acid group in a photoexcited state.
11. The photosensitive composition according to claim 9 or 10, which satisfies the requirement (V01), and the compound beta is a compound B having a structure capable of accepting electrons from the acid group contained in the compound A in a photoexcited state,
in the photosensitive composition, the total number of the electron-accepting structures included in the compound B is 1 mol% or more with respect to the total number of the acid groups included in the compound a.
12. The photosensitive composition according to any one of claims 1 to 11, wherein,
the compound a includes a polymer having an acid group.
13. The photosensitive composition according to claim 12, wherein,
the polymer has a polymerizable group.
14. The photosensitive composition according to any one of claims 1 to 13, wherein,
the photosensitive composition further comprises a polymerizable compound.
15. The photosensitive composition according to any one of claims 1 to 14, wherein,
the photosensitive composition further comprises a photopolymerization initiator.
16. A transfer film, comprising:
temporary support: a kind of electronic device with high-pressure air-conditioning system
A photosensitive layer formed from the photosensitive composition of any one of claims 1 to 15.
17. A pattern forming method, comprising, in order:
a step of bringing the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film of claim 16 into contact with a substrate to bond the transfer film to the substrate;
exposing the photosensitive layer in a pattern; a kind of electronic device with high-pressure air-conditioning system
And developing the exposed photosensitive layer with an alkaline developer to form a pattern.
18. A method for manufacturing a circuit wiring includes, in order:
a step of bringing the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film of claim 16 into contact with the conductive layer in the substrate having a conductive layer, thereby bonding the transfer film to the substrate having a conductive layer;
exposing the photosensitive layer in a pattern;
developing the exposed photosensitive layer with an alkaline developer to form a patterned etching resist film; a kind of electronic device with high-pressure air-conditioning system
And a step of performing etching treatment on the conductive layer in a region where the etching resist film is not disposed.
19. A method for manufacturing a touch panel, which comprises the following steps in order:
a step of bringing the surface of the photosensitive layer on the side opposite to the temporary support side in the transfer film of claim 16 into contact with the conductive layer in the substrate having a conductive layer, thereby bonding the transfer film to the substrate having a conductive layer;
exposing the photosensitive layer in a pattern; a kind of electronic device with high-pressure air-conditioning system
And developing the exposed photosensitive layer with an alkaline developer to form a patterned protective film or insulating film of the conductive layer.
CN202280014728.2A 2021-02-26 2022-02-17 Photosensitive composition, transfer film, pattern forming method, circuit wiring manufacturing method, and touch panel manufacturing method Pending CN116888535A (en)

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JP2021-030620 2021-02-26
JP2021030620 2021-02-26
PCT/JP2022/006314 WO2022181431A1 (en) 2021-02-26 2022-02-17 Photosensitive composition, transfer film, pattern formation method, production method for circuit wiring, and production method for touch panel

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JP5387896B2 (en) * 2009-06-05 2014-01-15 日立化成株式会社 Photosensitive resin composition and photosensitive element using the same
JP5466522B2 (en) * 2010-02-08 2014-04-09 太陽ホールディングス株式会社 Photocurable resin composition, dry film and cured product thereof, and printed wiring board using them
JP5777461B2 (en) * 2011-09-14 2015-09-09 旭化成イーマテリアルズ株式会社 Photosensitive resin composition
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