CN116097171A - Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel - Google Patents

Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel Download PDF

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Publication number
CN116097171A
CN116097171A CN202180052348.3A CN202180052348A CN116097171A CN 116097171 A CN116097171 A CN 116097171A CN 202180052348 A CN202180052348 A CN 202180052348A CN 116097171 A CN116097171 A CN 116097171A
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resin layer
photosensitive resin
transfer material
photosensitive
layer
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松田知树
藤本进二
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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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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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  • 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)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention provides a photosensitive transfer material, a method for manufacturing a resin pattern using the photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel, wherein the photosensitive transfer material comprises: a temporary support; and a photocurable and photochromic photosensitive resin layer comprising an alkali-soluble polymer, an ethylenically unsaturated compound and a photopolymerization initiator, wherein the photosensitive resin layer has a layer thickness of 5 μm or less and is formed at 100mJ/cm by a high-pressure mercury lamp 2 When the photosensitive transfer material is exposed to light, the variation of the reflection concentration per unit thickness at the maximum absorption wavelength of the photosensitive transfer material in the range of 450nm to 800nm is 0.04 μm ‑1 The above.

Description

Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel
Technical Field
The invention relates to a photosensitive transfer material, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.
Background
In a display device (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 layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition portion, a peripheral wiring portion, and wiring of a lead-out wiring portion is provided inside the touch panel.
In general, in the formation of a patterned layer, the number of steps for obtaining a desired pattern shape is small, and therefore, the following method is widely used: the photosensitive transfer material is used to expose a layer of the photosensitive resin composition provided on an arbitrary substrate through a mask having a desired pattern, and then to develop the layer.
As a conventional photosensitive resin composition, a composition described in patent document 1 or patent document 2 is known.
Patent document 1 describes a photosensitive resin composition for forming protrusions for controlling the alignment of a liquid crystal display element, which contains a photopolymerization initiator, a polymerizable monomer, and a resin containing a crosslinkable group and an alkali-soluble group.
Patent document 2 describes a photosensitive resin composition comprising the following components:
(A) Alkali-soluble polymer,
(B) A compound having an olefinic double bond,
(C) Photopolymerization initiator
(D) The following general formula (I):
[ chemical formula 1]
Figure BDA0004092962780000021
{ in which R 1 ～R 4 Are respectively selected from hydrogen, alkyl and aromaticOne of the substituents of the group and the hetero atom. Wherein R is 1 Is a substituent that does not include a triarylimidazole structure. R is R 1 ～R 4 The two may be the same or different. And R is 3 、R 4 May be a condensed-cyclic compound present on the same ring. Compounds represented by }.
Patent document 1: japanese patent laid-open No. 2006-126478
Patent document 2: japanese patent application laid-open No. 2018-116146
Disclosure of Invention
Technical problem to be solved by the invention
An object of an embodiment of the present invention is to provide a photosensitive transfer material having excellent visibility and releasability.
Another object of the present invention is to provide a method for producing a resin pattern, a method for producing a circuit wiring, and a method for producing a touch panel, each of which uses the photosensitive transfer material.
Means for solving the technical problems
The following means are included in the method for solving the above-described problems.
<1>A photosensitive transfer material, comprising: a temporary support; and a photocurable and photochromic photosensitive resin layer containing an alkali-soluble polymer, an ethylenically unsaturated compound and a photopolymerization initiator, wherein the photosensitive resin layer has a layer thickness of 5 μm or less and is formed at 100mJ/cm by a high-pressure mercury lamp 2 When the photosensitive transfer material is exposed to light, the variation of the reflection concentration per unit thickness at the maximum absorption wavelength of the photosensitive transfer material in the range of 450nm to 800nm is 0.04 μm -1 The above.
<2> the photosensitive transfer material according to <1>, wherein,
the variation of the reflection concentration before and after exposure was 0.05 μm -1 The above.
<3> the photosensitive transfer material according to <1> or <2>, wherein,
the thickness of the photosensitive resin layer is 4 μm or less.
<4> the photosensitive transfer material according to any one of <1> to <3>, wherein,
the photopolymerization initiator contains a hexaarylbiimidazole compound.
<5> the photosensitive transfer material according to <4>, wherein,
the content of the hexaarylbiimidazole compound is 1 mass% or more relative to the total mass of the photosensitive resin layer.
<6> the photosensitive transfer material according to <4> or <5>, wherein,
the content of the hexaarylbiimidazole compound is 2 mass% or more relative to the total mass of the photosensitive resin layer.
<7> the photosensitive transfer material according to any one of <1> to <6>, wherein,
the photosensitive resin layer further contains a compound represented by the following formula (1).
[ chemical formula 2]
Figure BDA0004092962780000031
In the formula (1), R 1 ～R 6 Each independently represents an alkyl group having 1 to 6 carbon atoms.
<8> the photosensitive transfer material according to <7>, wherein,
the content of the compound represented by the formula (1) is 1 to 10% by mass based on the total mass of the photosensitive resin layer.
<9> the photosensitive transfer material according to <7> or <8>, wherein,
the content of the compound represented by the formula (1) is 1.5 to 10% by mass based on the total mass of the photosensitive resin layer.
<10> the photosensitive transfer material according to any one of <7> to <9>, wherein,
the content M of the photopolymerization initiator contained in the photosensitive resin layer A And the content M of the compound represented by the above formula (1) B Mass ratio M of (2) A /M B 0.3 to 5.0.
<11> a method for producing a resin pattern, comprising, in order: a step of bringing an outermost layer of the photosensitive transfer material according to any one of <1> to <10> on the side having the photosensitive resin layer with respect to the temporary support into contact with a substrate and bonding the outermost layer; a step of exposing the photosensitive resin layer to a pattern; and developing the exposed photosensitive resin layer to form a resin pattern.
<12> a method for manufacturing a circuit wiring, comprising, in order: a step of bonding the outermost layer of the photosensitive transfer material according to any one of <1> to <10> on the side having the photosensitive resin layer with respect to the temporary support, by contacting the outermost layer with a substrate having a conductive layer; a step of exposing the photosensitive resin layer to a pattern; developing the exposed photosensitive resin layer to form a resin pattern; and etching the substrate in the region where the resin pattern is not arranged.
<13> a method for manufacturing a touch panel, comprising, in order: a step of bonding the outermost layer of the photosensitive transfer material according to any one of <1> to <10> on the side having the photosensitive resin layer with respect to the temporary support, by contacting the outermost layer with a substrate having a conductive layer; a step of exposing the photosensitive resin layer to a pattern; developing the exposed photosensitive resin layer to form a resin pattern; and etching the substrate in the region where the resin pattern is not arranged.
Effects of the invention
According to an embodiment of the present invention, a photosensitive transfer material excellent in visibility and peelability can be provided.
Further, according to another embodiment of the present invention, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel using the photosensitive transfer material can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a layer structure of a photosensitive transfer material used in the present invention.
Fig. 2 is a schematic plan view showing the pattern a.
Fig. 3 is a schematic plan view showing a pattern B.
Detailed Description
The following describes the content of the present invention. In addition, although the description is made with reference to the drawings, the symbols may be omitted.
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 present specification, "(meth) acrylic acid" means either or both of acrylic acid and methacrylic acid, "(meth) acrylic acid ester" means either or both of acrylic acid ester and methacrylic acid ester, "(meth) acryl" means either or both of acryl and methacryl.
In the present specification, the amount of each component in the composition refers to the total amount of the corresponding plurality of substances present in the composition unless otherwise specified, in the case where a plurality of substances corresponding to each component are present in the composition.
In the present specification, the term "process" refers not only to an independent process but also to a process that is not clearly distinguished from other processes, if the desired purpose of the process is achieved.
In the labeling of groups (atomic groups) in the present specification, the label that is not labeled with a substituent and is unsubstituted includes a group having no substituent and a group having a substituent. For example, the term "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" in the present specification includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. The light used for exposure generally includes an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and activation rays (active energy rays) such as electron beams.
In addition, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.
In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are the molecular weights obtained as follows: the samples were measured by a Gel Permeation Chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSK gel G2000HxL (both trade names manufactured by TOSOH CORPORATION), and converted using a solvent THF (tetrahydrofuran) and a differential refractometer, and polystyrene was used as a standard substance.
(photosensitive transfer Material)
The photosensitive transfer material according to the present invention comprises: a temporary support; and a photocurable and photochromic photosensitive resin layer comprising an alkali-soluble polymer, an ethylenically unsaturated compound and a photopolymerization initiator, wherein the photosensitive resin layer has a layer thickness of 5 μm or less and is formed at 100mJ/cm by a high-pressure mercury lamp 2 When the photosensitive transfer material is exposed to light, the variation of the reflection concentration per unit thickness at the maximum absorption wavelength of the photosensitive transfer material in the range of 450nm to 800nm is 0.04 μm -1 The above.
As a result of the detailed study by the present inventors, the present inventors have found that it is difficult to achieve both visibility and resolution in a photosensitive transfer material having a conventional negative photosensitive resin layer as described in patent document 1, patent document 2, or the like. Specifically, the present inventors have found that, in the case where a large amount of a color former is added to a conventional negative photosensitive resin layer, for example, in order to improve visibility, the curing ratio of an ethylenically unsaturated compound is increased and the releasability is deteriorated.
In the photosensitive transfer material according to the present invention, the layer thickness of the photocurable and photochromic photosensitive resin layer is 5 μm or less, and 100mJ/cm is obtained by a high-pressure mercury lamp 2 When the photosensitive transfer material is exposed to light, the variation of the reflection concentration per unit thickness at the maximum absorption wavelength of the photosensitive transfer material in the range of 450nm to 800nm is 0.04 μm -1 As described above, it is estimated that the visibility is excellent, and that the thickness of the photosensitive resin layer is 5 μm or less, so that the penetration of the release liquid into the cured photosensitive resin layer is fast, and the releasability is excellent.
In the photosensitive transfer material according to the present invention, the transfer material was subjected to a high-pressure mercury lamp at a rate of 100mJ/cm 2 When the photosensitive transfer material is exposed to light, the variation of the reflection concentration per unit thickness at the maximum absorption wavelength of the photosensitive transfer material in the range of 450nm to 800nm is 0.04 μm -1 The above.
In the photosensitive transfer material according to the present invention, the change in the reflection density before and after exposure is preferably 0.05 μm from the viewpoints of visibility, releasability and resolution -1 The above is more preferably 0.05. Mu.m -1 ～0.2μm -1 Particularly preferably 0.07. Mu.m -1 ～0.15μm -1 。
The maximum absorption wavelength of the photosensitive transfer material in the range of 450nm to 800nm, more preferably in the range of 450nm to 750nm, still more preferably in the range of 500nm to 700nm, and particularly preferably in the range of 550nm to 650nm when the photosensitive transfer material is exposed to light with an exposure of 100mJ/cm2 by a high-pressure mercury lamp.
The maximum absorption wavelength of the photosensitive transfer material of the present invention in the range of 450nm to 800nm was measured by the following method.
The photosensitive transfer material was laminated on a copper-layer-equipped PET substrate having a copper layer of 200nm thickness produced by sputtering on a polyethylene terephthalate (PET) film of 100 μm thickness under lamination conditions of a roll temperature of 95℃and a line pressure of 0.9MPa and a line speed of 2.0 m/min. A high-pressure mercury lamp was used without peeling off the temporary support and the cumulative exposure at a wavelength of 365nm was set to 100mJ/cm 2 Is exposed to light of the amount of light. Reflectance at a wavelength of 450nm to 800nm was measured from a direction perpendicular to a surface direction of the photosensitive transfer material on the temporary support side using a reflectance spectrocolorimeter (cM-700d,Konica Minolta,Inc, manufactured by measuring diameter 3 mm. Phi., SCI mode), and a wavelength at which reflectance was smallest in the above wavelength range was set as a maximum absorption wavelength.
The change in the reflection concentration per unit thickness at the maximum absorption wavelength in the photosensitive transfer material of the present invention before and after exposure was measured by the following method.
Under the same conditions as described above, a photosensitive transfer material was laminated on the copper-layer-equipped PET substrate. The reflectance at the maximum absorption wavelength was measured from a direction perpendicular to the surface direction of the photosensitive transfer material on the temporary support side using a reflectance spectrocolorimeter (manufactured by cM-700d,Konica Minolta,Inc, measurement diameter 3 mm. Phi., SCI mode) without peeling the temporary support. Thereafter, the resultant exposure was set to 100mJ/cm at a wavelength of 365nm using a high-pressure mercury lamp 2 The light quantity of (C) was exposed, and the reflectance at the maximum absorption wavelength was measured again by using a reflection type spectrocolorimeter (CM-700d,Konica Minolta,Inc. Measurement diameter: 3 mm. Phi., SCI mode).
The reflectance before and after exposure was converted into reflectance concentration using the following formula, and the absolute value (Δo.d.) of the difference between the reflectance concentration before and after exposure (o.d.) was calculated, and the value obtained by dividing Δo.d. by the layer thickness (μm) of the photosensitive resin layer was obtained.
Reflection concentration (o.d.) = -log 10 (reflectivity)
The photosensitive transfer material according to the present invention comprises: a temporary support; and a photocurable and photochromic photosensitive resin layer containing an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.
In the photosensitive transfer material, the temporary support and the photosensitive resin layer may be directly laminated without other layers or may be laminated with other layers interposed therebetween. Further, another layer may be laminated on the surface of the photosensitive resin layer opposite to the surface facing the temporary support.
Examples of the other layers other than the temporary support and the photosensitive resin layer include a thermoplastic resin layer, an intermediate layer, and a protective film.
[ temporary support ]
The photosensitive transfer material used in the present invention has a temporary support.
The temporary support is a support that supports the photosensitive resin layer or a laminate including the photosensitive resin layer and is releasable.
The temporary support preferably has light transmittance from the viewpoint that exposure of the photosensitive resin layer via the temporary support can be performed when pattern exposure is performed on the photosensitive resin layer. In the present specification, "light-transmitting" means that the transmittance of light of a wavelength used for pattern exposure is 50% or more.
From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of light of a wavelength (more preferably, 365nm wavelength) used for pattern exposure of the temporary support is preferably 60% or more, more preferably 70% or more.
The transmittance of the layer included in the photosensitive transfer material is a ratio of the intensity of the light emitted from the layer when the light is incident in a direction perpendicular to the main surface of the layer (thickness direction) to the intensity of the incident light, and is measured using MCPD Series manufactured by Otsuka Flectronics co.
Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and from the viewpoints of strength, flexibility, and light transmittance, the resin film is preferable.
Examples of the resin film include polyethylene terephthalate (PET: polyethylene tere phthalate) film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.
The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of the strength as a support, flexibility required for bonding to the circuit wiring forming substrate, and light transmittance required in the initial exposure step.
The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, and particularly preferably in the range of 10 μm to 16 μm from the viewpoints of ease of handling and versatility.
Further, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, from the viewpoints of resolution and linearity in exposure through the support.
Further, it is preferable that the film used as the temporary support is free from deformation such as wrinkles, scratches, defects, and the like.
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, defects, precipitates, and the like contained in the temporary support be small. The number of particles, foreign matters, and defects having a diameter of 1 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 Hereinafter, it is particularly preferably 0/10 mm 2 。
Preferable modes of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of International publication No. 2012/081680, paragraphs 0029 to 0040 of International publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese patent application laid-open No. 2019-101405, the contents of which are incorporated herein by reference.
[ photosensitive resin layer ]
The photosensitive transfer material used in the present invention has a photosensitive resin layer.
The photosensitive resin layer is preferably a negative type photosensitive resin layer in which the solubility of the exposed portion in the developer is reduced by exposure and the non-exposed portion is removed by development.
The photosensitive resin layer contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator, and preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, a hexaarylbiimidazole compound, and a compound having a trityl structure described later, more preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, a hexaarylbiimidazole compound, and a compound represented by formula (1) described later, from the viewpoints of visibility, releasability, and resolution.
The photosensitive resin layer preferably contains an alkali-soluble polymer based on the total mass of the photosensitive resin layer: 10 to 90 mass percent; olefinically unsaturated compounds: 5 to 70 mass percent; photopolymerization initiator: 0.01 to 20 mass%.
The respective components will be described in order below.
< alkali-soluble Polymer >
The photosensitive resin layer contains an alkali-soluble polymer.
In the present specification, "alkali-soluble" means that the solubility in 100g of a 1 mass% aqueous solution of sodium carbonate is 0.1g or more at 22 ℃.
The alkali-soluble polymer is not particularly limited, and for example, a known alkali-soluble polymer used for an etching resist can be preferably used.
The alkali-soluble polymer is preferably a binder polymer.
The alkali-soluble polymer is preferably an alkali-soluble polymer having an acid group.
Among them, the alkali-soluble polymer a described below is preferable.
Polymer A-
The alkali-soluble polymer preferably contains a polymer a.
The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and even more preferably less than 190mgKOH/g, from the viewpoint of further excellent resolution by suppressing swelling of the photosensitive resin layer due to the developer.
The lower limit of the acid value of the polymer A is not particularly limited, but is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, particularly preferably 170mgKOH/g or more, from the viewpoint of further excellent developability.
The acid value was the mass [ mg ] of potassium hydroxide required for neutralization of 1g of the sample,
in the present specification, the unit is referred to as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
The acid value of the polymer a may be adjusted according to the type of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.
The weight average molecular weight of polymer a is preferably 5,000 ～ 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge meltability and chipping property when the photosensitive resin laminate is produced, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge meltability means the ease with which the photosensitive resin layer overflows from the end surface of the roller when the photosensitive transfer material is wound into a roll shape. The chipability refers to the degree of difficulty in chipping when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, the chips are transferred to a mask in a subsequent exposure step or the like, and cause defective products. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, still more preferably 1.0 to 3.0. In the present invention, the molecular weight is a value measured by gel permeation chromatography. And the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
From the viewpoint of suppressing the line width from becoming thicker or the resolution from deteriorating when the focus position is shifted during exposure, the photosensitive resin layer preferably contains a monomer component having an aromatic hydrocarbon as the polymer a. Examples of such aromatic hydrocarbons include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content ratio of the monomer component having an aromatic hydrocarbon in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more, based on the total mass of the total monomer components. The upper limit is not particularly limited, but is preferably 95 mass% or less, more preferably 85 mass% or less. The content of the monomer component having aromatic hydrocarbon when the plurality of polymers a are contained was determined as a weight average value.
Examples of the monomer having an aromatic hydrocarbon include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, a styrene dimer, a styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is styrene, the content of the styrene monomer component is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of the total monomer components.
Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.
Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group, for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like; vinyl monomers having a benzyl group, for example, vinylbenzyl chloride, vinylbenzyl alcohol, and the like. Among them, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is benzyl (meth) acrylate, the content of the benzyl (meth) acrylate monomer component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of the total monomer components.
The polymer a containing a monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon with at least 1 of the first monomers described later and/or at least 1 of the second monomers described later.
The polymer a containing no monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing at least 1 kind of a first monomer described later, more preferably by copolymerizing at least 1 kind of the first monomer with at least 1 kind of a second monomer described later.
The first monomer is a monomer having a carboxyl group in a molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is preferable.
The content of the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of the total monomer components.
The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of the total monomer components. The copolymerization ratio is preferably 10 mass% or more, more preferably 15 mass% or more, and even more preferably 20 mass% or more from the viewpoint of exhibiting good developability, controlling edge meltability, and the like. The copolymerization ratio is preferably 50 mass% or less from the viewpoint of high resolution of the resist pattern and the curl shape, and more preferably 35 mass% or less, further preferably 30 mass% or less, particularly preferably 27 mass% or less from the viewpoint of chemical resistance of the resist pattern.
The second monomer is a non-acidic monomer having at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth) acrylonitrile, etc. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable.
The content of the second monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass, based on the total mass of the total monomer components.
From the viewpoint of suppressing the line width thickening or the deterioration of resolution at the time of focus position shift at the time of exposure, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.
In one embodiment, the polymer a preferably contains 25 to 40% by mass of a monomer component having an aromatic hydrocarbon, 20 to 35% by mass of a first monomer component, and 30 to 45% by mass of a second monomer component. In another embodiment, the polymer preferably contains 70 to 90 mass% of the monomer component having an aromatic hydrocarbon and 10 to 25 mass% of the first monomer component.
The polymer a may have any one of a linear structure, a branched structure, and an alicyclic structure in a side chain. The branched structure or alicyclic structure can be introduced into the side chain of the polymer a by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. The group having an alicyclic structure may be monocyclic or polycyclic.
Specific examples of the monomer having a group with a branched structure in the side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl methacrylate are preferable, and isopropyl methacrylate or t-butyl methacrylate is more preferable.
Specific examples of the monomer having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms is exemplified. More specific examples thereof include (meth) acrylic acid (bicyclo [ 2.2.1] heptyl-2) ester, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyl adamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) acrylate, 3, 5-methyl-5-ethyl-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) acrylate, 1-menthyl (meth) acrylate 3-hydroxy-2, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Among these (meth) acrylic esters, cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecane (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is more preferable.
The polymer a may be used alone or in combination of 2 or more. When 2 or more kinds of polymers are used in combination, it is preferable to use 2 kinds of polymers a containing a monomer component having an aromatic hydrocarbon in combination, or to use a polymer a containing a monomer component having an aromatic hydrocarbon in combination with a polymer a not containing a monomer component having an aromatic hydrocarbon. In the latter case, the ratio of the polymer a containing the monomer component having an aromatic hydrocarbon to be used is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, relative to the whole of the polymer a.
Regarding the synthesis of polymer a, it is preferable to proceed as follows: to a solution obtained by diluting one or more of the above-described monomers with a solvent such as acetone, methyl ethyl ketone, isopropyl alcohol, etc., a proper amount of a radical polymerization initiator such as benzoyl peroxide, azoisobutyronitrile, etc., is added, and heating and stirring are performed. In some cases, synthesis may be performed while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, in addition to the solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.
The glass transition temperature Tg of the polymer A is preferably 30℃or more and 180℃or less. By using the polymer a having Tg of 180 ℃ or less in the photosensitive resin layer, it is possible to suppress the line width from becoming thicker or the resolution from deteriorating when the focus position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 180℃or lower, still more preferably 170℃or lower, and particularly preferably 160℃or lower. Further, from the viewpoint of improving the edge melting resistance, it is preferable to use the polymer a having Tg of 30 ℃ or higher. From this viewpoint, the Tg of the polymer A is more preferably 40℃or higher, still more preferably 50℃or higher, particularly preferably 60℃or higher, and most preferably 70℃or higher.
The photosensitive resin layer may contain a resin other than an alkali-soluble polymer.
Examples of the resin other than the alkali-soluble polymer include acrylic resins, styrene-acrylic copolymers (copolymers having a styrene content of 40 mass% or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
The alkali-soluble polymer may be used alone or in combination of 2 or more kinds.
The proportion of the alkali-soluble polymer to the total mass of the photosensitive resin layer is preferably in the range of 10 to 90 mass%, more preferably 30 to 70 mass%, and even more preferably 40 to 60 mass%. From the viewpoint of controlling the development time, the proportion of the alkali-soluble polymer to the photosensitive resin layer is preferably 90 mass% or less. On the other hand, from the viewpoint of improving the edge melting resistance, the ratio of the alkali-soluble polymer to the photosensitive resin layer is preferably 10 mass% or more.
(ethylenically unsaturated Compound)
The photosensitive resin layer contains an ethylenically unsaturated compound.
In the present specification, the term "ethylenically unsaturated compound" means a compound that is polymerized by the action of a photopolymerization initiator described later, and is a compound different from the alkali-soluble polymer described above.
As the ethylenically unsaturated compound, an ethylenically unsaturated compound is preferable.
The ethylenically unsaturated compound is a component contributing to photosensitivity (i.e., photocurability) of the negative photosensitive resin layer and strength of the cured film.
The ethylenically unsaturated compound is a compound having 1 or more ethylenically unsaturated groups.
The photosensitive resin layer preferably contains an ethylenically unsaturated compound having 2 or more functions.
The ethylenically unsaturated compound having 2 or more functions herein means a compound having 2 or more ethylenically unsaturated groups in 1 molecule.
As the ethylenically unsaturated group, (meth) acryl is more preferable.
As the ethylenically unsaturated compound, (meth) acrylate compounds are preferred.
The photosensitive resin layer preferably contains an ethylenically unsaturated compound having a polymerizable group.
The polymerizable group of the ethylenically unsaturated compound is not particularly limited as long as it is a group involved in polymerization reaction, and examples thereof include a group having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group; and a group having a cationically polymerizable group such as an epoxy group and an oxetanyl group.
The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group.
The ethylenically unsaturated compound is preferably a compound having 2 or more ethylenically unsaturated groups in 1 molecule (polyfunctional ethylenically unsaturated compound) from the viewpoint of more excellent photosensitivity of the photosensitive resin layer.
Further, from the viewpoint of further excellent resolution and releasability, the number of the ethylenically unsaturated groups in 1 molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and still more preferably 2 or less.
From the viewpoint of more excellent balance of photosensitivity, resolution and releasability of the photosensitive resin layer, the photosensitive resin layer preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in 1 molecule, more preferably contains a 2-functional ethylenically unsaturated compound having 2 ethylenically unsaturated groups in 1 molecule.
From the viewpoint of excellent releasability, the content of the 2-functional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60 mass% or more, more preferably more than 70 mass%, and still more preferably 90 mass% or more with respect to the content of the ethylenically unsaturated compound. The upper limit is not particularly limited, and may be 100 mass%. That is, all of the ethylenically unsaturated compounds contained in the photosensitive resin layer may be 2-functional ethylenically unsaturated compounds.
Further, as the ethylenically unsaturated compound, (meth) acrylate compounds having a (meth) acryloyl group as a polymerizable group are preferable.
Olefinically unsaturated compounds B1-
The photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and 2 ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in 1 molecule among the above ethylenically unsaturated compounds.
From the viewpoint of more excellent resolution, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 55 mass% or more, and particularly preferably 60 mass% or more. The upper limit is not particularly limited, but is preferably 99 mass% or less, more preferably 95 mass% or less, further preferably 90 mass% or less, and particularly preferably 85 mass% or less from the viewpoint of releasability.
Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferable, and benzene ring is more preferable. The aromatic ring may have a substituent.
The ethylenically unsaturated compound B1 may have only 1 aromatic ring or may have 2 or more aromatic rings.
The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive resin layer due to the developer.
Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and a bisphenol a structure is preferable.
Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure.
The bisphenol structure may be directly bonded to both ends of 2 polymerizable groups, or may be bonded to each other through 1 or more alkylene oxide groups. As the alkylene oxide group added to both ends of the bisphenol structure, ethylene oxide group or propylene oxide group is preferable, and ethylene oxide group is more preferable. The number of alkylene oxide groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule.
The olefinically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated into the present specification.
As the ethylenically unsaturated compound B1, a 2-functional ethylenically unsaturated compound having a bisphenol a structure is preferable, and 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.
Examples of the 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitac hi Chemical Co, ltd.) propane, 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecyloxypropoxy) phenyl) propane (manufactured by FA-3200MY,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxypentadecoxy) phenyl) propane (BPE-1300, shin-Nak amura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical, manufactured by NK-37co.), and bis (10, ltd.) acrylate (manufactured by ltd.) and bis (10, ltd.) acrylate.
As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.
[ chemical formula 3]
Figure BDA0004092962780000181
In the formula (Bis), R 1 R is R 2 Each independently represents a hydrogen atom or a methyl group, A is C 2 H 4 B is C 3 H 6 ，n 1 N is as follows 3 Each independently is an integer of 1 to 39 and n 1 +n 3 Is an integer of 2 to 40, n 2 N is as follows 4 Each independently is an integer of 0 to 29 and n 2 +n 4 The repeating units of- (A-O) -and- (B-O) -may be arranged in a random or block form, and are integers of 0 to 30. Also, in the case of the block, either one of- (A-O) -and- (B-O) -may be on the bisphenol structure side.
In one aspect, n 1 +n 2 +n 3 +n 4 PreferablyAn integer of 2 to 20, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 12. And n is 2 +n 4 Preferably an integer of 0 to 10, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2, and particularly preferably 0.
The ethylenically unsaturated compound B1 may be used alone or in combination of 2 or more.
From the viewpoint of further excellent resolution, the content of the ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 70 mass% or less, more preferably 60 mass% or less, from the viewpoints of transferability and edge melting (a phenomenon in which components in the photosensitive resin layer bleed out from the end portion of the photosensitive transfer material).
The photosensitive resin layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1.
The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited, and may be appropriately selected from known compounds. Examples thereof include compounds having 1 ethylenically unsaturated group in 1 molecule (monofunctional ethylenically unsaturated compounds), 2-functional ethylenically unsaturated compounds having no aromatic ring, and ethylenically unsaturated compounds having 3 or more functions.
Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.
Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
Examples of alkylene glycol di (meth) acrylates 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.), 1, 6-hexanediol diacrylate (A-HD-N, shin-Nakamura Chemical Co., ltd.), ethylene glycol dimethacrylate, 1, 10-decane diol diacrylate and neopentyl glycol di (meth) acrylate.
Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
Examples of urethane di (meth) acrylates include propylene oxide modified urethane di (meth) acrylates and ethylene oxide and propylene oxide modified urethane di (meth) acrylates. Examples of the commercial products include 8UX-015A (Taisei Line Chemic al Co., ltd.), UA-32P (Shin-Nakamura Chemical Co., ltd.), and UA-11OOH (Shin-Nakamura Chemical Co., ltd.).
Examples of the ethylenically unsaturated 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, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof.
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. In one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 3 or more functional ethylenically unsaturated compounds, and more preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 2 or more ethylenically unsaturated compounds 3 or more functional ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the ethylenically unsaturated compound having 3 or more functions is preferably (total mass of the ethylenically unsaturated compounds B1): (total mass of the ethylenically unsaturated compounds having 3 or more functions) =1:1 to 5:1, more preferably 1.2:1 to 4:1, still more preferably 1.5:1 to 3:1.
In one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and 2 or more kinds of 3-functional ethylenically unsaturated compounds.
Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical Co., ltd., A-9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD RP-1040, shin-Nakamura Chemical Co., ltd., ATM-35E and A-9300, DAICEL-ALLNEXLTD, EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., ltd., A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (AGOSEI CO., LTD. Etc.), ARONIX M-520 (AGOSEI CO., LTD. TOOSEI. CO., LTD. TOEI. 510).
Further, as the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, the ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of japanese unexamined patent publication No. 2004-239942 can be used.
From the viewpoints of resolution and linearity, the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound to the content Mb of the alkali-soluble polymer in the photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 to 0.9.
Further, from the viewpoint of curability and resolution, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth) acryloxy compound.
Further, from the viewpoints of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive resin layer more preferably contains a (meth) acryloyloxy compound, and the content of the acryloyloxy compound is 60 mass% or less relative to the total mass of the (meth) acryloyloxy compound contained in the photosensitive resin layer.
The molecular weight (weight average molecular weight (Mw) in the case of having a distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.
The ethylenically unsaturated compound may be used alone or in combination of at least 2 kinds.
The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.
< photopolymerization initiator >
The photosensitive resin layer contains a photopolymerization initiator.
The photopolymerization initiator is a compound that starts polymerization of an ethylenically unsaturated compound upon receiving activation light such as ultraviolet light, visible light, or X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.
Examples of the photo-radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a hexaarylbiimidazole compound.
Among them, the photopolymerization initiator preferably contains a hexaarylbiimidazole compound, more preferably contains a hexaarylbiimidazole compound and a compound represented by the following formula (1) from the viewpoints of visibility, releasability and resolution.
Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.
The content of the hexaarylbiimidazole compound is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 2 to 10 mass%, and particularly preferably 2 to 7 mass% relative to the total mass of the photosensitive resin layer, from the viewpoints of visibility, releasability, and resolution.
As the photo radical polymerization initiator, for example, those described in paragraphs 0031 to 0042 of JP 2011-95716 and 0064 to 0081 of JP 2015-14783 can be used.
Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p ' -dimethoxybenzyl) anisyl ester, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF corporation), omnirad651 and 369 (trade name: IGM Resins B.V. Co., ltd.), and 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bisimidazole (Tokyo Chemical Industry Co., ltd.).
Examples of the commercially available photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (o-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG,IGM Resins B.V. Manufactured by Omni), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: omni 907,IGM Resins B.V. Manufactured by Omni 907,IGM Resins B.V), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropoyl) benzyl ] phenyl } -2-methylpropanene (trade name: omni-4-morpholino-1-butanone (trade name: omni-3, manufactured by Omni-4-morpholino) phenyl ] -1-butanone (trade name: omni 3, manufactured by Omni-4-methylphenyl) methyl ] -1-butanone, IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: omnirad 1173,IGM Resins B.V), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184,IGM Resins B.V, manufactured) 2, 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad651,IGM Resins B.V, manufactured), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (trade name: omnirad TPOH, IGM Resins b.v.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819,IGM Resins B.V), oxime ester-based photopolymerization initiator (trade name: lunar 6,DKSH Holding Ltd), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, hampford Co., ltd.) and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (Tokyo Chemical Industry Co., ltd.).
The photo cation polymerization initiator (photoacid generator) is a compound that receives activating light to generate an acid. The photo cation polymerization initiator is preferably a compound which generates an acid in response to an activating light having a wavelength of 300nm or more, preferably 300 to 450nm, but the chemical structure thereof is not limited. The photo cation polymerization initiator which does not directly induce the activating light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by inducing the activating light having a wavelength of 300nm or more by being used in combination with the sensitizer.
The photo-cation polymerization initiator is preferably a photo-cation polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, and is preferably-10.0 or more, for example.
Examples of the photo-cationic polymerization initiator include an ionic photo-cationic polymerization initiator and a nonionic photo-cationic polymerization initiator.
Examples of the ionic photo-cation polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photo-cation polymerization initiator, the ionic photo-cation polymerization initiator described in paragraphs 0114 to 0133 of Japanese unexamined patent publication No. 2014-85643 can be used.
Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-s-triazine, diazomethane compound and imide sulfonate compound, those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494 can be used. Further, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be used.
The photosensitive resin layer preferably contains a photo radical polymerization initiator, and more preferably contains at least 1 selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives thereof.
The photosensitive resin layer may contain 1 kind of photopolymerization initiator alone or 2 or more kinds of photopolymerization initiators.
The content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1.0 mass% or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10 mass% or less, more preferably 5 mass% or less, relative to the total mass of the photosensitive resin layer.
< pigment >
The photosensitive resin layer preferably contains a dye, and more preferably contains a dye having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm at the time of color development and a maximum absorption wavelength that changes by an acid, an alkali or a radical (also simply referred to as "dye N") from the viewpoints of visibility of an exposed portion and a non-exposed portion, visibility of a pattern after development, and resolution. When pigment N is contained, although the detailed mechanism is not clear, the adhesion to the adjacent layers (for example, the temporary support and the intermediate layer) is improved, and the resolution is further excellent.
In the present specification, the "dye whose wavelength is greatly changed by an acid, a base, or a radical" may refer to any one of a method in which a dye in a color-developed state is decolorized by an acid, a base, or a radical, a method in which a dye in a decolorized state is developed by an acid, a base, or a radical, and a method in which a dye in a color-developed state is changed to a color-developed state of another hue.
Specifically, the dye N may be a compound that changes color from a decolored state by exposure, or may be a compound that changes color from a decolored state by exposure. In this case, the coloring matter may be a coloring matter which changes the state of color development or decoloration by generating an acid, an alkali or a radical in the photosensitive resin layer by exposure, or may be a coloring matter which changes the state (for example, pH) in the photosensitive resin layer by an acid, an alkali or a radical, and changes the state of color development or decoloration. Further, the coloring matter may be a coloring matter which is directly subjected to an acid, an alkali or a radical as a stimulus without exposure to light, thereby changing the state of color development or decoloration.
Among them, from the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.
From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive resin layer preferably contains a dye whose maximum absorption wavelength is changed by radicals as both the dye N and the photo radical polymerization initiator.
Further, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, an alkali, or a radical.
Examples of the coloring mechanism of the coloring matter N in the present invention include the following: a photo radical polymerization initiator, a photo cation polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive resin layer, and a radical reactive pigment, an acid reactive pigment or a base reactive pigment (for example, a leuco pigment) develops color by radicals, acids or bases generated by the photo radical polymerization initiator, the photo cation polymerization initiator or the photobase generator after exposure.
The maximum absorption wavelength at the wavelength range of 400nm to 780nm at the time of color development of the dye N is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion.
The dye N may have only a maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of 1 color development, or may have 2 or more. When the dye N has a maximum absorption wavelength in the wavelength range of 40Onm to 780nm at the time of color development of 2 or more, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.
The maximum absorption wavelength of pigment N is obtained by: under atmospheric ambient gas, a spectrophotometer was used: UV3100 (manufactured by Shimadzu Corporation), the transmission spectrum of a solution containing pigment N (liquid temperature: 25 ℃ C.) was measured in a range of 400nm to 780nm, and the wavelength at which the intensity of light became extremely small (maximum absorption wavelength) was detected.
Examples of the coloring matter which is colored or decolored by exposure to light include colorless compounds.
Examples of the coloring matter to be decolorized by exposure to light include colorless compounds, diarylmethane-based coloring matters, oxazine-based coloring matters, xanthene-based coloring matters, iminonaphthoquinone-based coloring matters, azomethine-based coloring matters, and anthraquinone-based coloring matters.
The coloring matter N is preferably a colorless compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.
Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolyl phthalide skeleton (indolyl phthalide-based dye), and a colorless compound having a colorless gold amine skeleton (colorless gold amine-based dye).
Among them, triarylmethane-based pigments or fluoran-based pigments are preferable, and colorless compounds having a triphenylmethane skeleton (triphenylmethane-based pigments) or fluoran-based pigments are more preferable.
The colorless compound is preferably a lactone ring, a sultone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator, whereby the colorless compound is decolorized by changing to a closed-loop state or the colorless compound is decolorized by changing to an open-loop state. As the colorless compound, a compound having a lactone ring, a sultone ring, or a sultone ring and the lactone ring, the sultone ring, or the sultone ring is colored by free radical or acid ring opening is preferable, and a compound having a lactone ring and the lactone ring is colored by free radical or acid ring opening is more preferable.
Examples of the dye N include the following dyes and colorless compounds.
Specific examples of the dye in pigment N include brilliant green (briliant green), ethyl violet, methyl green, crystal violet, basic fuchsine (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal, metandil yellow (metandil yellow), thymolphthalein (thymol sulfonphthalein), xylenol (xylenol) blue, methyl orange, para-methyl red, congo red, benzopurphine (benzopurphine) 4B, alpha-naphthalene red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), parapin red (parafuchsin), victoria pure blue (victoria pure blue) -naphthalene sulfonate, victoria pure blue BOH (Hodogaya Chemical co., ltd, manufactured), oil blue #603 (0 rient Chemical Industries Co, ltd, manufactured), oil pink #312 (Orient Chemical Industries co, ltd, manufactured), oil red 5B (Orient Chemical Industries co, ltd, manufactured), oil scarlet (oil scarlet) #308 (Orient Chemical Industries co, ltd, manufactured), oil red OG (Orient Chemical Indu stries co, ltd, manufactured), oil red RR (Orient Chemical Industries co, ltd, manufactured), oil green #502 (0 rient Chemical Industries Co, ltd, manufactured), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co, ltd, manufactured), meta-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, gold amine, 4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxystearyl amino-4-p-N, n-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-beta-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.
Specific examples of the colorless compound in the dye N include p, p', p "-hexamethyltriphenylamine methane (colorless crystal violet), pergascript Blue SRB (Ciba-Geigy Co.), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidinyl) fluoran, 3, 6-dimethoxy fluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylanilino fluoran, 3- (N, N-diethylamino) -6-chloro-7-methylanilino-fluoran, 3- (N, N-diethylamino) -6-methyl-7-anilino-fluoran, 3- (N-dimethylamino) -fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino-fluoran, 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-dimethylanilinofluoran, 3-hydropyridyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-ethyl-2-methylindol-3-yl) phthalide, 3- (1-ethyl-2-methylindol-3-yl) phthalide, 6 '-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.
The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and more preferably a dye which develops color by radicals, from the viewpoints of visibility of the exposed portion and the non-exposed portion, visibility of the pattern after development, and resolution.
As pigment N, preference is given to leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate.
Further, from the viewpoints of visibility, releasability, and resolution, the photosensitive resin layer preferably contains a compound having a trityl structure (also referred to as a "triarylmethane structure").
The compound having a trityl structure preferably has 1 or more electron donating groups on the aryl groups in the trityl structure, more preferably 1 or more electron donating groups on the 3 aryl groups in the trityl structure, and particularly preferably electron donating groups on the p-position of the 3 aryl groups in the trityl structure, from the viewpoints of visibility, releasability and resolution.
The electron donating group is preferably an alkoxy group or an unsubstituted, mono-or di-substituted amino group, more preferably an unsubstituted, mono-or di-substituted amino group, and particularly preferably a dialkylamino group, from the viewpoints of visibility, releasability, and resolution. The alkyl group of the dialkylamino group is preferably an alkyl group having 1 to 6 carbon atoms.
Among them, the photosensitive resin layer preferably contains a compound represented by the following formula (1) from the viewpoints of visibility, releasability and resolution.
[ chemical formula 4]
Figure BDA0004092962780000271
In the formula (1), R 1 ～R 6 Each independently represents an alkyl group having 1 to 6 carbon atoms.
R in formula (1) 1 ～R 6 Each independently is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
The content of the compound represented by the formula (1) is preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass, even more preferably 1.5 to 10% by mass, and particularly preferably 1.5 to 5% by mass, based on the total mass of the photosensitive resin layer, from the viewpoints of visibility, releasability, and resolution.
From the viewpoints of visibility, releasability, and resolution, the content M of the photopolymerization initiator contained in the photosensitive resin layer A And the content M of the compound represented by the above formula (1) B Mass ratio M of (2) A /M B Preferably from 0.2 to 7.0, more preferably from 0.3 to 5.0, even more preferably from 0.5 to 4.0, particularly preferably from 0.7 to 3.5.
In addition, from the viewpoints of visibility, releasability, and resolution, the content M of the hexaarylbisimidazole compound contained in the photosensitive resin layer is Abi And the content M of the compound represented by the above formula (1) B Mass ratio M of (2) Abi /M B Preferably from 0.2 to 7.0, more preferably from 0.3 to 5.0, even more preferably from 0.5 to 4.0, particularly preferably from 0.7 to 3.5.
The pigment may be used alone or in combination of 1 or more than 2.
The content of the coloring matter is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, and even more preferably 0.1 mass% to 5 mass% with respect to the total mass of the photosensitive resin layer, from the viewpoints of visibility of the exposed portion and the non-exposed portion, visibility of the pattern after development, and resolution.
The content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, and even more preferably 0.1 mass% to 5 mass% with respect to the total mass of the photosensitive resin layer, from the viewpoints of visibility of the exposed portion and the non-exposed portion, visibility of the pattern after development, and resolution.
The content of the dye N is the content of the dye when all the dye N contained in the photosensitive resin layer is in a color development state. Hereinafter, a method for determining the content of the dye N will be described by taking a dye that develops color by a radical as an example.
2 solutions were prepared in which 0.001g or 0.01g of pigment was dissolved in 100mL of methyl ethyl ketone. To each of the obtained solutions, irgacure OXE01 (trade name, BASF Jap an ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated, thereby generating radicals to bring all the pigments into a color-developed state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under atmospheric air using a spectrophotometer (manufactured by UV3100, shimadzu Corpora tion), and a calibration curve was prepared.
Next, absorbance of the solution in which all the pigments were colored was measured in the same manner as described above, except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive resin layer was calculated based on the calibration curve from the absorbance of the obtained solution containing the photosensitive resin layer.
< other ingredients >
The photosensitive resin layer may contain components other than the alkali-soluble polymer, the ethylenically unsaturated compound, the photopolymerization initiator, and the pigment.
Surfactant-containing compositions
From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (Nonion) surfactants, and amphoteric surfactants. The surfactant is preferably a nonionic surfactant. The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant.
Examples of the commercial products of the fluorine-based surfactant include MEGAFAC (for example, 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, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21, DIC Corporation), FLUORAD (for example, FC430, FC431 and FC171, sumitomo 3M Limited), SURFLON (e.g., S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40, AGC Inc.), polyFox (e.g., PF636, PF656, PF6320, PF6520 and PF7002, OMNOVA Solutions Inc.) and FTERGENT (e.g., 710FM, 610FM, 601AD, 601ADH2, 602A, 215M and 245F, made by Neos Corporation).
Examples of the "programs" include EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603 (DIC Co-registration, supra), FTERGENT 710FL, 683 (Neos Corporation), and U-120E (Uni-chem Corporation).
As the fluorine-based surfactant, an acrylic compound having a molecular structure including a functional group containing a fluorine atom and having a portion of the functional group containing a fluorine atom broken at the time of heating so that the fluorine atom volatilizes may be used. Examples of the above-mentioned fluorine-based surfactant include MEGAFA CE DS series (chemical industry journal of date (2016, 2, 22 days) and daily industrial news (2016, 2, 23 days) manufactured by DIC Corporation, for example, 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 having a fluorinated alkyl group or a fluorinated alkylene ether group can also be used.
Block polymers may also be used as the fluorine-based surfactant.
As the fluorine-based surfactant, a fluorine-containing polymer compound including a structural unit derived from a (meth) acrylate compound containing a fluorine atom and a structural unit derived from a (meth) acrylate compound containing 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) may be used.
As the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain can also be used. As the above-mentioned commercial products of the fluorine-based surfactant, MEGAFAC (for example, RS-101, RS-102, RS-718K and RS-72-K, manufactured by DIC Corporation) can be cited.
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), from the viewpoint of improving environmental suitability.
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates (for example, glycerin ethoxylate) and propoxylates (for example, glycerin propoxylate) thereof. Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC (for example, L10, L31, L61, L62, 10R5, 17R2 and 25R2, manufactured by BASF), TETRONIC (for example, 304, 701, 704, 901, 904 and 150R1 manufactured by BASF), SOLSPERSE 20000 (manufactured by The Lubrinzol corporation), NCW-101 (manufactured by FUJIFILM Wako Pure Chemical Corporation), NCW-1001 (manufactured by FUJIFILM Wako Pure Chemical Corporation), NCW-1002 (manufactured by FUJIFILM Wako Pure Che mical Corporation), PIONIN (for example, D-6112-W and D-6315, take moto Oil & Fat Co., manufactured by Ltd.), OLN EE1010 (manufactured by Nissin Chemical Co., ltd.) and SUYNOL (for example, 104, 400 and Chemical Co., manufactured by RFTd. Co., ltd.).
Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminal ends.
Examples of the surfactant include DOWSIL8032 ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC11PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicon e SH30PA, and Toray Silicone SH8400 (Dow Corning Toray Co., ltd.).
Specific examples of the silicone surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (manufactured by DIC Corporation).
Examples of the surfactant include X-22-4952, X-22-4272, X-22-6266, KF-351A, K, L, KF-355, A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-626, KP-621, KP-652 (above), shin-Etsu Co., ltd.
Examples of the surfactant include F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive performance Materials Inc.).
Examples of the surfactant include BYK307, BYK323, BYK330, BYK300, BYK306, BYK310, BYK320, BYK325, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (above, BYK co., LTD).
The photosensitive resin layer may contain 1 or 2 or more surfactants.
The content of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, based on the total mass of the photosensitive resin layer.
Additive-
The photosensitive resin layer may contain a known additive as required in addition to the above components.
Examples of the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a benzotriazole, a carboxybenzotriazole, and a solvent. The photosensitive resin layer may contain 1 kind of each additive alone or 2 or more kinds of additives.
The photosensitive resin layer may contain a radical inhibitor.
Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenyl hydroxylamine aluminum salt, and diphenyl nitrosoamine. In order not to impair the sensitivity of the photosensitive resin layer, nitrosophenyl hydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor.
Examples of the benzotriazoles include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.
Examples of carboxybenzotriazoles include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. As the carboxybenzotriazoles, for example, commercially available products such as CBT-1 (JOHOKU CHEMICAL co., ltd., trade name) can be used.
When the total mass of the photosensitive resin layer is 100% by mass, the total content of the radical polymerization inhibitor, the benzotriazole and the carboxybenzotriazole is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass. The content is preferably 0.01 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin layer. On the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, the content is preferably 3 mass% or less.
The photosensitive resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone (xanthone) compound, a thioxanthone (thioxanthone) compound, an acridone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (e.g., 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.
The photosensitive resin layer may contain 1 sensitizer alone or 2 or more sensitizers.
When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing speed by balancing the polymerization speed and chain transfer, the content is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% with respect to the total mass of the photosensitive resin layer.
The photosensitive resin layer may contain at least 1 selected from plasticizers and heterocyclic compounds.
Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International publication No. 2018/179640.
The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from the photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.
The photosensitive resin layer may contain known additives such as metal oxide particles, antioxidants, dispersants, acid-proliferation agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents.
The additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643, the contents of which are incorporated herein by reference.
< physical Properties etc.)
The layer thickness of the photosensitive resin layer is 5 μm or less, preferably less than 5 μm, more preferably 4 μm or less, further preferably 1 μm or more and 4 μm or less, and particularly preferably 2 μm or more and 4 μm or less from the viewpoints of visibility, releasability and resolution.
The layer thicknesses of the layers included in the photosensitive transfer material were measured as follows: a cross section in a direction perpendicular to the main surface of the photosensitive transfer material was observed by a scanning electron microscope (SEM: scanning Flectron Microscope), and the thickness of each layer was measured at 10 points or more based on the obtained observation image, and the average value was calculated.
Further, from the viewpoint of further excellent adhesion, the light transmittance of the photosensitive resin layer at 365nm is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.
< method of Forming >
The method for forming the photosensitive resin layer is not particularly limited as long as the layer containing the above components can be formed.
As a method for forming the photosensitive resin layer, for example, the following methods are mentioned: a photosensitive resin composition containing an alkali-soluble polymer, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, and the like is prepared, and the photosensitive resin composition is applied to a surface of a temporary support or the like, and a coating film of the photosensitive resin composition is dried to form the photosensitive resin composition.
Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing an alkali-soluble polymer, an ethylenically unsaturated compound, a photopolymerization initiator, any of the above components, and a solvent.
In order to adjust the viscosity of the photosensitive resin composition and facilitate formation of the photosensitive resin layer, the photosensitive resin composition preferably contains a solvent.
Solvent-
The solvent contained in the photosensitive resin composition is not particularly limited as long as it is a solvent capable of dissolving or dispersing the alkali-soluble polymer, the ethylenically unsaturated compound, the photopolymerization initiator, and any of the above components, and a known solvent can be used.
Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing 2 or more of these solvents.
In the case of producing a photosensitive transfer material including a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these, a mixed solvent containing at least 1 selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 selected from a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least 3 selected from at least 1 selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent is still more preferable.
Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.
Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
As the solvent, a solvent described in paragraphs 0092 to 0094 of international publication No. 2018/179640 and a solvent described in paragraph 0014 of japanese patent application laid-open No. 2018-177889, which are incorporated herein by reference, can be used.
The photosensitive resin composition may contain 1 kind of solvent alone or 2 or more kinds of solvents.
The content of the solvent in coating the photosensitive resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.
The method for producing the photosensitive resin composition is not particularly limited, and the following methods are exemplified: a solution in which each component is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed in a predetermined ratio to prepare a photosensitive resin composition.
Before forming the photosensitive resin layer, the photosensitive resin composition is preferably filtered using a filter having a pore diameter of 0.2 μm to 30 μm.
The method of applying the photosensitive resin composition is not particularly limited, and the photosensitive resin composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
The photosensitive resin layer may be formed by applying a photosensitive resin composition to a protective film described later and drying the same.
[ thermoplastic resin layer ]
The photosensitive transfer material may also include a thermoplastic resin layer.
The photosensitive transfer material preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. This is because, by providing the photosensitive transfer material with the thermoplastic resin layer between the temporary support and the photosensitive resin layer, the following property to the substrate in the bonding step with the substrate is improved, and thus the mixing of bubbles between the substrate and the photosensitive transfer material is suppressed, and the adhesion with the adjacent layer (for example, temporary support) is improved.
< alkali-soluble resin >
The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.
As the alkali-soluble resin, an acrylic resin is preferable from the viewpoints of developability and adhesion to an adjacent layer.
The acrylic resin is a resin having at least 1 structural unit selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide.
The total content of the structural units derived from (meth) acrylic acid, the structural units derived from (meth) acrylic acid ester, and the structural units derived from (meth) acrylic acid amide in the acrylic resin is preferably 50 mass% or more based on the total mass of the acrylic resin.
Wherein the total content of the structural units derived from (meth) acrylic acid and the structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.
Also, the alkali-soluble resin is preferably a polymer having an acid group.
Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonate group, and a carboxyl group is preferable.
From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, and still more preferably an acrylic resin containing a carboxyl group having an acid value of 60mgKOH/g or more.
The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.
The acrylic resin having an acid value of 60mgKOH/g or more and containing a carboxyl group is not particularly limited, and can be suitably selected from known resins and used.
Examples of the acrylic resin include an alkali-soluble resin as an acrylic resin having an acid value of 60mgKOH/g or more and containing carboxyl groups in the polymer described in paragraph 0025 of JP 2011-95716, an acrylic resin having an acid value of 60mgKOH/g or more and containing carboxyl groups in the polymer described in paragraphs 0033 to 0052 of JP 2010-237589, and an acrylic resin having an acid value of 60mgKOH/g or more and containing carboxyl groups in the alkali-soluble polymer described in paragraphs 0053 to 0068 of JP 2016-224162.
The copolymerization ratio of the carboxyl group-containing structural units in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.
The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoints of developability and adhesion to an adjacent layer.
The alkali-soluble resin may have a reactive group. The reactive group may be any group capable of addition polymerization, and examples thereof include an ethylenically unsaturated group; a polycondensate group such as a hydroxyl group or a carboxyl group; polyaddition reactive groups such as epoxy groups, (block) isocyanate groups, and the like.
The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 1 to 10 tens of thousands, and still more preferably 2 to 5 tens of thousands.
The thermoplastic resin layer may contain 1 alkali-soluble resin alone or 2 or more kinds.
The content of the alkali-soluble resin is preferably 10 to 99 mass%, more preferably 20 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 50 to 70 mass% with respect to the total mass of the thermoplastic resin layer from the viewpoints of developability and adhesion to the adjacent layer.
< pigment >
The thermoplastic resin layer preferably contains a dye (also simply referred to as "dye B") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm at the time of coloring, and the maximum absorption wavelength is changed by an acid, an alkali or a radical.
The preferred embodiment of the dye B is the same as that of the dye N except for the points described below.
From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid.
From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength changes by the acid as the dye B and a compound which generates an acid by the light, which will be described later.
The pigment B may be used alone or in combination of 1 or 2 or more.
The content of the dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, further preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass% relative to the total mass of the thermoplastic resin layer, from the viewpoint of visibility of the exposed portion and the non-exposed portion.
The content of the dye B is a content of the dye when all the dye B contained in the thermoplastic resin layer is in a color-developed state. Hereinafter, a method for quantifying the content of the dye B will be described by taking a dye that develops color by a radical as an example.
A solution was prepared by dissolving 0.001g and 0.01g of pigment in 100mL of methyl ethyl ketone. To each of the obtained solutions, irgacure OXE01 (trade name, BASF Jap an ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated, thereby generating radicals to bring all the pigments into a color-developed state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under atmospheric air using a spectrophotometer (manufactured by UV3100, shimadzu Corpora tion), and a calibration curve was prepared.
Next, absorbance of the solution in which the pigment was entirely colored was measured in the same manner as described above except that 0.1g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. The amount of the pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer and based on the calibration curve.
< Compounds that generate acid, base or free radical by light >
The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (also simply referred to as "compound C").
The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving activation light such as ultraviolet light or visible light.
As the compound C, a known photoacid generator, photobase generator, and photo radical polymerization initiator (photo radical generator) can be used. Among them, photoacid generators are preferable.
Photoacid generator
From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator.
The photo-acid generator may be a photo-cation polymerization initiator which may be contained in the photosensitive resin layer, and the same is preferable except for the point described below.
The photoacid generator preferably contains at least 1 compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.
The photoacid generator preferably has the following structure.
[ chemical formula 5]
Figure BDA0004092962780000381
Photo radical polymerization initiator
The thermoplastic resin layer may contain a photo radical polymerization initiator (photo radical polymerization initiator).
The photo radical polymerization initiator may be the photo radical polymerization initiator which the photosensitive resin layer may contain, and the same preferable mode is also adopted.
Photobase generator
The thermoplastic resin layer may also contain a photobase generator.
The photobase generator is not particularly limited as long as it is a known photobase generator, and examples thereof include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, o-carbamoyl hydroxyamide, o-carbamoyl oxime, { [ (2, 6-dinitrobenzyl) oxy ] carbonyl } cyclohexylamine, bis { [ (2-nitrobenzyl) oxy ] carbonyl } hexane-1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaminocobalt (III) tris (triphenylmethyl borate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine and 2, 6-dimethyl-3, 5-diacetyl-4- (2-dinitrophenyl) -1, 4-dihydropyridine.
The thermoplastic resin layer may contain 1 kind alone or 2 or more kinds of compound C.
The content of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass% with respect to the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion.
< plasticizer >
The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to an adjacent layer, and developability.
It is preferable that the molecular weight (weight average molecular weight (Mw)) of the plasticizer (oligomer or polymer) is smaller than the molecular weight of the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.
The plasticizer is not particularly limited as long as it is a compound that exhibits plasticity by being compatible with the alkali-soluble resin, and from the viewpoint of imparting plasticity, the plasticizer preferably has an alkylene oxide group in a molecule, and more preferably is a polyalkylene glycol compound. The alkylene oxide group contained in the plasticizer more preferably has a polyethylene oxide structure or a polypropylene oxide structure.
Further, the plasticizer preferably contains a (meth) acrylate compound from the viewpoints of resolution and storage stability. From the viewpoints of compatibility, resolution, and adhesion to an adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
The (meth) acrylate compound used as the plasticizer includes (meth) acrylate compounds described as the ethylenically unsaturated compounds contained in the photosensitive resin layer.
In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive resin layer are stacked in direct contact, it is preferable that the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth) acrylate compound. This is because the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth) acrylate compound, so that the diffusion of components between layers is suppressed and the storage stability is improved.
In the case where the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the adjacent layer.
Further, from the viewpoints of resolution, adhesion to an adjacent layer, and developability, a polyfunctional (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule is preferable as the (meth) acrylate compound used as the plasticizer.
Further, as the (meth) acrylate compound used as the plasticizer, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.
The thermoplastic resin layer may contain 1 kind of plasticizer alone or 2 or more kinds of plasticizers.
The content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion to an adjacent layer, and developability.
< surfactant >
From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant.
The surfactant may be the same as the surfactant that the photosensitive resin layer may contain.
The thermoplastic resin layer may contain 1 kind of surfactant alone or 2 or more kinds of surfactants.
The content of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, relative to the total mass of the thermoplastic resin layer.
< sensitizer >
The thermoplastic resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and examples thereof include the sensitizer that may be contained in the photosensitive resin layer.
The thermoplastic resin layer may contain 1 sensitizer alone or 2 or more kinds of sensitizers.
The content of the sensitizer may be appropriately selected according to the purpose, but is preferably in the range of 0.01 to 5 mass%, more preferably in the range of 0.05 to 1 mass% relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed portion and the non-exposed portion.
< additives etc.)
The thermoplastic resin layer may contain known additives, if necessary, in addition to the above components.
The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese patent application laid-open No. 2014-85643, the contents of which are incorporated herein by reference.
< physical Properties etc.)
The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to an adjacent layer. The upper limit is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less from the viewpoints of developability and resolution.
< method of Forming >
The method for forming the thermoplastic resin layer is not particularly limited as long as the layer containing the above components can be formed.
As a method for forming the thermoplastic resin layer, for example, the following methods can be mentioned: the thermoplastic resin composition containing the above components and a solvent is prepared, and the thermoplastic resin composition is coated on the surface of a support or the like, and a coating film of the thermoplastic resin composition is dried.
In order to adjust the viscosity of the thermoplastic resin composition to facilitate formation of the thermoplastic resin layer, the thermoplastic resin composition preferably contains a solvent.
(solvent)
The solvent contained in the thermoplastic resin composition is not particularly limited as long as the above-mentioned components contained in the thermoplastic resin layer can be dissolved or dispersed.
The solvent contained in the thermoplastic resin composition may be the same as the solvent that the photosensitive resin composition may contain.
The number of the solvents contained in the thermoplastic resin composition may be 1 or 2 or more.
The content of the solvent in coating the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition.
The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be performed in accordance with the above-described method for preparing the photosensitive resin composition and method for forming the photosensitive resin layer.
For example, a thermoplastic resin layer is formed by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in the above-mentioned solvent, mixing the obtained solution at a predetermined ratio to prepare a thermoplastic resin composition, then coating the obtained thermoplastic resin composition on the surface of the temporary support, and drying the coating film of the thermoplastic resin composition.
Further, after forming the photosensitive resin layer and the intermediate layer on the protective film described later, a thermoplastic resin layer may be formed on the surface of the intermediate layer.
[ intermediate layer ]
The photosensitive transfer material preferably includes an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. By providing the intermediate layer, mixing of components at the time of coating the plurality of layers and at the time of storage after coating can be suppressed.
The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppression of mixing of components at the time of coating a plurality of layers and at the time of storage after coating.
In the present specification, "water-soluble" means that the solubility of 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more.
The intermediate layer may be an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. If the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and the productivity is improved, so that it is preferable.
The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the above-mentioned publications and the like. Among them, an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22 ℃) is preferable.
The intermediate layer preferably contains a resin.
Examples of the resin contained in the intermediate layer include resins such as polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof.
The resin contained in the intermediate layer is preferably a water-soluble resin.
In addition, from the viewpoint of suppressing mixing of components between the plurality of layers, the resin contained in the intermediate layer is preferably a resin different from both the polymer a contained in the photosensitive resin layer and the thermoplastic resin (for example, alkali-soluble resin) contained in the thermoplastic resin layer.
The intermediate layer preferably contains polyvinyl alcohol, more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoints of oxygen barrier properties and suppression of mixing of components at the time of coating the multilayer and at the time of storage after coating.
The intermediate layer may contain 1 kind of the above resin alone or 2 or more kinds of the above resins.
The content of the resin in the intermediate layer is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass relative to the total mass of the intermediate layer, from the viewpoints of oxygen barrier property and suppression of mixing of components at the time of coating a plurality of layers and at the time of storage after coating.
The intermediate layer may contain an additive such as a surfactant, if necessary.
The thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm.
This is because, if the thickness of the intermediate layer is within the above range, the mixing of components at the time of coating the multilayer and at the time of storage after coating can be suppressed without reducing the oxygen barrier property, and an increase in the intermediate layer removal time at the time of development can be suppressed.
The method for forming the intermediate layer is not particularly limited, and for example, the following methods are given: an intermediate layer composition containing the above resin and any additives is prepared, applied to the surface of a thermoplastic resin layer or a photosensitive resin layer, and a coating film of the intermediate layer composition is dried, thereby forming an intermediate layer.
In order to adjust the viscosity of the intermediate layer composition to facilitate formation of the intermediate layer, the intermediate layer composition preferably contains a solvent.
The solvent contained in the intermediate layer composition is not particularly limited as long as the resin can be dissolved or dispersed, and is preferably at least 1 selected from water and water-miscible organic solvents, more preferably water or a mixed solvent of water and water-miscible organic solvents.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.
[ protective film ]
The photosensitive transfer material preferably includes a protective film that contacts a surface of the photosensitive resin layer that does not face the temporary support.
As a material constituting the protective film, a resin film and paper are exemplified, and from the viewpoint of strength and flexibility, a resin film is preferable.
Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.
The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.
Further, from the viewpoint of further excellent resolution, the arithmetic average roughness Ra value of the surface of the protective film (hereinafter, also simply referred to as "surface of the protective film") in contact with the photosensitive resin layer is preferably 0.3 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less. This is considered to be because the Ra value of the surface of the protective film is in the above range, and the uniformity of the layer thickness of the photosensitive resin layer and the resin pattern formed is improved.
The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more.
The Ra value of the surface of the protective film was measured by the following method.
The surface profile of the protective film was measured using a three-dimensional optical profiler (New View7300, manufactured by Zygo corporation) under the following conditions, to obtain the surface profile of the optical film.
As the measurement/analysis software, microscope Application of MetroPro ver8.3.2 was used. Then, the Surface Map screen is displayed by the analysis software, and histogram data is obtained in the Surface Map screen. An arithmetic average roughness is calculated from the obtained histogram data, thereby obtaining an Ra value of the surface of the protective film.
When the protective film is attached to the photosensitive transfer material, the protective film may be peeled off from the photosensitive transfer material, and the Ra value of the peeled surface may be measured.
The photosensitive transfer material may include a layer other than the above layers (hereinafter, also referred to as "other layer"). As the other layer, for example, a contrast enhancement layer can be cited.
The contrast enhancement layer is described in paragraph 0134 of International publication No. 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of Japanese patent application laid-open No. 2014-85643. The contents of these publications are incorporated into the present specification.
From the viewpoint of further exhibiting the effects of the present invention, the total thickness of each layer of the photosensitive transfer material other than the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.
Further, from the viewpoint of further exhibiting the effects of the present invention, the total thickness of the photosensitive resin layer, the intermediate layer, and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.
The photosensitive transfer material according to the present invention can be preferably used in various applications requiring precise micromachining by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be etched as a coating film, or electroforming mainly including electroplating may be performed. The cured film obtained by patterning can be used as a permanent film, for example, an interlayer insulating film, a wiring protective film having an index matching layer, or the like. The photosensitive transfer material according to the present invention can be preferably used for various wiring formation applications of semiconductor packages, printed boards, sensor boards, touch panels, electromagnetic shield materials, conductive films such as film heaters, liquid crystal sealing materials, and formation of structures in the micro-mechanical or micro-electronic fields.
[ method for producing photosensitive transfer Material ]
The method for producing the photosensitive transfer material used in the present invention is not particularly limited, and a known production method, for example, a known method for forming each layer, can be used.
A method for producing the photosensitive transfer material used in the present invention will be described below with reference to fig. 1. However, the photosensitive transfer material used in the present invention is not limited to the photosensitive transfer material having the structure shown in fig. 1.
Fig. 1 is a schematic cross-sectional view showing an example of the structure of a photosensitive transfer material used in the present invention. The photosensitive transfer material 100 shown in fig. 1 has a structure in which a temporary support 10, a thermoplastic resin layer 12, an intermediate layer 14, a photosensitive resin layer 16, and a protective film 18 are laminated in this order.
As a method for producing the photosensitive transfer material 100, for example, a method including the steps of: a step of forming a thermoplastic resin layer 12 by coating a thermoplastic resin composition on the surface of the temporary support 10 and then drying a coating film of the thermoplastic resin composition; a step of forming an intermediate layer 14 by applying an intermediate layer composition to the surface of the thermoplastic resin layer 12 and then drying a coating film of the intermediate layer composition; and a step of forming a photosensitive resin layer 16 by applying a photosensitive resin composition containing an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator to the surface of the intermediate layer 14, and then drying the coating film of the photosensitive resin composition.
In the above-described production method, the following composition is preferably used: a thermoplastic resin composition containing at least 1 selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents; an intermediate layer composition containing at least 1 selected from water and water-miscible organic solvents; and a photosensitive resin composition containing an alkali-soluble polymer, an ethylenically unsaturated compound, a photopolymerization initiator, and at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This can suppress the application of the intermediate layer composition to the surface of the thermoplastic resin layer 12 and/or the mixing of the component contained in the thermoplastic resin layer 12 and the component contained in the intermediate layer 14 during the storage of the laminate having the coating film of the intermediate layer composition, and can suppress the application of the photosensitive resin composition to the surface of the intermediate layer 14 and/or the mixing of the component contained in the intermediate layer 14 and the component contained in the photosensitive resin layer 16 during the storage of the laminate having the coating film of the photosensitive resin composition.
The photosensitive transfer material 100 is manufactured by pressing the protective film 18 against the photosensitive resin layer 16 of the laminate manufactured by the above-described manufacturing method.
As a method for producing the photosensitive transfer material used in the present invention, it is preferable to produce the photosensitive transfer material 100 including the temporary support 10, the thermoplastic resin layer 12, the intermediate layer 14, the photosensitive resin layer 16, and the protective film 18 by including a step of providing the protective film 18 so as to be in contact with the photosensitive resin layer 16.
After the photosensitive transfer material 100 is manufactured by the above manufacturing method, the photosensitive transfer material 100 may be wound up to manufacture and store a photosensitive transfer material in a wound form. The photosensitive transfer material in the roll form can be directly supplied in this form to a bonding step with a substrate in a roll-to-roll system described later.
(method for producing resin Pattern)
The method for producing a resin pattern according to the present invention is a method for producing a resin pattern on a substrate by using a photosensitive transfer material having a temporary support and a photosensitive resin layer.
As a method for producing the resin pattern, a method comprising the following steps in this order is preferable: a step of bonding the outermost layer of the photosensitive transfer material according to the present invention, which is on the side having the photosensitive resin layer with respect to the temporary support, to the substrate in contact therewith (hereinafter, also referred to as a "bonding step"); a step of exposing the photosensitive resin layer to a pattern (hereinafter, also referred to as an "exposure step"); and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, also referred to as a "developing step").
< bonding Process >
The method for producing the resin pattern preferably includes a bonding step.
In the bonding step, it is preferable that the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support is brought into contact with the substrate (the conductive layer in the case where the conductive layer is provided on the surface of the substrate), so that the photosensitive transfer material is pressed against the substrate. In the above-described aspect, the adhesion between the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support and the substrate is improved, and therefore, the photosensitive transfer material can be preferably used as an etching resist for etching the photosensitive resin layer conductive layer formed by the pattern after exposure and development.
In the case where the photosensitive transfer material includes a protective film, the protective film may be removed from the surface of the photosensitive resin layer and then bonded.
In the bonding step, when the photosensitive transfer material further includes a layer (e.g., a high refractive index layer and/or a low refractive index layer) other than the protective film on the surface of the photosensitive resin layer on the side not facing the temporary support, the surface of the photosensitive resin layer on the side not facing the temporary support is bonded to the substrate with the layer interposed therebetween.
The method for pressing the substrate against the photosensitive transfer material is not particularly limited, and a known transfer method and lamination method can be used.
The photosensitive transfer material is preferably bonded to the substrate by superposing an outermost layer of the photosensitive transfer material on the side of the temporary support having the photosensitive resin layer on the substrate, and applying pressure and heat by a mechanism such as a roller. For lamination, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used.
The method for manufacturing the resin pattern and the method for manufacturing the circuit wiring including the bonding step are preferably performed in a roll-to-roll manner.
The roll-to-roll system will be described below.
The roll-to-roll system is the following system: as the substrate, a substrate that can be wound and unwound is used, and a step of winding out the substrate or a structure including the substrate (also referred to as a "winding-out step") and a step of winding up the substrate or a structure including the substrate (also referred to as a "winding-up step") are included before any step included in the method for manufacturing a resin pattern or the method for manufacturing a circuit wiring, and at least any step (preferably all steps or all steps except for a heating step) is performed while carrying the substrate or the structure including the substrate.
The winding-out method in the winding-out step and the winding-up method in the winding-up step are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.
< substrate >
As the substrate used in the method for producing a resin pattern according to the present invention, a known substrate can be used, but a substrate having a conductive layer is preferable, and a conductive layer is more preferable on the surface of the substrate.
The substrate may have any layer other than the conductive layer as needed.
Examples of the base material constituting the substrate include glass, silicon, and a thin film.
The base material constituting the substrate is preferably transparent. In the present specification, "transparent" means that the transmittance of light having a wavelength of 400nm to 700nm is 80% or more.
The refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.
As the transparent glass substrate, tempered glass typified by gorilla glass of Corning Incorporated can be given. As the transparent glass substrate, materials used in japanese patent application laid-open publication nos. 2010-86684 and 2010-152809 and 2010-257492 can be used.
When a thin film substrate is used as the substrate, a thin film substrate having a small optical strain and/or high transparency is preferably used. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymer.
When the substrate is manufactured by a roll-to-roll method, a thin film substrate is preferable. In the case of manufacturing a circuit wiring for a touch panel by a roll-to-roll method, it is preferable that the substrate is a sheet-like resin composition.
Examples of the conductive layer included in the substrate include a conductive layer used for a normal circuit wiring or a touch panel wiring.
The conductive layer is preferably at least 1 layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer, from the viewpoints of conductivity and fine line formability.
The substrate may have 1 conductive layer alone or 2 or more layers. In the case of having 2 or more conductive layers, conductive layers of different materials are preferable.
As a material of the conductive layer, a metal and a conductive metal oxide can be given.
As the metal, al, zn, cu, fe, ni, cr, mo, ag and Au are exemplified.
Examples of the conductive metal oxide include ITO (indium tin oxide), IZO (indium zinc oxide) and SiO 2 。
In the present specification, the term "conductivity" means that the volume resistivity is less than 1×10 6 Omega cm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ωcm。
In the case of manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.
The conductive layer is preferably an electrode pattern of a sensor corresponding to a visual recognition portion used in a capacitive touch panel or a wiring of a peripheral lead portion.
< Exposure procedure >
In the method for producing a resin pattern, it is preferable that the method further includes a step of exposing the photosensitive resin layer to a pattern after the bonding step (exposure step).
The detailed arrangement and specific dimensions of the pattern in the pattern exposure are not particularly limited. In order to improve the display quality of a display device (e.g., a touch panel) including an input device having circuit wiring manufactured by a circuit wiring manufacturing method and to reduce the area occupied by lead-out wiring, at least a part of the pattern (preferably, an electrode pattern of the touch panel and/or a portion of the lead-out wiring) preferably includes a thin line having a width of 20 μm or less, and more preferably includes a thin line having a width of 10 μm or less.
The light source used for exposure may be appropriately selected and used as long as it is a light source that irradiates light (e.g., 365nm or 405 nm) of a wavelength at which the photosensitive resin layer can be exposed. Specifically, an ultra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode: light emitting diode) are mentioned.
As the exposure amount, 5mJ/cm is preferable 2 ～200mJ/cm 2 More preferably 10mJ/cm 2 ～100mJ/cm 2 。
In the exposure step, the temporary support may be removed from the photosensitive resin layer and then subjected to pattern exposure, or the temporary support may be removed after pattern exposure is performed through the temporary support before the temporary support is removed. In the case of peeling the temporary support before exposure, the mask may be exposed in contact with the photosensitive resin layer or may be exposed close to it without contact. In the case of exposing without peeling the temporary support, the mask may be exposed in contact with the temporary support or may be exposed in the vicinity of the temporary support without contact. In order to prevent contamination of the mask due to contact between the photosensitive resin layer and the mask and to avoid influence on exposure by foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling off the temporary support. In addition, in the exposure system, the contact exposure system can be appropriately selected and used in the case of contact exposure, and in the case of non-contact exposure system, the proximity exposure system, the projection exposure system of a lens system or a mirror system, the direct exposure system using exposure laser, or the like can be appropriately selected and used. In the case of projection exposure by a lens system or a mirror system, an exposure machine having an appropriate number of openings (NA) of lenses can be used depending on the required resolution and focal depth. In the case of the direct exposure method, the photosensitive resin layer may be directly drawn, or the photosensitive resin layer may be subjected to reduced projection exposure via a lens. The exposure may be performed not only under the atmosphere but also under reduced pressure or vacuum, and may be performed by separating a liquid such as water between the light source and the photosensitive resin layer.
< developing Process >
In the method for producing a resin pattern, it is preferable that the method further includes a step of developing the exposed photosensitive resin layer to form a resin pattern (developing step) after the exposure step.
In the case where the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and the intermediate layer in the non-exposed portion are removed together with the photosensitive resin layer in the non-exposed portion in the developing step. In the developing step, the thermoplastic resin layer and the intermediate layer in the exposed portion may be removed in a form of being dissolved or dispersed in a developing solution.
The exposed photosensitive resin layer in the developing step can be developed with a developer.
The developer is not particularly limited as long as the non-image portion (non-exposed portion) of the photosensitive resin layer can be removed, and for example, a known developer such as the developer described in japanese unexamined patent publication No. 5-72724 can be used.
The developer is preferably an aqueous alkali developer containing a compound having pka=7 to 13 at a concentration of 0.05mol/L to 5mol/L (liter). The developer may contain a water-soluble organic solvent and/or a surfactant. The developer described in paragraph 0194 of International publication No. 2015/093271 is also preferable.
The development method is not particularly limited, and may be any of spin-coating immersion development, shower and spin development, and immersion development. The development by showering is a development process in which a developing solution is sprayed onto the photosensitive resin layer after exposure by showering to remove the non-exposed portion.
Preferably, after the developing step, the cleaning agent is sprayed and sprayed, and the developing residues are removed while wiping with a brush.
The liquid temperature of the developer is not particularly limited, but is preferably 20 to 40 ℃.
< protective film peeling Process >
In the case where the photosensitive transfer material has a protective film, the method for producing the resin pattern preferably includes a step of peeling the protective film from the photosensitive transfer material. The method of peeling the protective film is not limited, and a known method can be applied.
< other procedure >
The method for producing a resin pattern may include any process (other process) other than the above process. For example, the steps described in the following method for producing a circuit wiring or method for producing a touch panel may be mentioned, but the method is not limited to these steps.
(method for manufacturing Circuit Wiring)
The method for producing the circuit wiring according to the present invention is not particularly limited as long as the method using the photosensitive transfer material according to the present invention is used.
As a method for manufacturing a circuit wiring according to the present invention, it is preferable to sequentially include the steps of: a step of bonding the outermost layer of the photosensitive transfer material according to the present invention, which is on the side having the photosensitive resin layer with respect to the temporary support, to a substrate having a conductive layer by contact; a step of exposing the photosensitive resin layer to a pattern; developing the exposed photosensitive resin layer to form a resin pattern; and a step of etching the substrate in a region where the resin pattern is not arranged (hereinafter, also referred to as "etching step").
Hereinafter, each step included in the method for manufacturing a circuit wiring will be described, but unless otherwise mentioned, the description of each step included in the method for manufacturing a resin pattern is also applicable to each step included in the method for manufacturing a circuit wiring.
< etching Process >
The method for manufacturing the circuit wiring preferably includes a step of etching the substrate in a region where the resin pattern is not arranged (etching step).
In the etching step, a resin pattern formed of a photosensitive resin layer is used as an etching resist, and an etching treatment of the conductive layer is performed.
As a method of etching treatment, known methods can be applied, and examples thereof include the method described in paragraphs 0209 to 0210 of japanese patent application laid-open publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of japanese patent application laid-open publication No. 2010-152155, a wet etching method in which an etching solution is immersed, and a dry etching method by plasma etching or the like.
The etching liquid used in the wet etching may be appropriately selected from acidic or alkaline etching liquids according to the object to be etched.
Examples of the acidic etching liquid include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components.
Examples of the alkaline etching liquid include an aqueous solution of an alkali component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine and a salt of an organic amine (such as tetramethylammonium hydroxide), and a mixed aqueous solution of an alkali component and a salt (such as potassium permanganate). The alkali component may be a component obtained by combining a plurality of alkali components.
< removal Process >
In the method for manufacturing the circuit wiring, a step of removing the remaining resin pattern (removal step) is preferably performed.
The removal step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.
The method for removing the residual resin pattern is not particularly limited, and a method for removing the residual resin pattern by chemical treatment is preferable, and a method for removing the residual resin pattern by using a removing liquid is preferable.
The photosensitive resin layer is removed by immersing the substrate having the remaining resin pattern in a removing liquid under stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes.
Examples of the removing liquid include a removing liquid obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.
The removal liquid may be removed by a known method such as spraying, showering, spin-coating or immersing.
< other procedure >
The method for manufacturing the circuit wiring may include any process (other process) other than the above process. For example, the following steps may be mentioned, but the present invention is not limited to these steps.
Further, examples of the exposure step, the development step, and other steps which can be applied to the method for producing a circuit wiring include the steps described in paragraphs 0035 to 0051 of JP 2006-23696A.
Procedure for reducing the reflectivity of visible light
The method for manufacturing the circuit wiring may include a step of performing a process of reducing the visible ray reflectance of a part or all of the plurality of conductive layers included in the substrate.
As the treatment for reducing the reflectance of visible light, an oxidation treatment is given. When the substrate has a conductive layer containing copper, the visible ray reflectance of the conductive layer can be reduced by oxidizing copper to produce copper oxide and blackening the conductive layer.
The treatment for reducing the reflectance of visible light is described in paragraphs 0017 to 0025 of Japanese unexamined patent publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese unexamined patent publication No. 2013-206315, and the contents of these publications are incorporated herein by reference.
A step of forming an insulating film, a step of forming a new conductive layer on the surface of the insulating film
The method for manufacturing the circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.
Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film may be used. Further, an insulating film having a desired pattern can be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.
In the method for manufacturing the circuit wiring, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and to form circuits successively or simultaneously with respect to the conductive layers formed on both surfaces of the substrate. With this structure, a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a substrate and a second conductive pattern is formed on the other surface can be formed. Further, it is also preferable to form the circuit wiring for the touch panel having such a structure from both sides of the substrate in a roll-to-roll manner.
< use of Circuit Wiring >
The circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices. As a device including the circuit wiring manufactured by the above-described manufacturing method, for example, an input device is given, and a touch panel is preferable, and a capacitive touch panel is more preferable. The input device can be applied to a display device such as an organic EL display device or a liquid crystal display device.
(method for manufacturing touch Panel)
The method for manufacturing a touch panel according to the present invention is not particularly limited as long as the method using the photosensitive transfer material according to the present invention is used.
As a method for manufacturing a touch panel according to the present invention, it is preferable to sequentially include the steps of: a step of bonding the outermost layer of the photosensitive transfer material according to the present invention, which is on the side having the photosensitive resin layer with respect to the temporary support, to a substrate having a conductive layer by contact; a step of exposing the photosensitive resin layer to a pattern; developing the exposed photosensitive resin layer to form a resin pattern; and etching the substrate in the region where the resin pattern is not arranged.
The specific modes of the steps in the method for manufacturing a touch panel, the order in which the steps are performed, and the like are preferably the same as those described in the above-described items of "method for manufacturing a resin pattern" and "method for manufacturing a circuit wiring".
As a method for manufacturing a touch panel, a known method for manufacturing a touch panel may be referred to in addition to forming a wiring for a touch panel by the above-described method.
The method for manufacturing the touch panel may include any step (other step) other than the above.
Fig. 2 and 3 show an example of a pattern of a mask used for manufacturing a touch panel.
In the pattern a shown in fig. 2 and the pattern B shown in fig. 3, GR is a non-image portion (light shielding portion), EX is an image portion (exposure portion), and DL virtually represents an alignment frame. In the method for manufacturing a touch panel, for example, the photosensitive resin layer is exposed to light through a mask having a pattern a shown in fig. 2, whereby a touch panel having a circuit wiring having a pattern a corresponding to EX can be manufactured. Specifically, the method described in FIG. 1 of International publication No. 2016/190405 can be used. In an example of the manufactured touch panel, the central portion (pattern portion to be qualified for connection) of the exposure portion EX is a portion where a transparent electrode (electrode for touch panel) is formed, and the peripheral portion (thin line portion) of the exposure portion EX is a portion where wiring of the peripheral lead-out portion is formed.
The touch panel having at least the wiring for the touch panel is manufactured by the above-described method for manufacturing a touch panel. The touch panel preferably has a transparent substrate, an electrode, an insulating layer, or a protective layer.
As a detection method in the touch panel, a known method such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method can be given. Among them, the electrostatic capacitance system is preferable.
Examples of the Touch panel type include a so-called in-line type (for example, those described in fig. 5, 6, 7, and 8 of japanese patent application laid-open publication No. 2012-517051), a so-called out-line type (for example, those described in fig. 19 of japanese patent application laid-open publication No. 2013-168125, and those described in fig. 1 and 5 of japanese patent application laid-open publication No. 2012-89102), an OGS (One Glass Solution: monolithic glass Touch technology), a TOL (Touch-on-Lens: overlay Touch) type (for example, those described in fig. 2 of japanese patent application laid-open publication No. 2013-54727), and various types of plug-ins (for example, those described in fig. 6 of japanese patent application laid-open publication No. 2013-164871, such as GG 1-G2, GFF 2, GF1, and G1F).
Examples of the touch panel include the touch panel described in paragraph 0229 of japanese patent application laid-open No. 2017-120435.
Examples
Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. The materials, amounts used, proportions, processing contents, processing order, and the like shown in the examples below can be appropriately modified without departing from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.
The following abbreviations represent the following compounds, respectively.
MFG: propylene glycol 1-monomethyl ether (FUJIFILM Wako Pure Chemical Corporation)
AIBN:2,2' -azobis (isobutyronitrile) (FUJIFILM Wako Pure Chemical Corpor ation)
(examples 1 to 11 and comparative examples 1 to 3)
< preparation of photosensitive resin composition >
Each photosensitive resin composition having a solid content concentration of 25 mass% was prepared by mixing the components described in table 1 below and adding methyl ethyl ketone.
< preparation of photosensitive transfer Material >
A PET film (manufactured by TORAY INDUSTRIES, INC., lumiror 16QS62, arithmetic average roughness (Ra value) of 0.02 μm) having a thickness of 16 μm was prepared as a temporary support. The photosensitive resin composition was applied to the surface of the temporary support using a slit nozzle so that the application width became 1.0m and the layer thickness after drying became the values described in table 1. The formed coating film of the photosensitive resin composition was dried at 95 ℃ for 100 seconds, thereby forming a photosensitive resin layer.
The photosensitive transfer materials of each example and comparative example were produced by pressing a polyethylene film (tamopo co., ltd. Manufactured by GF-818) having a thickness of 19 μm as a protective film on the surface of the formed photosensitive resin layer. The photosensitive transfer material thus obtained was wound up to produce a photosensitive transfer material in a roll form.
< evaluation of Performance >
A PET substrate with a copper layer was used, which was prepared by sputtering a polyethylene terephthalate (PET) film having a thickness of 100 μm and a copper layer having a thickness of 200 nm.
< method for measuring maximum absorption wavelength >
The photosensitive transfer material thus produced was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 95℃and a linear pressure of 0.9MPa and a linear velocity of 2.0 m/min. A high-pressure mercury lamp was used without peeling off the temporary support and the cumulative exposure at a wavelength of 365nm was set to 100mJ/cm 2 Is exposed to light of the amount of light. Reflectance at a wavelength of 450nm to 800nm was measured from a direction perpendicular to a surface direction of the photosensitive transfer material on the temporary support side using a reflectance spectrocolorimeter (CM-700d,Konica Minolta,Inc, manufactured by measuring diameter 3mm Φ, SCI mode), and a wavelength at which reflectance was smallest in the above wavelength range was set as a maximum absorption wavelength. The measured values are shown in table 1.
< evaluation of resolution >
After the photosensitive transfer material was wound out, it was laminated on the copper-clad PET substrate under a lamination condition of a roll temperature of 120℃and a linear pressure of 1.0MPa and a linear velocity of 0.5 m/min. The temporary support was not peeled off, and after exposure was performed by a high-pressure mercury lamp through a line-space pattern mask (Duty ratio 1:1, line width 1 μm to 20 μm, stepwise changes every 1 μm), the temporary support was peeled off, and development was performed. For development, a 1.0% aqueous sodium carbonate solution at 25 ℃ was used, and development by spraying was performed for 30 seconds.
When a line and space pattern of 20 μm was formed by the above method, residues in the space were observed by a Scanning Electron Microscope (SEM), and when exposure was performed with an exposure amount at which the resist line width was just 20 μm, the minimum line width at which the resist pattern could be resolved without peeling and residues was evaluated as resolution. The smaller the value, the better the resolution.
5: resolution of less than 4 mu m
4: resolution is 5 μm or more and 6 μm or less
3: resolution is 7 μm or more and 8 μm or less
2: resolution is 9 μm or more and 10 μm or less
1: resolution of 11 μm or more
Preferably 2 or more.
< evaluation of visibility of exposed portion and non-exposed portion >
The photosensitive transfer material thus produced was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 95℃and a linear pressure of 0.9MPa and a linear velocity of 2.0 m/min. The reflectance at the maximum absorption wavelength (for example, wavelength 590 nm) was measured from a direction perpendicular to the surface direction of the photosensitive transfer material on the temporary support side using a reflection spectrocolorimeter (CM-700d,Konica Minolta,Inc, manufactured by measuring diameter 3mm Φ, SCI mode) without peeling the temporary support. Thereafter, the resultant exposure was set to 100mJ/cm at a wavelength of 365nm using a high-pressure mercury lamp 2 The maximum absorption wavelength (for example, 590 nm) was measured for reflectance by exposure and re-use of a reflection type spectrocolorimeter (CM-700d,Konica Minolta,Inc, measurement of 3mm diameter, SCI mode).
The reflectance before and after exposure was converted into reflectance concentration, and the absolute value (Δo.d.) of the difference between the reflectance concentration before and after exposure (o.d.) was evaluated as the visibility of the exposed portion and the non-exposed portion, respectively, using the following formula. The larger the difference in reflection density before and after exposure, the better the visibility.
Reflection concentration (o.d.) = -log 10 (reflectivity)
For example, the reflectance 1 (=100%) is o.d. =0, the reflectance 0.6 (=60%) is 0.D.=0.22, the reflectance 0.2 (=20%) is o.d. =0.7, and the like.
< evaluation of peelability >
After the photosensitive transfer material was wound out, it was laminated on the copper-clad PET substrate under a lamination condition of a roll temperature of 110℃and a linear pressure of 1.0MPa and a linear velocity of 1.0 m/min. A high-pressure mercury lamp was used without peeling off the temporary support and the cumulative exposure at a wavelength of 365nm was set to 100mJ/cm 2 Is exposed to light of the amount of light. The irradiated photosensitive transfer material was cut into 10cm squares, and the temporary support was peeled off to obtain a test piece.
The test piece was immersed in a 50 ℃ aqueous solution of monoethanolamine in 10 mass% with stirring, and the time from the time of immersion (the start of immersion) until the laminate was completely peeled off from the copper-clad PET substrate (the completion of peeling) was measured. The peeling time was classified as follows.
5: the peeling time is less than 20 seconds
4: the peeling time exceeds 20 seconds and is less than 30 seconds
3: the peeling time exceeds 30 seconds and is less than 40 seconds
2: the peeling time exceeds 40 seconds and is less than 50 seconds
1: peeling time exceeds 50 seconds
Preferably 3 or more.
The evaluation results are summarized in table 1.
TABLE 1
Figure BDA0004092962780000581
The abbreviations described in table 1 are shown in detail below.
A-1 to A-3: resin (alkali-soluble polymer) synthesized by the following synthesis method
BPE-500:2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane, shin-Nakamura Chemical co., ltd
BPE-200:2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane, shin-Nakamura Chemical co., ltd
Dimethacrylate of polyethylene glycol to which an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide were added at both ends of bisphenol a: compounds synthesized by the following synthetic methods
M-270: polypropylene glycol diacrylate, TOAGOSEI co., ltd. Manufactured
a-TMPT: trimethylolpropane triacrylate, shin-Nakamura Chemical co., ltd
SR-454: ethoxylated (3) trimethylolpropane triacrylate, manufactured by Sartomer Company, inc
SR-502: ethoxylated (9) trimethylolpropane triacrylate, manufactured by Sartomer Company, inc
A-9300-CL1: epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, shin-Nakamura Chemical co., ltd
Colorless crystal violet: color former, tris (4-dimethylaminophenyl) methane, tokyo Chemical Industry co., ltd.)
Colorless malachite green: color former, bis (4-dimethylaminophenyl) phenyl methane, tokyo Chemical Industry co., ltd
CBT-1: rust inhibitor, carboxybenzotriazole, JOHOKU CHEMICAL co., LTD
TDP-G: polymerization inhibitor, phenothiazine, kawaguchi Chemical Industry co., ltd
Irganox245: hindered phenol polymerization inhibitor, manufactured by BASF corporation
F-552: fluorine-based surfactant, MEGAFAC F552, manufactured by DIC Corporation
< synthetic example of Polymer A-1 >
To a three-necked flask, MFG (75.0 g) was added, and the temperature was raised to 90℃under a nitrogen atmosphere. A solution of styrene (32.0 g), methacrylic acid (28.0 g), methyl methacrylate (40.0 g), AIBN (0.8 g) and MFG (75.0 g) was added thereto and the mixture was added dropwise to a three-necked flask solution maintained at 90.+ -. 2 ℃ over 2 hours. After completion of the dropwise addition, the mixture was stirred at 90.+ -. 2 ℃ for 2 hours, whereby polymer A-1 (solid content: 40.0%) was obtained.
< synthetic example of Polymer A-2 and A-3 >
The types of monomers and the like were changed as shown in Table 1, and the other conditions were changed, and the synthesis was performed in the same manner as for the polymer A-1. The solid content concentration of the polymers A-2 and A-3 was set to 40% by mass, respectively. The monomer ratios shown in Table 1 are shown in mass%.
< method for synthesizing dimethacrylate of polyethylene glycol to which an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide are added at both ends of bisphenol A)
A500 mL pressure-resistant reaction vessel was charged with 22.83g (0.1 mol) of bisphenol A, 30g of toluene as a solvent, and 0.3g of triethylamine as a catalyst, the inside of the reaction vessel was replaced with nitrogen gas, and the nitrogen gas pressure was set to 0.2kg/cm 2 The temperature was raised to 80℃with stirring. 132.15g (3.0 mol) of ethylene oxide and 23.24g (0.4 mol) of propylene oxide were successively introduced so as to be kept at about 2kg/cm 2 Is heated to 150 c while the pressure is increased. After being kept at 150℃for 1 hour, the reaction mixture was cooled, the obtained reaction mixture was neutralized with oxalic acid, 50g of ion-exchanged water was added thereto and stirred, and then, the mixture was left to stand, whereby a separated organic layer was extracted. After the obtained organic layer was washed 3 times with 50g of ion-exchanged water, the pressure was reduced to 30Torr at a temperature of 50℃and the solvent was removed to obtain 105.1g of a diol.
A three-necked flask having an internal volume of 1L was charged with 100.0g (0.044 mol) of the obtained diol, 11.5g of methacrylic acid, 0.9g of 70 mass% aqueous methanesulfonic acid, 0.2g of hydroquinone and 200mL of toluene, and esterification was carried out under reflux of toluene for 8 hours. The water generated in the reaction was removed by a Dean-Stark trap. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the obtained organic layer was washed with 50g of 5% aqueous sodium hydroxide solution 1 time, followed by washing with 50g of ion-exchanged water 3 times. By adding 0.09g of hydroquinone Monomethyl Ether (MEHQ) to the organic layer, depressurizing to 30Torr at a temperature of 50℃and removing the solvent, 90.0g of the objective 2-functional methacrylate was obtained.
As shown in table 1, the photosensitive transfer materials of examples 1 to 11 were more excellent in visibility and releasability than the photosensitive transfer materials of comparative examples 1 to 3.
The photosensitive transfer materials of examples 1 to 11 also have excellent resolution.
Example 101 (second: PET stripping Exposure)
An ITO film was formed as a conductive layer of the second layer by sputtering on a PET substrate having a thickness of 100 μm, and a copper film was formed as a conductive layer of the first layer by vacuum evaporation with a thickness of 200nm thereon, thereby producing a circuit-forming substrate.
The photosensitive transfer material obtained in example 1 (laminating roller temperature 120 ℃, line pressure 0.8MPa, line speed 1.0 m/min.) was laminated on the copper layer. The laminated laminate was subjected to contact pattern exposure using a photomask provided with a pattern a shown in fig. 2, which has a structure in which a conductive layer pad was connected in one direction without peeling off a temporary support. Thereafter, the temporary support was peeled off, and developed and washed with water to obtain a pattern a. Next, after etching the copper layer using a copper etching solution (KANTO CHEMICAL co., inc. Cu-02), the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., inc. ITO-02), whereby a substrate on which both copper and ITO were drawn by pattern a was obtained.
The remaining photosensitive resin layer (pattern a) was peeled off using a peeling liquid (KANTO CHEMICAL co., inc. KP-301), and the photosensitive transfer material obtained in example 1 (laminating roller temperature 120 ℃, line pressure 0.8MPa, line speed 1.0 m/min.) was laminated again on the copper layer.
Next, in an aligned state, pattern exposure was performed using a photomask of a pattern B shown in fig. 3, and development and water washing were performed. Thereafter, the copper layer was etched with Cu-02, and the remaining photosensitive resin layer (pattern B) was peeled off with a peeling liquid (KANTO CHEMICAL CO., INC. KP-301).
The obtained circuit board was observed by a microscope, and was found to be a perfect pattern without peeling, chipping, and the like.
In the pattern a shown in fig. 2, the gray portion GR is a light shielding portion, the EX is an exposure portion, and the dotted portion DL virtually represents an alignment frame.
In the pattern B shown in fig. 3, similarly to fig. 2, the gray portion GR is a light shielding portion, the EX is an exposure portion, and the dotted portion DL virtually represents an alignment frame.
The disclosure of japanese patent application No. 2020-141774, filed 8/25/2020, is incorporated herein by reference in its entirety.
All documents, patent applications and technical standards described in this specification are incorporated by reference into this specification to the same extent as if each document, patent application and technical standard was specifically and individually described to be incorporated by reference.
Symbol description
10-temporary support, 12-thermoplastic resin layer, 14-intermediate layer, 16-photosensitive resin layer, 18-protective film, 100-photosensitive transfer material, GR-light shielding portion (non-image portion), EX-exposure portion (image portion), DL-alignment frame.

Claims (13)

1. A photosensitive transfer material, comprising:
a temporary support; a kind of electronic device with high-pressure air-conditioning system
A photocurable and photochromic photosensitive resin layer containing an alkali-soluble polymer, an ethylenically unsaturated compound and a photopolymerization initiator,
the photosensitive resin layer has a layer thickness of 5 μm or less,
by means of a high-pressure mercury lamp at 100mJ/cm 2 When the photosensitive transfer material is exposed to light, the variation of the reflection concentration per unit thickness at the maximum absorption wavelength of the photosensitive transfer material in the range of 450nm to 800nm is 0.04 μm -1 The above.
2. The photosensitive transfer material according to claim 1, wherein,
the variation of the reflection concentration before and after exposure is 0.05 μm -1 The above.
3. The photosensitive transfer material according to claim 1 or 2, wherein,
the photosensitive resin layer has a layer thickness of 4 μm or less.
4. The photosensitive transfer material according to any one of claims 1 to 3, wherein,
the photopolymerization initiator comprises a hexaarylbiimidazole compound.
5. The photosensitive transfer material according to claim 4, wherein,
the content of the hexaarylbiimidazole compound is 1 mass% or more relative to the total mass of the photosensitive resin layer.
6. The photosensitive transfer material according to claim 4 or 5, wherein,
the content of the hexaarylbiimidazole compound is 2 mass% or more relative to the total mass of the photosensitive resin layer.
7. The photosensitive transfer material according to any one of claims 1 to 6, wherein,
the photosensitive resin layer further comprises a compound represented by the following formula (1),
Figure FDA0004092962770000011
in the formula (1), R 1 ～R 6 Each independently represents an alkyl group having 1 to 6 carbon atoms.
8. The photosensitive transfer material according to claim 7, wherein,
the content of the compound represented by the formula (1) is 1 to 10% by mass relative to the total mass of the photosensitive resin layer.
9. The photosensitive transfer material according to claim 7 or 8, wherein,
The content of the compound represented by the formula (1) is 1.5 to 10% by mass relative to the total mass of the photosensitive resin layer.
10. The photosensitive transfer material according to any one of claims 7 to 9, wherein,
the content M of the photopolymerization initiator contained in the photosensitive resin layer A And the content M of the compound represented by the formula (1) B Mass ratio M of (2) A /M B 0.3 to 5.0.
11. A method for manufacturing a resin pattern, comprising, in order:
a step of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 10 on the side having the photosensitive resin layer with respect to the temporary support, by contacting the outermost layer with a substrate having a conductive layer;
a step of exposing the photosensitive resin layer to a pattern; a kind of electronic device with high-pressure air-conditioning system
And developing the exposed photosensitive resin layer to form a resin pattern.
12. A method for manufacturing a circuit wiring includes, in order:
a step of bringing an outermost layer of the photosensitive transfer material according to any one of claims 1 to 10, which is on the side having the photosensitive resin layer with respect to the temporary support, into contact with a substrate and bonding the outermost layer;
a step of exposing the photosensitive resin layer to a pattern;
Developing the exposed photosensitive resin layer to form a resin pattern; a kind of electronic device with high-pressure air-conditioning system
And a step of etching the substrate in the region where the resin pattern is not arranged.
13. A method for manufacturing a touch panel, which comprises the following steps in order:
a step of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 10 on the side having the photosensitive resin layer with respect to the temporary support, by contacting the outermost layer with a substrate having a conductive layer;
a step of exposing the photosensitive resin layer to a pattern;
developing the exposed photosensitive resin layer to form a resin pattern; a kind of electronic device with high-pressure air-conditioning system
And a step of etching the substrate in the region where the resin pattern is not arranged.
CN202180052348.3A 2020-08-25 2021-08-12 Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel Pending CN116097171A (en)

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JP2005148236A (en) * 2003-11-12 2005-06-09 Fuji Photo Film Co Ltd Dry film photoresist
JP2006003436A (en) * 2004-06-15 2006-01-05 Fuji Photo Film Co Ltd Pattern forming material, pattern forming apparatus, and pattern forming method
CN102844709B (en) * 2010-04-15 2014-08-20 日合墨东株式会社 Photosensitive resin composition, photoresist film using same, method for forming resist pattern, and method for manufacturing printed wiring board
JP2016099374A (en) * 2014-11-18 2016-05-30 日立化成株式会社 Photosensitive element, method for manufacturing substrate with resist pattern, method for manufacturing printed wiring board, and method for manufacturing touch panel
JP6832899B2 (en) * 2018-02-05 2021-02-24 富士フイルム株式会社 Photosensitive transfer material, circuit wiring manufacturing method, and touch panel manufacturing method
WO2020203502A1 (en) * 2019-04-05 2020-10-08 富士フイルム株式会社 Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring line, and method for producing touch panel

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