CN116235111A - 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
CN116235111A
CN116235111A CN202180063610.4A CN202180063610A CN116235111A CN 116235111 A CN116235111 A CN 116235111A CN 202180063610 A CN202180063610 A CN 202180063610A CN 116235111 A CN116235111 A CN 116235111A
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Prior art keywords
resin layer
photosensitive resin
compound
meth
mass
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片山晃男
有富隆志
望月英宏
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/004—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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Human Computer Interaction (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (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 photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound and a photopolymerization initiator, wherein the photosensitive resin layer is used for mJ/cm 2 The width (W) of the double bond reaction region after exposure of the line and space pattern of 10 μm/10 μm in terms of exposure dose (Ep) per unit time was 3 hours 3 ) Width of double bond reaction region (W) with passage of 24 hours 24 ) Satisfy W 24 /W 3 ≤1.05。

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 wiring of a peripheral wiring portion, and a 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, a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate through a mask having a desired pattern by using a photosensitive transfer material and then developing the exposed layer is widely used.
As a conventional photosensitive resin composition, a composition described in patent document 1 is known.
Patent document 1 discloses a photosensitive resin composition characterized in that after an exposure curing reaction is performed so that the reaction rate of an ethylenically unsaturated compound contained as a photosensitive component in an exposure surface becomes 70%, the reaction rate of the unsaturated compound of the entire plate remains substantially unchanged when the plate is stored in a dark place, and the difference between the partial reaction rates in the exposure surface and the non-exposure surface remains 20% or more after 24 hours.
Patent document 1: japanese patent laid-open No. 2001-356493
Disclosure of Invention
Technical problem to be solved by the invention
In a wiring formation process using a photosensitive transfer material, when a photosensitive resin layer bonded to a substrate having a conductive layer is exposed, a difference may occur in the time elapsed from the completion of exposure to development in each photosensitive resin layer, and the difference may be about several hours in some cases. In addition, the exposed photosensitive resin layer may not be immediately developed but left for a certain period of time, and in this case, the elapsed time from the completion of exposure may be further prolonged. In particular, in the case of performing the roll-to-roll process, since the time required for transferring from the roll unwinding section to the roll core section is long after the exposure, the time tends to be long.
An object of an embodiment of the present invention is to provide a photosensitive transfer material in which a change in line width of a resin pattern is small with the lapse of a post-exposure standing time.
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 means for solving the above problems.
<1>A photosensitive transfer material, comprising: a temporary support; and a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound and a photopolymerization initiator, wherein the photosensitive resin layer is used for mJ/cm 2 The width W of the double bond reaction region after exposure of the line and space pattern of 10 μm/10 μm with the exposure dose Ep of unit time of 3 hours 3 Width of double bond reaction region W after 24 hours 24 Satisfy W 24 /W 3 ≤1.05。
W 3 W and W 24 The width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material,
the above Ep satisfies ep=2×eb,
the Eb is set to be 20mW/cm of illuminance through a 15-step wedge (stepwedge) after the photosensitive resin layer is attached to the substrate 2 Is exposed to 180mJ/cm 2 Exposure is performed to give an exposure amount of an order of + -1% of a residual layer thickness of the developed photosensitive resin layer。
<2> the photosensitive transfer material according to <1>, wherein,
the double bond reaction area width W after 3 hours after exposing the photosensitive resin layer to the light Ep in a line and space pattern of 10 μm/10 μm 3 Width of double bond reaction region W at 72 hours 72 Satisfy W 72 /W 3 ≤1.10。
W 72 The width of the double bond reaction region obtained by the secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material was set.
<3> the photosensitive transfer material according to <1> or <2>, wherein,
the above-mentioned ethylenically unsaturated compound contains an ethylenically unsaturated compound having a bisphenol structure.
<4> the photosensitive transfer material according to any one of <1> to <3>, wherein,
the photopolymerization initiator includes a bisimidazole compound and a benzophenone compound.
<5> the photosensitive transfer material according to any one of <1> to <4>, wherein,
the photosensitive resin layer further includes a polymerization inhibitor.
<6> the photosensitive transfer material according to <5>, wherein,
the polymerization inhibitor contains at least 1 compound selected from phenothiazine, phenoxazine and a compound having a hindered phenol structure.
<7> the photosensitive transfer material according to <5> or <6>, wherein,
when the content of the photopolymerization initiator in the photosensitive resin layer is Rc and the content of the polymerization inhibitor is Rd, the mass ratio Rd/Rc is 0.02 to 0.1.
<8> the photosensitive transfer material according to <7>, wherein,
the mass ratio Rd/Rc is 0.03 to 0.05.
<9> 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 <8> 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.
<10> the method for producing a resin pattern according to <9>, wherein,
at least a part of the resin pattern includes a line-space pattern, and at least 1 group of lines and spaces in the line-space pattern have a total width of 20 μm or less.
<11> 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 <8> 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.
<12> 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 <8> 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 having a small change in line width of a resin pattern with the lapse of a post-exposure standing time 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 diagram showing an example of the structure of a photosensitive transfer material according to the first embodiment.
Fig. 2 is a schematic diagram showing an example of the structure of the photosensitive transfer material according to the second embodiment.
Fig. 3 is a schematic plan view showing the pattern a.
Fig. 4 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 unsubstituted and unsubstituted labels include groups having no substituent and groups having substituents. For example, "alkyl" means to include not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, in the present specification, "exposure" means 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 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 two or more preferred embodiments is a more preferred embodiment.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are the following molecular weights unless otherwise specified: the samples were measured by a Gel Permeation Chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel 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.
In the present specification, "total solid component" means the total mass of components after removal of solvent from the total composition of the composition. As described above, the term "solid component" means a component from which the solvent has been removed, and may be solid or liquid at 25 ℃.
(photosensitive transfer Material)
The photosensitive transfer material according to the present invention comprises: a temporary support; and a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound and a photopolymerization initiator, wherein the photosensitive resin layer is used for mJ/cm 2 Exposure to light of 10 μm/10 in units of exposure quantity EpWidth W of double bond reaction region after 3 hours after line and space pattern of μm 3 Width of double bond reaction region W after 24 hours 24 Satisfy W 24 /W 3 ≤1.05。
W 3 W and W 24 The width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material,
the above Ep satisfies ep=2×eb,
eb is set to be 20mW/cm of illuminance passing through the 15-step wedge after the photosensitive resin layer is attached to the substrate 2 Is exposed to 180mJ/cm 2 Exposure is performed to give an exposure amount of an order of ±1% of the residual layer thickness of the developed photosensitive resin layer.
As a result of the detailed study by the present inventors, the present inventors have found that there is a problem in that, in a photosensitive transfer material having a conventional negative photosensitive resin layer formed from the photosensitive resin composition described in patent document 1, the line width of the resin pattern greatly varies with the lapse of the standing time after exposure.
In the photosensitive transfer material according to the present invention, the photosensitive resin layer is used as mJ/cm 2 The width W of the double bond reaction region after exposure of the line and space pattern of 10 μm/10 μm with the exposure dose Ep of unit time of 3 hours 3 Width of double bond reaction region W after 24 hours 24 Satisfy W 24 /W 3 As described above, the photosensitive resin layer having a small temporal change in the width of the double bond reaction region is sufficiently suppressed from reacting in the half-exposed portion at the end of the exposed region, and the difference between the polymerization reactivity of the exposed region and the polymerization reactivity of the unexposed region becomes large. Therefore, the following is estimated: even if there is a slight variation in development conditions such as the post-exposure set time, dissolution in developing the region where the polymerization reaction is sufficiently performed is suppressed, and a change in line width of the resin pattern (also referred to as a "set time line width change") with the passage of the post-exposure set time is small.
The invention relates to a photosensitive transferIn the printing material, the photosensitive resin layer is used for mJ/cm 2 The width W of the double bond reaction region after exposure of the line and space pattern of 10 μm/10 μm with the exposure dose Ep of unit time of 3 hours 3 Width of double bond reaction region W after 24 hours 24 Satisfy W 24 /W 3 ≤1.05。
W 3 W and W 24 The width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material,
the above Ep satisfies ep=2×eb,
eb is set to be 20mW/cm of illuminance passing through the 15-step wedge after the photosensitive resin layer is attached to the substrate 2 Is exposed to 180mJ/cm 2 Exposure is performed to give an exposure amount of an order of ±1% of the residual layer thickness of the developed photosensitive resin layer.
The photosensitive transfer material according to the present invention preferably satisfies W from the viewpoints of a change in line width over time, a change in line width of a resin pattern accompanying a change in development temperature (also referred to as "development temperature line width change"), and sensitivity 24 /W 3 Less than or equal to 1.04, more preferably meeting W 24 /W 3 Less than or equal to 1.03, particularly preferably less than or equal to 1.00 and less than or equal to W 24 /W 3 ≤1.03。
In the photosensitive transfer material according to the present invention, the photosensitive resin layer is exposed to the exposure Ep in a line and space pattern of 10 μm/10 μm from the viewpoint of the change in the line width of the holding time and the change in the line width of the developing temperature, and then the double bond reaction region width W is 3 hours after that 3 Width of double bond reaction region W at 72 hours 72 Preferably satisfy W 72 /W 3 Less than or equal to 1.15, more preferably meeting W 72 /W 3 Less than or equal to 1.10, particularly preferably less than or equal to 1.00 and less than or equal to W 72 /W 3 ≤1.10。
In addition, W 72 The width of the double bond reaction region obtained by the secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material was set.
The following shows the method for measuring Eb and the method for calculating Ep in the present invention.
The photosensitive transfer material was laminated on a substrate (a substrate obtained by producing a 200nm thick copper layer on a 100 μm polyethylene terephthalate (PET) film by sputtering) using a sheet laminator. The lamination conditions were set at a roll temperature of 100℃and a lamination speed of 2 m/min and a lamination pressure of 0.5MPa.
A 15-step wedge (Fujifilm Corporation) was placed on a temporary support of the laminated photosensitive transfer material, and 20mW/cm was used 2 180mJ/cm of high-pressure mercury lamp 2 Is a single-layer exposure. After exposure, the support was peeled off, developed with a 25℃aqueous solution of 0.9% by mass sodium carbonate for 30 seconds, and Eb was obtained from the residual film thickness in each step (indicating that the photosensitive resin layer was attached to the substrate and then passed through an illuminance of 20mW/cm with a 15-step wedge therebetween 2 Is exposed to 180mJ/cm 2 Exposure is performed to give an exposure amount of the order of the remaining layer thickness of ±1% of the layer thickness of the photosensitive resin layer after development).
And, by the Eb (mJ/cm) 2 ) Ep (mJ/cm) was calculated using the following formula 2 )。
Ep＝2×Eb
The width W of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material in the present invention is shown below 3 、W 24 W and W 72 Is a measurement method of (2).
The photosensitive transfer material was laminated on a substrate (a substrate obtained by producing a copper layer of 200nm thickness on a 100 μm pet film by sputtering) using a sheet laminator. The lamination conditions were set at a roll temperature of 100℃and a lamination speed of 2 m/min and a lamination pressure of 0.5MPa.
The line was brought into contact with a photomask having a space=10 μm/10 μm and a temporary support, and the line was brought into contact with a photomask having a space of ep=2×eb (mJ/cm) 2 ) Exposing the photosensitive transfer material laminated on the substrate. After exposure for 3 hours, 24 hours or 72 hours, the temporary support, thermoplastic resin layer and intermediate layer were peeled off with an adhesive tape, and 5mL of bromine water (0.2%) was separated in a 50mL container, andthe sample was fixed in the vessel without contacting the separated liquid, and left standing at room temperature (25 ℃) for 5 minutes. After that, the solution was stored under high vacuum for half a day to degas the residual bromine. Thus, a sample in which a carbon-carbon double bond was bromine-modified was produced.
The sample was analyzed by secondary ION mass spectrometry (SIMS 5 from ION-TOF Co., ltd., primary ION source: bi) 3+ (30 kV), measurement range: 50mm, area resolution: 512×512pixel, integration: 32 times, measurement mode: high spatial resolution mode (Fast Imaging: fast Imaging), charged correction: using electron gun), evaluation C 2 HBr - Width of the region. Determination 3C 2 HBr - The width of the portion with small strength was obtained by taking the average of the measured values at 3 places and was defined as the width W of the region where polymerization was performed 3 、W 24 Or W 72 。
The value of Eb in the photosensitive transfer material according to the present invention is preferably 20mJ/cm from the viewpoints of change in line width over time, change in line width at development temperature, and sensitivity 2 ～200mJ/cm 2 More preferably 30mJ/cm 2 ～150mJ/cm 2 Further preferably 35mJ/cm 2 ～100mJ/cm 2 Particularly preferably 35mJ/cm 2 ～70mJ/cm 2 。
Further, W in the photosensitive transfer material according to the present invention is from the viewpoints of a change in the line width of the holding time, a change in the line width of the developing temperature, and sensitivity 3 The value of (2) is preferably 9.0 μm to 10.5. Mu.m, more preferably 9.2 μm to 10.3. Mu.m, particularly preferably 9.5 μm to 10.2. Mu.m.
From the viewpoints of change in line width of standing time, change in line width of developing temperature, and sensitivity, W in the photosensitive transfer material according to the present invention 24 The value of (2) is preferably 9.0 μm to 11.0. Mu.m, more preferably 9.3 μm to 10.7. Mu.m, particularly preferably 9.5 μm to 10.5. Mu.m.
From the viewpoints of change in line width of standing time, change in line width of developing temperature, and sensitivity, W in the photosensitive transfer material according to the present invention 72 The value of (2) is preferably 9.0 μm to 12.0. Mu.m, more preferably 9.5 μm to 11.5. Mu.m, particularly preferably 9.7 μm to 11.0. Mu.m.
The photosensitive transfer material of the present invention comprises a temporary support and a photosensitive resin layer containing an alkali-soluble resin, 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.
An example of the photosensitive transfer material according to the present invention is shown below, but is not limited thereto.
(1) "temporary support/photosensitive resin layer/refractive index adjustment layer/protective film"
(2) "temporary support/photosensitive resin layer/protective film"
(3) "temporary support/intermediate layer/photosensitive resin layer/protective film"
(4) "temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer/protective film"
In each of the above structures, the photosensitive resin layer is preferably a negative photosensitive resin layer. The photosensitive resin layer is preferably a colored resin layer. As described later, the photosensitive transfer material according to the present invention can be used as a photosensitive transfer material for a wiring protective film or as a photosensitive transfer material for an etching resist.
In the case of using the photosensitive transfer material for a wiring protective film, the photosensitive transfer material is preferably, for example, the structure (1) or (2) described above.
In the case of using the photosensitive transfer material for an etching resist, the photosensitive transfer material is preferably, for example, the structures (2) to (4) described above.
In the case where the photosensitive transfer material has a structure in which the photosensitive resin layer further has another layer on the side opposite to the temporary support side, the total thickness of the other layers disposed on the side opposite to the temporary support side of the photosensitive resin layer is preferably 0.1% to 30%, more preferably 0.1% to 20%, with respect to the layer thickness of the photosensitive resin layer.
Hereinafter, a photosensitive transfer material according to the present invention will be described by taking a specific example of an embodiment. The photosensitive transfer material according to the first embodiment described below can be preferably used as a photosensitive transfer material for an etching resist, and the photosensitive transfer material according to the second embodiment described below can be preferably used as a photosensitive transfer material for a wiring protective film.
[ photosensitive transfer material of the first embodiment ]
Hereinafter, a photosensitive transfer material according to a first embodiment will be described by way of example.
The photosensitive transfer material 20 shown in fig. 1 includes, in order, a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, an intermediate layer 15, and a photosensitive resin layer 17, and a protective film 19.
The photosensitive transfer material 320 shown in fig. 1 is configured to have the protective film 19, but the protective film 19 may not be provided.
The photosensitive transfer material 20 shown in fig. 1 is configured such that the thermoplastic resin layer 13 and the intermediate layer 15 are disposed, but the thermoplastic resin layer 13 and the intermediate layer 15 may not be disposed.
The following describes the respective elements constituting the photosensitive transfer material of the first embodiment.
[ 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.
In addition, the transmittance of the layer of the photosensitive transfer material, the ratio of the intensity of the light emitted through the layer when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction) to the intensity of the incident light was measured using MCPD Series manufactured by ltd.
Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and the resin film is preferable from the viewpoints of strength, flexibility, and light transmittance.
Examples of the resin film include polyethylene terephthalate (PET: polyethylene terephthalate) 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 a temporary supportIn view of the pattern formability at the time of pattern exposure 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 embodiments 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 according to 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 resin, an ethylenically unsaturated compound, and a photopolymerization initiator, and preferably contains an alkali-soluble resin, an ethylenically unsaturated compound, a bisimidazole compound, and a benzophenone compound, more preferably contains an alkali-soluble resin, an ethylenically unsaturated compound, a hexaarylbisimidazole compound, and a benzophenone compound, from the viewpoints of a change in a line width of a standing time, a change in a line width of a developing temperature, and sensitivity.
Further, the photosensitive resin layer preferably further contains a polymerization inhibitor from the viewpoints of a change in line width in standing time, a change in line width in developing temperature, and sensitivity.
The photosensitive resin layer preferably contains an alkali-soluble resin with respect to 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 resin >
The photosensitive resin layer includes an alkali-soluble resin.
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 resin is not particularly limited, and for example, a known alkali-soluble resin used for an etching resist can be preferably used.
And, the alkali-soluble resin is preferably a binder polymer.
As the alkali-soluble resin, an alkali-soluble resin having an acid group is preferable.
Among them, the alkali-soluble resin is preferably a polymer a described later.
Polymer A-
As the alkali-soluble resin, polymer a is preferably contained.
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, particularly 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 based on the total mass of the total monomer components, 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.
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 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 particularly preferably 90% by mass or more, relative to the whole of the polymer a.
The polymer a may have a branched structure or an alicyclic structure in a side chain. The polymer a may have a linear structure in a side chain. For example, a branched structure or an 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.
Examples of the monomer having a group having a branched structure in a 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 the above, isopropyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate are preferable, and isopropyl (meth) acrylate or tert-butyl (meth) acrylate are 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. As the monomer containing a group having an alicyclic structure in a side chain, for example, examples thereof include (meth) acrylic acid (bicyclo [ 2.2.1] heptyl-2) ester, (meth) acrylic acid-1-adamantyl ester, (meth) acrylic acid-2-adamantyl ester, (meth) acrylic acid-3-methyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid-3-ethyladamantanyl ester, (meth) acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid-3, 5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid-2-methyl-2-adamantyl ester, (meth) acrylic acid-2-ethyl-2-adamantyl ester, (meth) acrylic acid-3-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4, 7-methanoindene (meth) 5-yl ester, (meth) acrylic acid octahydro-4, 7-methylindenyl ester, 1-methyl (meth) acrylic acid-1-menthyl ester, tricyclodecane (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 the above, cyclohexyl (meth) acrylate, (norbornyl) acrylate, (iso-bornyl) acrylate, (1-adamantyl (meth) acrylate, (2-adamantyl (meth) acrylate, (fenchyl) acrylate, (1-menthyl (meth) acrylate and tricyclodecane (meth) acrylate are preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (iso-bornyl (meth) acrylate, (2-adamantyl (meth) acrylate and tricyclodecane (meth) acrylate are more preferable.
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 135℃or less. By using the polymer a having a Tg of 135 ℃ 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 130℃or lower, still more preferably 120℃or lower, and particularly preferably 110℃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 the alkali-soluble resin.
Examples of the resin other than the alkali-soluble resin include acrylic resins, styrene-acrylic copolymers (wherein the styrene content is 40 mass% or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
The alkali-soluble resin may be used alone or in combination of 2 or more.
The proportion of the alkali-soluble resin 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 resin 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 resin 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 "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 above-described alkali-soluble resin.
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.
Further, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having a bisphenol structure from the viewpoints of a change in line width in standing time, a change in line width at developing temperature, and sensitivity.
As the ethylenically unsaturated compound having a bisphenol structure, an ethylenically unsaturated compound B1 having a bisphenol structure described below can be preferably exemplified.
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 more 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 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 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 may have only 1 aromatic ring or may have 2 or more aromatic rings.
The ethylenically unsaturated compound 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 having a bisphenol structure include a compound 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 bisphenol structure of an ethylenically unsaturated compound is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated herein by reference.
As the ethylenically unsaturated compound groveling, 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 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitachi 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-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical, manufactured by NK-37co.), and bis (NK-10, manufactured by NK-10, ltd.) phenol.
The ethylenically unsaturated compound preferably contains a compound represented by the following formula (Bis) from the viewpoints of line width change in time of placement, line width change in development temperature, and sensitivity.
[ chemical formula 1]
Figure BDA0004129129940000201
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 Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even 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 groveling.
The ethylenically unsaturated compounds other than the ethylenically unsaturated compound groveling 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 Fine Chemical Co., ltd.), UA-32P (Shin-Nakamura Chemical Co., ltd.), and UA-1100H (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 compound and an ethylenically unsaturated compound having 3 or more functions, and more preferably contains the above-mentioned ethylenically unsaturated compound and an ethylenically unsaturated compound having 2 or more functions and having 3 or more functions. 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 groveling): (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 aspect, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound groveling 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-ALLNEX LTD, EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., ltd., A-GLY-9E, etc.), ARONIX (registered trademark) T0-2349 (AGEI CO., LTD, manufactured), ARONIX M-520 (LTOSEI CO., TOAGEI) and TOID, manufactured by TOOTID, TOOTD 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 in the photosensitive resin layer to the content Mb of the alkali-soluble resin 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 distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound groveling is preferably 200 to 3,000, more preferably 280 to 2,200, and further 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. The photopolymerization initiator of the present invention further contains a sensitizer.
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 -hydroxyalkyl benzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a bisimidazole compound.
Among them, the photopolymerization initiator preferably contains a biimidazole compound, more preferably contains a biimidazole compound and a benzophenone compound, from the viewpoints of a change in line width over time, a change in line width at development temperature, and sensitivity.
Further, as the bisimidazole compound, a hexaarylbisimidazole compound is preferably used.
Examples of the bisimidazole 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 photosensitive resin layer may contain 1 kind of biimidazole compound alone as a photopolymerization initiator, or may contain 2 or more kinds.
The content of the biimidazole compound is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% to 10 mass%, and particularly preferably 5 mass% to 10 mass% with respect to the total mass of the photosensitive resin layer, from the viewpoints of change in the line width over time, change in the line width at the development temperature, and sensitivity.
The photopolymerization initiator preferably contains a benzophenone compound, more preferably a dialkylaminobenzophenone compound, from the viewpoints of change in line width over time, change in line width at development temperature, and sensitivity.
As the benzophenone compound, for example, examples include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4' -bis (dimethylamino) benzophenone, and 4,4' -bis (dicyclohexylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -bis (dihydroxyethylamino) benzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 4' -dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4 ' -methylphenylsulfide, and the like.
The photosensitive resin layer may contain 1 kind of benzophenone compound alone as a photopolymerization initiator, or may contain 2 or more kinds.
The content of the benzophenone compound is preferably 0.05 to 5 mass%, more preferably 0.1 to 2 mass%, even more preferably 0.2 to 1.5 mass%, and particularly preferably 0.4 to 0.8 mass% with respect to the total mass of the photosensitive resin layer from the viewpoints of change in line width over time, change in line width at development temperature, and sensitivity.
In the case where the photopolymerization initiator contains a bisimidazole compound and a benzophenone compound, the content of the benzophenone compound is preferably smaller than the content of the bisimidazole compound from the viewpoints of line width change in time of placement, line width change in development temperature, and sensitivity.
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 trade name) 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 0XE-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, manufactured by IGM Resins B.V. manufactured by Omni), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl } -2-Omni-phenyl) methyl ] -1-butanone (trade name: omni-4-morpholino-methyl ] -1-butanone (trade name: omni 379EG,IGM Resins B.V. Manufactured by Omni, and 3-yl) 2-morpholino-1-one (trade name: om-2-hydroxy-2-methylpropanoyl) benzyl ] -2- (3-yl) butanone (manufactured by BASF) 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.), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651, IGM Resins b.v.), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (trade name: omnirad TPO H, IGM Resins b.v.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnired 819, IGM Resins b.v.), oxime ester-based photopolymerization initiator (trade name: lunar 6, DKSH Holding ltd. Times.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford corporation) and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, 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. In addition, for the photo-cation polymerization initiator which does not directly induce the activating light with the wavelength of 300nm or more, the compound may be used in combination with a sensitizer, and may be preferably used as long as it generates an acid by sensing an activating light having a wavelength of 300nm or more.
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 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 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 "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 the dye in a color developed state is decolorized by an acid, a base or a radical, a method in which the dye in a decolorized state is developed by an acid, a base or a radical, and a method in which the 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 to light and causing a reaction, or a coloring matter which changes the state of color development or decoloration by changing the state (for example, pH) in the photosensitive resin layer by an acid, an alkali or a radical. Further, the coloring matter may be a coloring matter which is not exposed to light but is directly stimulated by an acid, an alkali or a radical to change 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, the coloring matter N is preferably a coloring matter that develops color by an acid, an alkali or a radical from the viewpoint of visibility of the exposed portion and the non-exposed portion.
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 (photo acid generator) or a photo alkali 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 photo alkali 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, still 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 1 maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development, or may have 2 or more. When the dye N has a maximum absorption wavelength in the wavelength range of 400nm 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 developed 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 changed to a closed-loop state to be decolorized, or the colorless compound is changed to an open-loop state to be developed. 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 developed by free radical or acid ring opening is preferable, and a compound having a lactone ring and the lactone ring is developed 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 (brillon green), ethyl violet, methyl green, crystal violet, basic fuchsine (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metandine yellow (metandil yellow), thymol sulfophthalein (thymol sulfonphthalein), xylenol blue, methyl orange, para-methyl red, congo red, benzored violet (4B, alpha-naphthalene red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), paragood red (parafuchsin), victoria pure blue (victoria pure blue) -naphthalene sulfonate, victoria pure blue (Hodogaya Chemical co., ltd), oil blue #603 (Orient Chemical Industries co., ltd), oil pink #312 (Orient Chemical Industries co., ltd), oil red 5B (Orient Chemical Industries co., ltd), oil scarlet #308 (Orient Chemical Industries co., ltd), oil red OG (Orient Chemical Industries co., ltd), oil red RR (0 rient Chemical Industries Co, ltd), oil green #502 (Orient Chemical Industries co., ltd), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co., ltd), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, gold amine, 4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyl iminonaphthoquinone, gold amine, 2-carboxyoctadecylamino-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-dimethoxyfluoran, 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) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-anilino-fluoran, and 4-dimethylamino-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 whose color is developed 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.
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%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative 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%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative 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 Japan ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated, thereby generating radicals and bringing all the pigments into a color development 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 Corporation), and a calibration curve was prepared.
Next, absorbance of the solution in which all the pigments were developed 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.
< polymerization inhibitor >
The photosensitive resin layer preferably further contains a polymerization inhibitor from the viewpoints of storage stability, change in line width over time, and change in line width at development temperature.
The polymerization inhibitor preferably contains a radical polymerization inhibitor.
The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used.
Examples of the polymerization inhibitor include phenothiazine, phenoxazine, hydroquinone, tetrachlorobenzoquinone, sodium phenoindophenol, m-aminophenol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenyl hydroxylamine salt (ammonium salt, cerium salt, etc.), 2, 6-tetramethylpiperidine-1-oxyl, etc. In addition, the polymerization inhibitor may also function as an antioxidant.
Further, examples of the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784.
Examples of the other 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.
Among them, the polymerization inhibitor is preferably one containing at least 1 compound selected from the group consisting of phenothiazine, phenoxazine, and a compound having a hindered phenol structure, more preferably one containing at least 1 compound selected from the group consisting of phenothiazine and phenoxazine, and particularly preferably one containing phenothiazine, from the viewpoints of storage stability, change in line width over time, change in line width at development temperature, and sensitivity.
The polymerization inhibitor may be used alone or in combination of 2 or more.
The content of the polymerization inhibitor is preferably 0.005 to 2 mass%, more preferably 0.01 to 1 mass%, even more preferably 0.05 to 0.5 mass%, and particularly preferably 0.2 to 0.4 mass% based on the total mass of the photosensitive resin layer, from the viewpoints of storage stability, change in line width over time, change in line width at development temperature, and sensitivity.
When the content of the photopolymerization initiator in the photosensitive resin layer is Rc and the content of the polymerization inhibitor is Rd, the value of the mass ratio Rd/Rc is preferably 0.01 to 0.2, more preferably 0.02 to 0.1, even more preferably 0.03 to 0.05, from the viewpoints of change in line width over time, change in line width at development temperature, and sensitivity.
< thermally crosslinkable Compound >
The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as an ethylenically unsaturated compound but is treated as a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound. Among them, blocked isocyanate compounds are preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
Since the blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group, for example, in the case where the alkali-soluble resin and/or the ethylenically unsaturated compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the film formed is reduced, and the function when the film obtained by curing the photosensitive resin layer is used as a protective film tends to be enhanced.
The blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".
The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100℃to 160℃and more preferably 130℃to 150 ℃.
The dissociation temperature of the blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured using a differential scanning calorimeter and analyzed by DSC (Differential scanning calorimetry: differential scanning calorimeter)".
As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments inc (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited thereto.
Examples of the blocking agent having a dissociation temperature of 100℃to 160℃include active methylene compounds [ malonic acid diesters (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc. ] ], oxime compounds (formaldehyde oxime, aldoxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, etc. ] having a structure represented by-C (=N-OH) -, in the molecule).
Among these, as the blocking agent having a dissociation temperature of 100 to 160 ℃, for example, an oxime compound is preferably contained from the viewpoint of storage stability.
For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesion to the transfer object, and the like.
The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, subjecting hexamethylene diisocyanate to isocyanurate protection.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferable from the viewpoint of easier setting of the dissociation temperature within a preferable range and easier reduction of development residues than a compound having no oxime structure.
The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferable.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, (meth) acrylamide group and styryl group, and a group having an epoxy group such as a glycidyl group.
Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and further preferably an acryloyloxy group.
As the blocked isocyanate compound, commercially available ones can be used.
Examples of the commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, etc. (the above is made by SHOWA DENKO K.K.), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, etc., asahi Kasei Chemicals Corporation).
As the blocked isocyanate compound, a compound having the following structure can be used.
[ chemical formula 2]
Figure BDA0004129129940000331
The thermally crosslinkable compound may be used alone or in combination of 1 or 2 or more.
When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the photosensitive resin layer.
< other ingredients >
The photosensitive resin layer may contain components other than the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, the pigment, the polymerization inhibitor, and the thermally crosslinkable compound.
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, and nonionic surfactants are preferable.
Examples of the surfactant include surfactants described in paragraphs 0060 to 0071 of JP-A-2009-237362 in paragraph 0017 of JP-A-4502784.
As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.
As a commercial product of the fluorine-based surfactant, for example, examples of the materials include Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, 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, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, F-565, and EXP.MFS-578R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above DIC Corporation), fluorad (trade name) FC430, FC431, FC171 (above Sumitomo 3M Limited), surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above AGC Inc. system), polyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (above OMNOVA Solutions Inc. system), ftergent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by Neos Company Limited above), U-120E (Uni-chem Co., ltd.), and the like.
The fluorine-based surfactant may preferably be an acrylic compound having a molecular structure including a functional group containing a fluorine atom, and the fluorine atom may be volatilized by cutting a portion of the functional group containing a fluorine atom when heat is applied. Examples of the fluorine-containing surfactant include Megafac (trade name) DS series (chemical industry daily report (2016, 2, 22 days), daily necessities, news (2016, 2, 23 days)) manufactured by DIC Corporation, for example Megafac (trade name) DS-21.
The fluorine-based surfactant is preferably a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound, each of which has a fluorinated alkyl group or a fluorinated alkylene ether group.
The fluorine-based surfactant may be a block polymer. The fluorine-containing surfactant may preferably be a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom, and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).
The fluorine-based surfactant may be a fluoropolymer having an ethylenically unsaturated group in a side chain. Examples of the "Megafac" (trade name) include RS-101, RS-102, RS-718K, RS-72-K (DIC Corporation).
Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol octacosanoate, sorbitan fatty acid ester, pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (trade name) manufactured by BASF corporation), tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYOPALAT WE 3323 (trade name) manufactured by BASF corporation), solsperse (trade name) 20000 (trade name) manufactured by Lubrizol Japan Limited, NCW-101, NCW-1001, NCW-1002 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-1105, D-6112, D-6161, and/or the like, and the range of which is manufactured by Talcin, such as Talcum.g., talcum.15, talcum.375, talcum.37.15, talcum.375, talcum.Ln.375, talcum.Ln.Ln.Lvy.5.
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.
The silicone surfactant includes a linear polymer composed of siloxane bonds, and a modified siloxane polymer having an organic group introduced into a side chain or a terminal thereof.
Specific examples of the silicone surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (manufactured by DIC Corporation, supra), DOWSIL (trade name) 8032ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicone SH PA, toray Silicone SH8400 (Dow Corning Toray Co., supra), ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354-A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, 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-621, KP-626, KP-652 (above, et-su Co.); ltd), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured above as Momentive Performance Materials inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (the above is manufactured by BYK Chemie corporation), and the like.
In recent years, since environmental suitability of compounds having a linear perfluoroalkyl group having 7 or more carbon atoms is a concern, surfactants using a substitute for perfluorooctane acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are preferably used.
The photosensitive 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%, 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 plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide and the like), purine bases (adenine and the like) and solvents. The photosensitive resin layer may contain 1 kind of each additive alone or 2 or more kinds of additives.
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.
The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass% based on the total mass of the photosensitive resin layer. 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 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.
< impurities etc.)
The photosensitive resin layer may contain a prescribed amount of impurities.
Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, the halide ion, sodium ion and potassium ion are easily mixed as impurities, and therefore, the following contents are preferable.
The content of impurities in the photosensitive resin layer is preferably 80ppm or less, more preferably 10ppm or less, and further preferably 2ppm or less on a mass basis. The content of the impurities may be 1ppb or more or 0.1ppm or more on a mass basis.
Examples of the method for setting the impurity in the above range include a method for selecting a raw material having a small impurity content as a raw material of the composition, a method for preventing the impurity from being mixed in when the photosensitive resin layer is produced, and a method for cleaning and removing the same. In this way, the impurity amount can be set within the above range.
The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma: inductively coupled plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.
The photosensitive resin layer preferably contains a small amount of a compound such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane. The content of these compounds relative to the total mass of the photosensitive resin layer is preferably 100ppm or less, more preferably 20ppm or less, and still more preferably 4ppm or less on a mass basis.
The lower limit may be 10ppb or more or 100ppb or more relative to the total mass of the photosensitive resin layer on a mass basis. These compounds can be suppressed in content by the same method as the impurities of the above metals. Further, the quantitative determination can be performed by a known measurement method.
The water content in the photosensitive resin layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, from the viewpoint of improving reliability and lamination.
< residual monomer >
The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the alkali-soluble resin.
The content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, relative to the total mass of the alkali-soluble resin, from the viewpoints of patterning property and reliability. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
From the viewpoints of patterning properties and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.
The residual monomer amount of the monomer in synthesizing the alkali-soluble resin by the polymer reaction is also preferably set within the above range. For example, in the case of synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set within the above range.
The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.
< physical Properties etc.)
The layer thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and particularly preferably 1 μm or more and 5 μm or less from the viewpoints of developability 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 Electron 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 even 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 resin, 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 resin, 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 resin, 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. More preferably, the solvent mixture contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 selected from the group consisting of a ketone solvent and a cyclic ether solvent, and still more preferably contains at least 3 selected from the group consisting of at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent.
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 the application of the photosensitive resin composition is preferably 50 to 1 part 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 a printing method, a spraying method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (i.e., a slit coating method).
The photosensitive resin layer may be formed by applying a photosensitive resin composition to a protective film described later and drying the same.
As a method for drying the coating film of the photosensitive resin composition, heat drying and reduced pressure drying are preferable.
The drying temperature is preferably 80℃or higher, more preferably 90℃or higher. The upper limit is preferably 130℃or lower, more preferably 120℃or lower. The temperature can be continuously changed to be dried.
The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and still more preferably 60 seconds or longer. The upper limit is not particularly limited, but is preferably 600 seconds or less, more preferably 300 seconds or less.
[ 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, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, 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 resin 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") whose maximum absorption wavelength at the wavelength range of 400nm to 780nm at the time of color development is 450nm or more, and whose 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 pigment B is a content of the pigment when all the pigments B contained in the thermoplastic resin layer are in a color development 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 OXE 01 (trade name, BASF Japan ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated, whereby radicals were generated and all pigments were brought into a color development 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 Corporation), and a calibration curve was prepared.
Next, absorbance of the solution in which the pigment was developed entirely 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 3]
Figure BDA0004129129940000441
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 viewpoints of improvement of sensitivity to a light source and visibility of an exposed portion and a 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 part 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 polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether 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 method of attaching the protective film to the photosensitive resin layer or the like is not particularly limited, and a known method may be used.
Examples of the means for attaching the protective film to the photosensitive resin layer or the like include known laminators such as vacuum laminators and automatic cutting laminators.
The laminator preferably includes an arbitrary heatable roller such as a rubber roller and can perform pressurization and heating.
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, conductive films such as touch panels, electromagnetic shield materials, and 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 a photosensitive transfer material according to the present invention will be described below with reference to fig. 1. However, the photosensitive transfer material according to 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 a layer structure in an embodiment of the photosensitive transfer material according to the present invention. The photosensitive transfer material 20 shown in fig. 1 has a structure in which a temporary support 11, a thermoplastic resin layer 13, a water-soluble resin layer 15, a photosensitive resin layer 17, and a protective film 19 are laminated in this order.
As a method for producing the photosensitive transfer material 20, for example, a method including the steps of: a step of forming a thermoplastic resin layer 13 by applying a thermoplastic resin composition to the surface of the temporary support 11 and then drying a coating film of the thermoplastic resin composition; a step of forming a water-soluble resin layer 15 by applying a water-soluble resin layer composition to the surface of the thermoplastic resin layer 13 and then drying a coating film of the water-soluble resin layer composition; and a step of forming a photosensitive resin layer 17 by applying a photosensitive resin composition containing an alkali-soluble resin and an ethylenically unsaturated compound to the surface of the water-soluble resin layer 15 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 the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents; a water-soluble resin layer composition containing at least 1 selected from water and water-miscible organic solvents; and at least 1 photosensitive resin composition comprising an alkali-soluble resin, an ethylenically unsaturated compound, and at least one 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 water-soluble resin layer composition to the surface of the thermoplastic resin layer 13 and/or the mixing of the component contained in the thermoplastic resin layer 13 and the component contained in the water-soluble resin layer 15 during the storage of the laminate having the coating film of the water-soluble resin layer composition, and can suppress the application of the photosensitive resin composition to the surface of the water-soluble resin layer 15 and/or the mixing of the component contained in the water-soluble resin layer 15 and the component contained in the photosensitive resin layer 17 during the storage of the laminate having the coating film of the photosensitive resin composition.
The photosensitive transfer material 20 is manufactured by pressing the protective film 19 against the photosensitive resin layer 17 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 20 including the temporary support 11, the thermoplastic resin layer 13, the water-soluble resin layer 15, the photosensitive resin layer 17, and the protective film 19 by including a step of providing the protective film 19 so as to be in contact with the second surface of the photosensitive resin layer 17.
After the photosensitive transfer material 20 is manufactured by the above manufacturing method, the photosensitive transfer material 20 may be wound up to manufacture and store the 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.
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, conductive films such as touch panels, electromagnetic shield materials, and film heaters, liquid crystal sealing materials, and formation of structures in the micro-mechanical or micro-electronic fields.
The photosensitive transfer material of the first embodiment may preferably be a photosensitive resin layer including a colored resin layer containing a pigment.
The use of the colored resin layer is suitable for, for example, the use of forming colored pixels or black matrices such as color filters for liquid crystal display devices (LCDs) and solid-state imaging devices (CCDs) and CMOS (complementary metal oxide semiconductor: complementary metal oxide semiconductors), in addition to the above.
The method for coloring the resin layer other than pigment is the same as described above.
< pigment >
The photosensitive resin layer may be a colored resin layer containing a pigment.
In a liquid crystal display window included in recent electronic devices, a cover glass (cover glass) in which a black frame-like light shielding layer is formed on a rear surface peripheral edge portion of a transparent glass substrate or the like is sometimes mounted in order to protect the liquid crystal display window. In order to form such a light shielding layer, a colored resin layer may be used.
The pigment may be appropriately selected according to a desired hue, and may be selected from black pigments, white pigments, and color pigments other than black and white. Among them, in the case of forming a black pattern, a black pigment is preferably selected as the pigment.
As the black pigment, a known black pigment (organic pigment, inorganic pigment, or the like) can be appropriately selected as long as the effect in the present invention is not impaired. Among them, carbon black, titanium oxide, titanium carbide, iron oxide, graphite, and the like are preferable as black pigment from the viewpoint of optical density, and carbon black is particularly preferable. As the carbon black, carbon black having at least a part of the surface coated with a resin is preferable from the viewpoint of surface resistance.
From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm in terms of the number average particle diameter.
The particle diameter is an average value obtained by obtaining the particle diameter of any 100 particles from a photographic image of pigment particles taken by an electron microscope, taking into consideration the diameter of a circle having the same area as the area of the pigment particles, and averaging the obtained 100 particle diameters.
As the pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of jp 2005-007765 a can be used as the white pigment. Specifically, among the white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable as the inorganic pigment, titanium oxide or zinc oxide is more preferable, and titanium oxide is further preferable. The inorganic pigment is more preferably rutile-type or anatase-type titanium oxide, and particularly preferably rutile-type titanium oxide.
The surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more kinds of treatments. Thus, the catalytic activity of titanium oxide is suppressed, and heat resistance, gloss fading, and the like are improved.
From the viewpoint of reducing the thickness of the heated photosensitive resin layer, at least one of an alumina treatment and a zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both of the alumina treatment and the zirconia treatment are particularly preferable.
In addition, when the photosensitive resin layer is a colored resin layer, it is preferable that the photosensitive resin layer further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability. When the color pigment is contained, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of further excellent dispersibility.
Examples of the Color pigments include victoria pure blue BO (Color Index) (hereinafter c.i.) 42595, gold amine (c.i. 41000), fat black (fat black) HB (c.i. 26150), monolite yellow (mount black) GT (c.i. pigment yellow 12), permanent yellow (mount yellow) GR (c.i. pigment yellow 17), permanent yellow HR (c.i. pigment yellow 83), permanent carmine (permanent carmine) FBB (c.i. pigment red 146), bastarum red (hostaperm red) ESB (c.i. pigment violet 19), permanent ruby red (peri ruby) FBH (c.i. pigment red 11), faster pink (mount red) B sepia (c.i. pigment red 81), mofety blue (c.i. pigment red monastralfast blue), permanent yellow HR (c.i. pigment red 15), permanent red c.i. pigment red (c.i. pigment red 149), and black pigment c.i. pigment red (c.i. pigment red) 180, c.i. pigment red (c.i. pigment red) green (c.i. pigment red) 15, c.i. pigment red (c.i. pigment red) green (c.i. pigment red) red (c.i. red) 15). 1. C.i. pigment blue 15: 4. c.i. pigment blue 22, c.i. pigment blue 60, c.i. pigment blue 64, c.i. pigment violet 23, and the like. Among them, c.i. pigment red 177 is preferred.
When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3 mass% and 40 mass% or less, more preferably more than 3 mass% and 35 mass% or less, still more preferably more than 5 mass% and 35 mass% or less, and particularly preferably 10 mass% or more and 35 mass% or less, relative to the total mass of the photosensitive resin layer.
When the photosensitive resin layer contains a pigment other than a black pigment (white pigment and color pigment), the content of the pigment other than the black pigment is preferably 30 mass% or less, more preferably 1 mass% to 20 mass%, and still more preferably 3 mass% to 15 mass% with respect to the black pigment.
In the case where the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed of a photosensitive resin composition, the black pigment (preferably, carbon black) is preferably introduced into the photosensitive resin composition as a pigment dispersion.
The dispersion liquid can be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or carrier) and dispersing it with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle is a medium portion for dispersing the pigment when the pigment dispersion is prepared, and is in a liquid state, and includes a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.
The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor (attritor), a super mill, a dissolver (distolver), a homomixer (homomixer), and a sand mill (sand mill). Further, the fine grinding may be performed by mechanical grinding by friction. For the disperser and the fine pulverization, a description of "pigment dictionary" (manufactured by kubang, first edition, kuku shop, 2000, page 438, page 310) can be referred to.
[ photosensitive transfer Material of the second embodiment ]
Hereinafter, a photosensitive transfer material according to a second embodiment will be described by way of example.
The photosensitive transfer material 10 shown in fig. 2 includes, in order, a temporary support 1, a transfer layer 2 including a photosensitive resin layer 3 and a refractive index adjustment layer 5, and a protective film 7.
The photosensitive transfer material 10 shown in fig. 2 is configured such that the refractive index adjustment layer 5 is disposed, but the refractive index adjustment layer 5 may not be disposed.
The following describes the respective elements constituting the photosensitive transfer material of the second embodiment.
The temporary support and the protective film used in the photosensitive transfer material of the second embodiment are preferably the same as those of the photosensitive transfer material of the first embodiment.
[ photosensitive resin layer ]
The photosensitive transfer material has a photosensitive resin layer.
After the photosensitive resin layer is transferred onto the transfer target, exposure and development are performed, whereby a pattern can be formed on the transfer target.
Hereinafter, the components that can be contained in the photosensitive resin layer will be described in detail.
< alkali-soluble resin >
The photosensitive resin layer includes an alkali-soluble resin.
Examples of the alkali-soluble resin include (meth) acrylic resins, styrene resins, epoxy resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, epoxy acrylate resins obtained by the reaction of an epoxy resin with (meth) acrylic acid, and acid-modified epoxy acrylate resins obtained by the reaction of an epoxy acrylate resin with an acid anhydride.
As one of preferable embodiments of the alkali-soluble resin, a (meth) acrylic resin is given from the viewpoint of excellent alkali developability and film formability.
In addition, in the present specification, (meth) acrylic resin means a resin having a structural unit derived from a (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, with respect to all the structural units of the (meth) acrylic resin.
The (meth) acrylic resin may be composed of only structural units derived from the (meth) acrylic compound, or may have structural units derived from a polymerizable monomer other than the (meth) acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100 mass% or less with respect to all the structural units of the (meth) acrylic resin.
Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylonitrile.
Examples of the (meth) acrylic acid ester include alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-trifluoroethyl (meth) acrylate, and 2, 3-tetrafluoropropyl (meth) acrylate, and alkyl (meth) acrylates are preferable.
Examples of the (meth) acrylamide include acrylamide such as diacetone acrylamide.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.
The (meth) acrylic acid ester is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and more preferably methyl (meth) acrylate or ethyl (meth) acrylate.
The (meth) acrylic resin may have structural units other than those derived from the (meth) acrylic compound.
The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than a (meth) acrylic compound that can be copolymerized with a (meth) acrylic compound, and examples thereof include styrene, vinyl toluene, and α -methylstyrene, and other styrene compounds that may have a substituent at the α -position or an aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, and maleic acid monoesters such as fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid, and crotonic acid.
These polymerizable monomers may be used in combination of 1 or 2 or more.
Further, from the viewpoint of improving the alkali developability, the (meth) acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonate group.
Among them, the (meth) acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably has a structural unit derived from the above (meth) acrylic acid.
From the viewpoint of excellent developability, the content of the structural unit having an acid group (preferably, the structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is preferably 10 mass% or more with respect to the total mass of the (meth) acrylic resin. The upper limit is not particularly limited, but is preferably 50 mass% or less, more preferably 40 mass% or less, from the viewpoint of excellent alkali resistance.
Further, the (meth) acrylic resin more preferably has a structural unit derived from the above alkyl (meth) acrylate.
The content of the structural unit derived from the alkyl (meth) acrylate in the (meth) acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 90% by mass, relative to all the structural units of the (meth) acrylic resin.
The (meth) acrylic resin is preferably a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester, and more preferably a resin composed of only a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid alkyl ester.
The (meth) acrylic resin is also preferably an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate.
Further, from the viewpoint of further excellent effects of the present invention, the (meth) acrylic resin preferably has at least 1 selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate.
From the viewpoint of further excellent effects of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate in the (meth) acrylic resin is preferably 40 mass% or more, more preferably 60 mass% or more, with respect to all the structural units of the (meth) acrylic resin. The upper limit is not particularly limited, and may be 100 mass% or less, preferably 80 mass% or less.
Further, from the viewpoint of further excellent effects of the present invention, the (meth) acrylic resin preferably has at least 1 selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylate and at least 1 selected from the group consisting of structural units derived from acrylic acid and structural units derived from alkyl acrylate.
From the viewpoint of the more excellent effect of the present invention, the total content of the structural units derived from methacrylic acid and the structural units derived from alkyl methacrylate is preferably 60/40 to 80/20 in terms of mass ratio to the total content of the structural units derived from acrylic acid and the structural units derived from alkyl acrylate.
From the viewpoint of excellent developability of the photosensitive resin layer after transfer, the (meth) acrylic resin preferably has an ester group at the terminal.
The terminal part of the (meth) acrylic resin is composed of a part derived from a polymerization initiator used for synthesis. The (meth) acrylic resin having an ester group at the end can be synthesized by using a polymerization initiator that generates a radical having an ester group.
In addition, from the viewpoint of developability, the alkali-soluble resin is preferably, for example, an alkali-soluble resin having an acid value of 60mgKOH/g or more.
Further, for example, from the viewpoint of easy formation of a firm film by heat crosslinking with a crosslinking component, the alkali-soluble resin is more preferably a resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing resin), and further preferably a (meth) acrylic resin having a carboxyl group with an acid value of 60mgKOH/g or more (so-called carboxyl group-containing (meth) acrylic resin).
If the alkali-soluble resin is a resin having a carboxyl group, for example, the three-dimensional crosslink density can be increased by adding a thermally crosslinkable compound such as a blocked isocyanate compound to perform thermal crosslinking. Further, if the carboxyl group of the resin having a carboxyl group is dehydrated and rendered hydrophobic, the wet heat resistance can be improved.
The (meth) acrylic resin having an acid value of 60mgKOH/g or more and containing a carboxyl group is not particularly limited as long as the above-mentioned acid value condition is satisfied, and can be appropriately selected from known (meth) acrylic resins.
For example, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of JP 2010-237589, or the like can be preferably used.
As another preferable mode of the alkali-soluble resin, a styrene-acrylic acid copolymer can be given. In the present specification, the styrene-acrylic acid copolymer means a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic acid compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth) acrylic acid compound is preferably 30 mass% or more, more preferably 50 mass% or more, with respect to all the structural units of the copolymer.
The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5% by mass to 80% by mass, based on the total structural units of the copolymer.
The content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass to 95% by mass, based on the total structural units of the copolymer.
From the viewpoint of more excellent effects in the present invention, the alkali-soluble resin preferably has an aromatic ring structure, more preferably has a structural unit containing an aromatic ring structure.
Examples of the monomer forming the structural unit having an aromatic ring structure include styrene compounds such as styrene, t-butoxystyrene, methyl styrene and α -methyl styrene, benzyl (meth) acrylate, and the like.
Among them, a styrene compound is preferable, and styrene is more preferable.
Further, from the viewpoint of more excellent effects in the present invention, the alkali-soluble resin more preferably has a structural unit (structural unit derived from styrene) represented by the following formula (S).
[ chemical formula 4]
Figure BDA0004129129940000591
In the case where the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass relative to all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present invention.
Further, from the viewpoint of more excellent effects in the present invention, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 60 mol% with respect to all the structural units of the alkali-soluble resin.
In addition, from the viewpoint of more excellent effects in the present invention, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol% with respect to all the structural units of the alkali-soluble resin.
In the present specification, when the content of the "structural unit" is defined in a molar ratio, the "structural unit" and the "monomer unit" are the same. In the present specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
From the viewpoint of more excellent effects in the present invention, the alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure. That is, the alkali-soluble resin preferably contains a structural unit having an aliphatic hydrocarbon ring structure. Among them, the alkali-soluble resin preferably has a ring structure in which aliphatic hydrocarbon rings having 2 or more rings are condensed.
Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include tricyclodecane ring, cyclohexane ring, cyclopentane ring, norbornane (norbornane) ring and isobornane ring.
Among them, from the viewpoint of more excellent effects in the present invention, a ring obtained by fusing aliphatic hydrocarbon rings having 2 or more rings is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 2，6 ]Decane ring).
Examples of the monomer forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Further, from the viewpoint of more excellent effects in the present invention, the alkali-soluble resin more preferably has a structural unit represented by the following formula (Cy), and even more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).
[ chemical formula 5]
Figure BDA0004129129940000601
In the formula (Cy), R M Represents a hydrogen atom or a methyl group, R Cy A monovalent group having an aliphatic hydrocarbon ring structure.
R in formula (Cy) M Preferably methyl.
From the viewpoint of more excellent effect in the present invention, R in formula (Cy) Cy The monovalent group is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.
R of formula (Cy) Cy The aliphatic hydrocarbon ring structure may have a single ring structure or a polycyclic structure.
Further, from the viewpoint of more excellent effects in the present inventionConsidering the R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in (a) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isobornane ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure.
In addition, from the viewpoint of more excellent effect in the present invention, R of formula (Cy) Cy The aliphatic hydrocarbon ring structure in (a) is preferably a ring structure in which an aliphatic hydrocarbon ring having 2 or more rings is condensed, and more preferably a ring in which an aliphatic hydrocarbon ring having 2 to 4 rings is condensed.
In addition, R in formula (Cy) is from the viewpoint of more excellent effect in the present invention Cy The oxygen atom of-C (=O) O-in the formula (Cy) is preferably an aliphatic hydrocarbon ring group which is a group directly bonded to an aliphatic hydrocarbon ring structure, more preferably a cyclohexyl group or a dicyclopentyl group, and still more preferably a dicyclopentyl group.
The alkali-soluble resin may have 1 structural unit having an aliphatic hydrocarbon ring structure alone or 2 or more.
In the case where the alkali-soluble resin contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass relative to all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present invention.
Further, from the viewpoint of more excellent effects in the present invention, the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol% with respect to all the structural units of the alkali-soluble resin.
In addition, from the viewpoint of more excellent effects in the present invention, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol% with respect to all the structural units of the alkali-soluble resin.
In the case where the alkali-soluble resin contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 40 to 75% by mass relative to all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present invention.
Further, from the viewpoint of more excellent effects in the present invention, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 40 to 60 mol% with respect to all the structural units of the alkali-soluble resin.
Further, from the viewpoint of more excellent effects in the present invention, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, still more preferably 40 to 60 mol% with respect to all the structural units of the alkali-soluble resin.
Further, from the viewpoint of further excellent effects in the present invention, the relation between the molar amount nS of the structural unit represented by the above formula (S) and the molar amount nCy of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably satisfied, more preferably satisfied, the following formula (SCy) is satisfied, still more preferably satisfied, the following formula (SCy-1) is satisfied, and still more preferably satisfied, the following formula (SCy-2) is satisfied.
nS/(nS+ nCy) of 0.2 to 0.8 (SCy)
nS/(nS+ nCy) of 0.30 to 0.75 (SCy-1)
nS/(nS+ nCy) of 0.40 to 0.70 (SCy-2)
From the viewpoint of more excellent effects in the present invention, the alkali-soluble resin preferably contains a structural unit having an acid group.
Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferable.
The structural unit having an acid group is preferably a structural unit derived from (meth) acrylic acid shown below, and more preferably a structural unit derived from methacrylic acid.
[ chemical formula 6]
Figure BDA0004129129940000621
The alkali-soluble resin may have 1 structural unit having an acid group alone or 2 or more.
In the case where the alkali-soluble resin contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass relative to all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present invention.
Further, from the viewpoint of more excellent effects in the present invention, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol% with respect to all the structural units of the alkali-soluble resin.
Further, from the viewpoint of more excellent effects in the present invention, the content of the structural unit derived from (meth) acrylic acid in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol% with respect to all the structural units of the alkali-soluble resin.
From the viewpoint of more excellent effects in the present invention, the alkali-soluble resin preferably has a reactive group, more preferably contains a structural unit having a reactive group.
The reactive group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. Also, in the case where the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably contains a structural unit having an ethylenically unsaturated group in a side chain.
In the present specification, "main chain" means a relatively longest connecting chain among molecules of a polymer compound constituting a resin, and "side chain" means an atomic group branched from the main chain.
As the ethylenically unsaturated group, an allyl group or a (meth) acryloxy group is more preferable.
Examples of the structural unit having a reactive group include the structural units shown below, but are not limited thereto.
[ chemical formula 7]
Figure BDA0004129129940000631
The alkali-soluble resin may have 1 structural unit having a reactive group alone or 2 or more.
In the case where the alkali-soluble resin contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, still more preferably 20 to 40% by mass, relative to all the structural units of the alkali-soluble resin, from the viewpoint of more excellent effects in the present invention.
Further, from the viewpoint of further excellent effects of the present invention, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol% with respect to all the structural units of the alkali-soluble resin.
Examples of the method for introducing the reactive group into the alkali-soluble resin include a method in which an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic anhydride or the like is reacted with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group (acetoacetyl group) or a sulfo group.
As a preferred example of the method for introducing the reactive group into the alkali-soluble resin, there is a method in which a polymer having a carboxyl group is synthesized by polymerization, and then glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the obtained resin by a polymer reaction to introduce a (meth) acryloyloxy group into the polymer. By this method, an alkali-soluble resin having a (meth) acryloyloxy group in a side chain can be obtained.
The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃, more preferably at a temperature of 80 to 90 ℃. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. The polymer reaction is preferably carried out at a temperature of 80℃to 110 ℃. In the above-mentioned polymer reaction, a catalyst such as an ammonium salt is preferably used.
As the alkali-soluble resin, the resins shown below are preferable from the viewpoint of more excellent effects in the present invention. The content ratios (a to d) and the weight average molecular weight Mw and the like of the respective structural units shown below can be appropriately changed according to the purpose.
[ chemical formula 8]
Figure BDA0004129129940000641
[ chemical formula 9]
Figure BDA0004129129940000642
Also, the alkali-soluble resin may contain a polymer including a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer X").
The carboxylic anhydride structure may be any of a chain carboxylic anhydride structure and a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.
The ring of the cyclic carboxylic acid anhydride structure is preferably a 5-to 7-membered ring, more preferably a 5-or 6-membered ring, and still more preferably a 5-membered ring.
The structural unit having a carboxylic anhydride structure is preferably a structural unit having a main chain containing a 2-valent group obtained by removing 2 hydrogen atoms from the compound represented by the following formula P-1 or a 1-valent group obtained by removing 1 hydrogen atom from the compound represented by the following formula P-1, and is bonded directly to the main chain or via a 2-valent linking group.
[ chemical formula 10]
Figure BDA0004129129940000651
In the formula P-1, R A1a Represents a substituent, n 1a R of each A1a May be the same or different, Z 1a Represents a group of valence 2 forming a ring comprising-C (=o) -O-C (=o) -n 1a And represents an integer of 0 or more.
As R A1a Examples of the substituent include alkyl groups.
As Z 1a The alkylene group is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and still more preferably an alkylene group having 2 carbon atoms.
n 1a And represents an integer of 0 or more. At Z 1a In the case of an alkylene group having 2 to 4 carbon atoms, n 1a Preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
At n 1a When an integer of 2 or more is represented, a plurality of R's are present A1a May be the same or different. And there are a plurality of R A1a May be bonded to each other to form a ring, but are preferably not bonded to each other to form a ring.
The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, even more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.
Specific examples of the structural unit having a carboxylic anhydride structure are given below, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the structural units described below, rx represents a hydrogen atom, a methyl group, or CH 2 OH groups or CF 3 The radical, me, represents methyl.
[ chemical formula 11]
Figure BDA0004129129940000661
[ chemical formula 12]
Figure BDA0004129129940000662
The number of structural units having a carboxylic anhydride structure in the polymer X may be 1 or 2 or more.
The total content of the structural units having the carboxylic anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and even more preferably 10 mol% to 35 mol% with respect to all the structural units of the polymer X.
The photosensitive resin layer may contain only 1 polymer X or 2 or more.
When the photosensitive resin layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30 mass%, more preferably 0.2 to 20 mass%, even more preferably 0.5 to 20 mass%, and even more preferably 1 to 20 mass% with respect to the total mass of the photosensitive resin layer, from the viewpoint of further excellent effects in the present invention.
From the viewpoint of more excellent effects in the present invention, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 ～ 50,000, and particularly preferably 20,000 ～ 30,000.
The acid value of the alkali-soluble resin is preferably 10mgKOH/g to 200mgKOH/g, more preferably 60mgKOH/g to 200mgKOH/g, still more preferably 60mgKOH/g to 150mgKOH/g, particularly preferably 60mgKOH/g to 110mgKOH/g.
The acid value of the alkali-soluble resin was determined according to JIS K0070: the values measured by the method described in 1992.
The photosensitive resin layer may contain only 1 alkali-soluble resin or 2 or more kinds of alkali-soluble resins.
From the viewpoint of more excellent effects in the present invention, the content of the alkali-soluble resin is preferably 10 to 9% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, relative to the total mass of the photosensitive resin layer.
< ethylenically unsaturated Compound >
The photosensitive resin layer contains an ethylenically unsaturated compound.
As the ethylenically unsaturated group, (meth) acryloyloxy is preferred.
The ethylenically unsaturated compound in the present specification is a compound other than the alkali-soluble resin, and preferably has a molecular weight of less than 5,000.
The preferred embodiment of the ethylenically unsaturated compound used in the second embodiment includes the preferred embodiment of the ethylenically unsaturated compound used in the first embodiment.
One preferable embodiment of the ethylenically unsaturated compound is a compound represented by the following formula (M) (also simply referred to as "compound M").
Q 2 -R 1 -Q 1 (M)
In the formula (M), Q 1 Q and Q 2 Each independently represents (meth) acryloyloxy, R 1 Represents a divalent linking group having a chain structure.
With respect to Q in formula (M) 1 Q and Q 2 The same groups are preferable from the viewpoint of ease of synthesis.
And, from the viewpoint of reactivity, Q in the formula (M) 1 Q and Q 2 Preference is given to acryloyloxy.
R as formula (M) 1 The effect from the invention is moreFrom the viewpoint of excellent properties, alkylene groups and alkyleneoxyalkylene groups (-L) are preferable 1 -O-L 1 (-) or polyalkoxyalkylene (- (L) 1 -O) p -L 1 Preferably a hydrocarbon group having 2 to 20 carbon atoms or a polyalkoxyalkylene group, more preferably an alkylene group having 4 to 20 carbon atoms, particularly preferably a linear alkylene group having 6 to 18 carbon atoms.
The hydrocarbon group is not particularly limited as long as at least a part thereof has a chain structure, and may be, for example, a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or a combination thereof, preferably an alkylene group or a group formed by combining 2 or more alkylene groups and 1 or more arylene groups, more preferably an alkylene group, and further preferably a linear alkylene group.
In addition, the L 1 Each independently represents an alkylene group, preferably ethylene, propylene or butylene, more preferably ethylene or 1, 2-propylene.
p represents an integer of 2 or more, preferably an integer of 2 to 10.
From the viewpoint of further excellent effect in the present invention, the bond Q in the compound M 1 And Q is equal to 2 The number of atoms of the shortest linking chain is preferably 3 to 50, more preferably 4 to 40, still more preferably 6 to 20, and particularly preferably 8 to 12.
In the present specification, "connection Q 1 And Q is equal to 2 The atomic number "of the shortest link chain between the two is the number of atoms linked to Q 1 R of the connection 1 Atom to Q of (B) 2 R of the connection 1 The shortest number of atoms in the group.
Specific examples of the compound M include 1, 3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 7-heptanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol/propylene glycol) di (meth) acrylate and polytetramethylene glycol di (meth) acrylate. The above ester monomers can also be used as mixtures.
Among the above compounds, from the viewpoint of more excellent effects in the present invention, at least 1 compound selected from 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate is preferable, at least 1 compound selected from 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable, and at least 1 compound selected from 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable.
Further, as one of preferable modes of the ethylenically unsaturated compound, an ethylenically unsaturated compound having 2 or more functions is exemplified.
In the present specification, "an ethylenically unsaturated compound having 2 or more functions" means a compound having 2 or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group in the ethylenically unsaturated compound, (meth) acryl is preferable.
As the ethylenically unsaturated compound, (meth) acrylate compounds are preferred.
The 2-functional ethylenically unsaturated compound is not particularly limited, and may be appropriately selected from known compounds.
Examples of the 2-functional ethylenically unsaturated compound other than the above compound M include tricyclodecane dimethanol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate.
Examples of commercial products of 2-functional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, shin-Nakamura Chemical Co., ltd.), and 1, 6-hexanediol diacrylate (trade name: NK Ester A-HD-N, shin-Nakamura Chemical Co., ltd.).
The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and may be appropriately selected from known compounds.
Examples of the ethylenically unsaturated compound having 3 or more functions include (meth) acrylate compounds having a dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate and glycerol tri (meth) acrylate skeleton.
Here, "tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
As the ethylenically unsaturated compound, caprolactone-modified compounds of (meth) acrylate compounds (Nippon Kayaku Co., ltd., manufactured by KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical Co., ltd., manufactured by A-9300-1CL, etc.), alkylene oxide-modified compounds of (meth) acrylate compounds (Nippon Kayaku Co., ltd., manufactured by KAYARAD (registered trademark) RP-1040, shin-Nakamura Chemical Co., ltd., manufactured by ATM-35E, A-9300, EBRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., manufactured by Ltd., NK Ester A-GLY-9E, etc.) may be mentioned.
As the ethylenically unsaturated compound, urethane (meth) acrylate compounds can be mentioned.
Examples of the urethane (meth) acrylate include urethane di (meth) acrylate, for example, propylene oxide modified urethane di (meth) acrylate and ethylene oxide and propylene oxide modified urethane di (meth) acrylate.
Further, as the urethane (meth) acrylate, urethane (meth) acrylates having 3 or more functions can be mentioned. The lower limit of the number of functional groups is more preferably 6 or more, and still more preferably 8 or more. The upper limit of the number of functional groups is preferably 20 or less. Examples of urethane (meth) acrylates having 3 or more functions include 8UX-015A (Taisei Fine Chemical co., ltd.), UA-32P (Shin-Nakamura Chemical co., ltd.), U-15HA (Shin-Nakamura chemical co., ltd.), UA-1100H (Shin-Nakamura Chemical co., ltd.), kyoeisha Chemical co., ltd., AH-600 (trade name) manufactured by ltd.), and UA-306H, UA-306T, UA-306I, UA-51OH and UX-5000 (both of Nippon Kayaku co., ltd.).
As a preferred embodiment of the ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group is mentioned.
Examples of the acid group include a phosphate group, a sulfo group and a carboxyl group.
Among these, a carboxyl group is preferable as the acid group.
Examples of the ethylenically unsaturated compound having an acid group include 3 to 4 functional ethylenically unsaturated compounds having an acid group [ ethylenically unsaturated compounds having a carboxyl group introduced into pentaerythritol tri-and tetra-acrylate (PETA) skeleton (acid value: 80mgKOH/g to 120 mgKOH/g) ] and 5 to 6 functional ethylenically unsaturated compounds having an acid group (ethylenically unsaturated compounds having a carboxyl group introduced into dipentaerythritol penta-and hexaacrylate (DPHA) skeleton [ acid value: 25mgKOH/g to 70 mgKOH/g) ].
These ethylenically unsaturated compounds having 3 or more functions of an acid group may be used in combination with the 2-functional ethylenically unsaturated compound having an acid group, if necessary.
The ethylenically unsaturated compound having an acid group is preferably at least 1 selected from ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof.
If the ethylenically unsaturated compound having an acid group is at least 1 selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof, the developability and film strength are further improved.
The ethylenically unsaturated compound having 2 or more functions of carboxyl group is not particularly limited, and can be appropriately selected from known compounds.
Examples of the ethylenically unsaturated compound having a carboxyl group and having 2 or more functions include ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (TOAGOSEI CO., LTD.), and ARONIX (registered trademark) M-510 (TOAGOSEI CO., LTD.).
As the ethylenically unsaturated compound having an acid group, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of Japanese unexamined patent publication No. 2004-239942, the contents of which are incorporated herein by reference, is preferable.
Examples of the ethylenically unsaturated compound include a compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, a compound obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, a urethane monomer such as a (meth) acrylate compound having a urethane bond, a phthalic acid compound such as γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, and β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, and an alkyl (meth) acrylate.
These may be used singly or in combination of 2 or more.
As the compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyol, for example, examples thereof include bisphenol A-based (meth) acrylate compounds such as 2, 2-bis (4- ((meth) acryloxypolyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolypropoxy) phenyl) propane, 2-bis (4- ((meth) acryloxypolyethoxy polypropoxy) phenyl) propane, polyethylene glycol di (meth) acrylate having a number of ethylene oxide groups of 2 to 14, polypropylene glycol di (meth) acrylate having a number of propylene oxide groups of 2 to 14, polyethylene glycol di (meth) acrylate having a number of ethylene oxide groups of 2 to 14 and a number of propylene oxide groups of 2 to 14, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxy tri (meth) acrylate, trimethylolpropane triethoxy tri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane tetramethyl) acrylate, tetramethyl) tetramethyl (tetramethyl) acrylate, tetramethyl (tetramethyl) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or di (trimethylolpropane) tetraacrylate is more preferable.
Examples of the ethylenically unsaturated compound include caprolactone-modified compounds (for example, nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical Co., ltd., A-9300-1CL, etc.), alkylene oxide-modified compounds (for example, nippon Kayaku Co., ltd., KAYARAD RP-1040, shin-Nakamura Chemical Co., ltd., ATM-35E, A-9300, DAICEL-ALLNEX LTD, manufactured ECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., ltd., A-GLY-9E, etc.), and the like.
Among them, the ethylenically unsaturated compound containing an ester bond is also preferable from the viewpoint of excellent developability of the photosensitive resin layer after transfer.
The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as the ester bond is contained in the molecule, but from the viewpoint of excellent effect in the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or di (trimethylolpropane) tetraacrylate is more preferable.
From the viewpoint of imparting reliability, the ethylenically unsaturated compound is preferably an ethylenically unsaturated compound containing an aliphatic group having 6 to 20 carbon atoms and the ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure.
Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate.
As a preferred embodiment of the ethylenically unsaturated compound, there may be mentioned an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a 2-functional ethylenically unsaturated compound).
The above-mentioned ethylenically unsaturated compound is preferably an ethylenically unsaturated compound having a ring structure in which an aliphatic hydrocarbon ring having 2 or more rings is condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a 2-functional ethylenically unsaturated compound having a ring structure in which an aliphatic hydrocarbon ring having 2 or more rings is condensed, and still more preferably tricyclodecane dimethanol di (meth) acrylate.
The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure or an isobornane structure, from the viewpoint of further excellent effects in the present invention.
The molecular weight of the olefinically unsaturated compound is preferably from 200 to 3,000, more preferably from 250 to 2,600, even more preferably from 280 to 2,200, particularly preferably from 300 to 2,200.
The ratio of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less in the ethylenically unsaturated compound contained in the photosensitive resin layer is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, relative to the content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.
As one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains an ethylenically unsaturated compound having 2 or more functions, more preferably contains an ethylenically unsaturated compound having 3 or more functions, and further preferably contains an ethylenically unsaturated compound having 3 or 4 functions.
Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin containing a structural unit having an aliphatic hydrocarbon ring.
Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and even more preferably contains succinic acid modified products of 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and dipentaerythritol pentaacrylate.
Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, more preferably contains a compound represented by the formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.
Further, as one of preferable embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a 2-functional ethylenically unsaturated compound (preferably a 2-functional (meth) acrylate compound) and a 3-functional or more ethylenically unsaturated compound (preferably a 3-functional or more (meth) acrylate compound).
In addition, as one of preferable embodiments of the photosensitive resin layer, from the viewpoint of rust resistance, the photosensitive resin layer preferably contains the compound M and a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure.
In addition, as one of preferable embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue inhibition property, and rust inhibitive property, the photosensitive resin layer preferably contains a compound M and an ethylenically unsaturated compound having an acid group, more preferably contains a compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, further preferably contains a compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a 3-functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains a compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a 3-functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound.
Further, as one of preferable embodiments of the photosensitive resin layer, from the viewpoints of substrate adhesion, development residue inhibition property, and rust resistance, the photosensitive resin layer preferably contains 1, 9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, further preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.
The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
The content of the 2-functional or more ethylenically unsaturated compound in the ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer.
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 1 to 70% by mass, more preferably 5 to 70% by mass, further preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass, relative to the total mass of the photosensitive resin layer.
< photopolymerization initiator >
The photosensitive resin layer includes a photopolymerization initiator.
A preferred embodiment of the photopolymerization initiator used in the second embodiment includes the photopolymerization initiator used in the first embodiment described above.
The photopolymerization initiator may be used alone or in combination of 2 or more.
The content of the photopolymerization initiator is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, based on the total mass of the photosensitive resin layer. The upper limit is preferably 10 mass% or less, more preferably 5 mass% or less, based on the total mass of the photosensitive resin layer.
< heterocyclic Compound >
The photosensitive resin layer may contain a heterocyclic compound.
The heterocycle of the heterocyclic compound may be a single ring or a multi-ring.
Examples of the hetero atom of the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. The heterocyclic compound preferably has at least 1 atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, more preferably has a nitrogen atom.
Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodamine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.
Among the above, as the heterocyclic compound, at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodamine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound is preferable, and at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound is more preferable.
Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.
[ chemical formula 13]
Figure BDA0004129129940000761
[ chemical formula 14]
Figure BDA0004129129940000762
As the tetrazolium compound, the following compounds can be exemplified.
[ chemical formula 15]
Figure BDA0004129129940000763
[ chemical formula 16]
Figure BDA0004129129940000764
As thiadiazole compounds, the following compounds can be exemplified.
[ chemical formula 17]
Figure BDA0004129129940000771
As the triazine compound, the following compounds can be exemplified.
[ chemical formula 18]
Figure BDA0004129129940000772
As the rhodanine compound, the following compounds can be exemplified.
[ chemical formula 19]
Figure BDA0004129129940000773
As the thiazole compounds, the following compounds can be exemplified.
[ chemical formula 20]
Figure BDA0004129129940000774
As benzothiazole compounds, the following compounds can be exemplified.
[ chemical formula 21]
Figure BDA0004129129940000781
As benzimidazole compounds, the following compounds can be exemplified.
[ chemical formula 22]
Figure BDA0004129129940000782
[ chemical formula 23]
Figure BDA0004129129940000783
As the benzoxazole compound, the following compounds can be exemplified.
[ chemical formula 24]
Figure BDA0004129129940000784
The heterocyclic compound may be used alone or in combination of 2 or more.
When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0 mass%, more preferably 0.10 to 10.0 mass%, even more preferably 0.30 to 8.0 mass%, and particularly preferably 0.50 to 5.0 mass% relative to the total mass of the photosensitive resin layer.
< aliphatic thiol Compound >
The photosensitive resin layer may contain an aliphatic thiol compound.
When the photosensitive resin layer contains an aliphatic thiol compound, an ene-thiol reaction proceeds between the aliphatic thiol compound and the ethylenically unsaturated compound, and thus curing shrinkage of the formed film is suppressed, and stress is relaxed.
As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) is preferable.
Among the above, the aliphatic thiol compound is more preferably a polyfunctional aliphatic thiol compound from the viewpoint of adhesion of the formed pattern (particularly adhesion after exposure).
In the present specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having 2 or more thiol groups (also referred to as "mercapto groups") in the molecule.
As the polyfunctional aliphatic thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.
The number of functional groups of the polyfunctional aliphatic thiol compound is preferably 2 to 10 functions, more preferably 2 to 8 functions, and even more preferably 2 to 6 functions, from the viewpoint of adhesion of the formed pattern, for example.
Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolethane tris (3-mercaptobutyrate), and tris [ (3-mercaptopropionyloxy) ethyl]Isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethyleneglycol dithiopropionate, 1, 4-bis (3-mercaptobutyryloxy) butane, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexamethylenedithiol, 2' - (ethylenedithiol) diethylenetriamine, meso (mes 0 ) -2, 3-dimercaptosuccinic acid and bis (mercaptoethyl) ether.
Among the above, at least 1 compound selected from trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane and 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione is preferable as the polyfunctional aliphatic thiol compound.
Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β -mercaptopropionic acid, methyl-3-mercaptopropionic acid ester, 2-ethylhexyl-3-mercaptopropionic acid ester, n-octyl-3-mercaptopropionic acid ester, methoxybutyl-3-mercaptopropionic acid ester, and octadecyl-3-mercaptopropionic acid ester.
The photosensitive resin layer may contain 1 kind of aliphatic thiol compound alone or 2 or more kinds of aliphatic thiol compounds.
When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5 mass% or more, more preferably 5 mass% to 50 mass%, further preferably 5 mass% to 30 mass%, and particularly preferably 8 mass% to 20 mass% relative to the total mass of the photosensitive resin layer.
< thermally crosslinkable Compound >
The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
As the thermally crosslinkable compound used in the photosensitive resin layer of the second embodiment, the thermally crosslinkable compound described above in the photosensitive resin layer of the first embodiment is preferably used.
The heat-crosslinkable compound may be used alone or in combination of 1 or more than 2.
When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the photosensitive resin layer.
< surfactant >
The photosensitive resin layer may contain a surfactant.
As the surfactant used in the photosensitive resin layer of the second embodiment, the surfactant described above in the photosensitive resin layer of the first embodiment is preferably used.
The surfactant may be used alone or in combination of 2 or more.
When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass%, more preferably 0.01 to 1.0 mass%, and even more preferably 0.05 to 0.80 mass% relative to the total mass of the photosensitive resin layer.
< polymerization inhibitor >
The photosensitive resin layer may contain a polymerization inhibitor.
The polymerization inhibitor is a compound having a function of delaying or inhibiting the polymerization reaction. As the polymerization inhibitor, for example, a known compound used as a polymerization inhibitor can be used.
Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, and 3, 7-dioctylphenothiazine; hindered phenol compounds such as bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid ] [ ethylenebis (oxyethylene) ]2, 4-bis [ (laurylsulfanyl) methyl ] -o-cresol, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl), 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl), 2, 4-bis- (n-octylsulfanyl) -6- (4-hydroxy-3, 5-di-tert-butylphenylamino) -1,3, 5-triazine and pentaerythritol tetrakis 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine and N-nitrosophenylhydroxylamine, or salts thereof; quinone compounds such as methyl hydroquinone, t-butyl hydroquinone, 2, 5-di-t-butyl hydroquinone and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol and t-butylcatechol; metal salt compounds such as copper dibutyl dithiocarbamate, copper diethyl dithiocarbamate, manganese diethyl dithiocarbamate and manganese diphenyl dithiocarbamate.
Among them, from the viewpoint of more excellent effects in the present invention, at least 1 selected from the group consisting of phenothiazine compounds, nitroso compounds or salts thereof and hindered phenol compounds is preferable, and phenothiazine, bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid ] [ ethylenebis (oxyethylene) ]2, 4-bis [ (laurylsulfanyl) methyl ] -o-cresol, 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) and N-nitrosophenyl hydroxylamine aluminum salt is more preferable.
The polymerization inhibitor may be used alone or in combination of at least 2 kinds.
When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 10.0 mass%, more preferably 0.01 to 5.0 mass%, and even more preferably 0.04 to 3.0 mass% relative to the total mass of the photosensitive resin layer.
< Hydrogen-donating Compound >
The photosensitive resin layer may contain a hydrogen-donating compound.
The hydrogen-donating compound has the effect of further improving the sensitivity of the photopolymerization initiator to active light, suppressing inhibition of polymerization of the ethylenically unsaturated compound by oxygen, and the like.
Examples of the hydrogen-donating compound include amines and amino acid compounds.
Examples of the amines include those disclosed in Japanese patent application laid-open No. 44-020189, japanese patent application laid-open No. 51-082102, japanese patent application laid-open No. 52-134692, japanese patent application laid-open No. 59-138205, japanese patent application laid-open No. 60-084305, japanese patent application laid-open No. 62-018537, japanese patent application laid-open No. 64-033104, research Disclosure 33825, and the like, as described in "Journal of Polymer Society" of M.R. Sander et al, volume 10, page 3173 (1972). More specifically, 4' -bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (alias: colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline may be mentioned.
Among them, from the viewpoint of more excellent effects in the present invention, at least 1 selected from 4,4' -bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane is preferable as the amine.
Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
Among them, N-phenylglycine is preferred as the amino acid compound from the viewpoint of more excellent effect in the present invention.
Examples of the hydrogen-donating compound include an organometallic compound (tributyltin acetate, etc.) described in Japanese patent publication No. 48-042965, a hydrogen donor described in Japanese patent publication No. 55-034414, and a sulfur compound (trithiane, etc.) described in Japanese patent application laid-open No. 6-308727.
The hydrogen-donating compound may be used alone or in combination of 1 or more than 2.
When the photosensitive resin layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01 to 10.0 mass%, more preferably 0.01 to 8.0 mass%, and even more preferably 0.03 to 5.0 mass% relative to the total mass of the photosensitive resin layer, from the viewpoint of improving the curing rate by balancing the polymerization growth rate and chain transfer.
< impurities etc.)
The photosensitive resin layer may contain a prescribed amount of impurities.
The impurities in the photosensitive resin layer of the second embodiment are the same as those described above in the photosensitive resin layer of the first embodiment.
< residual monomer >
The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the alkali-soluble resin.
The residual monomers corresponding to the respective structural units of the alkali-soluble resin in the photosensitive resin layer of the second embodiment are preferably the same as those of the alkali-soluble resin in the photosensitive resin layer of the first embodiment.
< other ingredients >
The photosensitive resin layer may contain components other than the components described above (hereinafter, also referred to as "other components"). Examples of the other component include a colorant, an antioxidant, and particles (for example, metal oxide particles). Further, as other components, other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 may be mentioned.
Particles-
As the particles, metal oxide particles are preferable.
The metal in the metal oxide particles further includes semi-metals such as B, si, ge, as, sb and Te.
For example, from the viewpoint of transparency of the cured film, the average primary particle diameter of the particles is preferably 1nm to 200nm, more preferably 3nm to 80nm.
The average primary particle diameter of the particles was calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. In addition, when the shape of the particles is not spherical, the longest side is set to have a particle diameter.
When the photosensitive resin layer contains particles, the photosensitive resin layer may contain only 1 kind of particles having different metal types and sizes, or may contain 2 or more kinds of particles.
When the photosensitive resin layer contains no particles or the photosensitive resin layer contains particles, the content of particles is preferably more than 0 mass% and 35 mass% or less relative to the total mass of the photosensitive resin layer, more preferably more than 0 mass% and 10 mass% or less relative to the total mass of the photosensitive resin layer, still more preferably more than 0 mass% and 5 mass% or less relative to the total mass of the photosensitive resin layer, still more preferably more than 0 mass% and 1 mass% or less relative to the total mass of the photosensitive resin layer.
Coloring agent-
The photosensitive resin layer may contain a colorant (pigment, dye, etc.), but from the viewpoint of transparency, for example, it is preferable that the colorant is substantially not contained.
In the case where the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1 mass%, more preferably less than 0.1 mass%, relative to the total mass of the photosensitive resin layer.
Antioxidant-
Examples of the antioxidant include 3-pyrazolidinones such as 1-phenyl-3-pyrazolidinone (referred to as "phenanthridinone"), 1-phenyl-4, 4-dimethyl-3-pyrazolidinone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone and chlorohydroquinone; para-methyl aminophenol, para-hydroxyphenylglycine, and para-phenylenediamine.
Among them, 3-pyrazolidinone is preferable, and 1-phenyl-3-pyrazolidinone is more preferable, from the viewpoint of more excellent effect in the present invention.
When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and still more preferably 0.01 mass% or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 1 mass% or less.
< layer thickness of photosensitive resin layer >
The layer thickness of the photosensitive resin layer is not particularly limited, but is more often 30 μm or less, and is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5.0 μm or less, from the viewpoint of further excellent effects in the present invention. The lower limit is preferably 0.60 μm or more, more preferably 1.5 μm or more, from the viewpoint of excellent strength of the film obtained by curing the photosensitive resin layer.
The thickness of the photosensitive resin layer can be calculated as an average value of 5 arbitrary points measured by cross-sectional observation using a Scanning Electron Microscope (SEM), for example.
< refractive index of photosensitive resin layer >
The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.
< color of photosensitive resin layer >
The photosensitive resin layer is preferably achromatic. Specifically, total reflection (incidence angle 8 °, light source: D-65 (2 ° field of view)) is observed in CIE1976 (L) * ，a * ，b * ) In color space, L * The value is preferably from 10 to 90, a * The value is preferably from-1.0 to 1.0, b * The value is preferably-1.0 to 1.0.
The pattern (cured film of the photosensitive resin layer) obtained by curing the photosensitive resin layer is preferably achromatic.
Specifically, total reflection (incidence angle 8 °, light source: D-65 (2 ° field of view)) is observed in CIE1976 (L) * ，a * ，b * ) In color space, L of pattern * The value is preferably 10 to 90, a of the pattern * The value is preferably-1.0 to 1.0, b of the pattern * The value is preferably-1.0 to 1.0.
[ refractive index adjusting layer ]
The photosensitive transfer material preferably has a refractive index adjustment layer.
As the refractive index adjustment layer, a known refractive index adjustment layer can be applied. Examples of the material contained in the refractive index adjustment layer include alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles.
The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a complex of a metal salt and a resin.
Examples of the alkali-soluble resin and the ethylenically unsaturated compound include those described in the above item of "photosensitive resin layer".
Examples of the particles include metal oxide particles and metal particles.
The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used. The metal in the metal oxide particles further includes semi-metals such as B, si, ge, as, sb and Te.
For example, from the viewpoint of transparency of the cured film, the average primary particle diameter of the particles is preferably 1nm to 200nm, more preferably 3nm to 80nm.
The average primary particle diameter of the particles was calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. In addition, when the shape of the particles is not spherical, the longest side is set to have a particle diameter.
The metal oxide particles are preferably selected from zirconium oxide particles (ZrO 2 Particles, nb 2 O 5 Particles, titanium oxide particles (TiO 2 Particles), silica particles (SiO 2 Particles) and their composite particles.
Among these, the metal oxide particles are more preferably at least 1 selected from the group consisting of zirconia particles and titania particles, for example, from the viewpoint of easy adjustment of refractive index.
Examples of the commercial products of the metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F74), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT% -F76), zirconia particles (manufactured by Nanouse OZ-S30M, nissan Chemical Industries, ltd. Times.) and zirconia particles (manufactured by Nanouse OZ-S30K, nissan Chemical Industries, ltd. Times.).
The particles may be used alone or in combination of 2 or more.
The content of the particles in the refractive index adjustment layer is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, based on the total mass of the refractive index adjustment layer.
When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass of the refractive index adjustment layer.
The refractive index of the refractive index adjustment layer is preferably higher than that of the photosensitive resin layer.
The refractive index of the refractive index adjustment layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.
The layer thickness of the refractive index adjusting layer is preferably 50nm to 500nm, more preferably 55nm to 110nm, and still more preferably 60nm to 100nm.
< method for producing photosensitive transfer Material of the second embodiment >
The method for producing the photosensitive transfer material according to the second embodiment is not particularly limited, and a known method can be used.
As a method for producing the photosensitive transfer material 10 shown in fig. 2, for example, a method including the steps of: a photosensitive resin composition is applied to the surface of the temporary support 1 to form a coating film, and the coating film is dried to form a photosensitive resin layer 3; and a step of forming a coating film by applying a composition for forming a refractive index adjusting layer to the surface of the photosensitive resin layer 3, and a step of drying the coating film to form a refractive index adjusting layer 5.
The photosensitive transfer material 10 is produced by pressing the protective film 7 against the refractive index adjustment layer 5 of the laminate produced by the above-described production method.
As a method for producing the photosensitive transfer material of the first embodiment, it is preferable to produce the photosensitive transfer material 10 including the temporary support 1, the photosensitive resin layer 3, the refractive index adjustment layer 5, and the protective film 7 by including a step of providing the protective film 7 so that the surface of the refractive index adjustment layer 5 on the side opposite to the side having the temporary support 1 contacts.
After the photosensitive transfer material 10 is manufactured by the above-described manufacturing method, the photosensitive transfer material 10 is wound up, whereby the photosensitive transfer material in a wound form can be manufactured and stored. 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.
The method for producing the photosensitive transfer material 10 may be a method in which the refractive index adjustment layer 5 is formed on the protective film 7, and then the photosensitive resin layer 3 is formed on the surface of the refractive index adjustment layer 5.
The above-described method for producing the photosensitive transfer material 10 may be a method in which the photosensitive resin layer 3 is formed on the temporary support 1, the refractive index adjustment layer 5 is formed on the protective film 7, and the photosensitive resin layer 3 and the refractive index adjustment layer 5 are bonded to each other.
The photosensitive resin composition and the method for forming the photosensitive resin layer in the second embodiment are preferably the same as those in the first embodiment.
< composition for Forming refractive index adjustment layer and method for Forming refractive index adjustment layer >
The composition for forming a refractive index adjustment layer preferably contains various components and solvents for forming the refractive index adjustment layer. In the composition for forming a refractive index adjustment layer, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the refractive index adjustment layer.
The solvent is not particularly limited as long as it can dissolve or disperse the component contained in the refractive index adjusting layer, 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.
The solvent may be used alone or in combination of 1 or more than 2.
The content of the solvent is preferably 50 to 2 parts by mass, more preferably 50 to 1 part by mass, and further preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.
The method for forming the refractive index adjusting layer is not particularly limited as long as the layer containing the above-described components can be formed, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, and the like).
Further, the photosensitive transfer material of the second embodiment can be manufactured by attaching a protective film to the refractive index adjustment layer.
The method of attaching the protective film to the refractive index adjusting layer is not particularly limited, and a known method may be used.
As a means for bonding the protective film to the refractive index adjusting layer, a known laminator such as a vacuum laminator and an automatic cutting laminator can be mentioned.
The laminator preferably includes an arbitrary heatable roller such as a rubber roller, and can be pressurized and heated.
(method for producing resin Pattern and method for producing laminate)
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").
In the method for producing a resin pattern according to the present invention, it is preferable that at least a part of the resin pattern contains a line-space pattern, and more preferable that at least a part of the resin pattern contains a line-space pattern, and that a total width of at least 1 group of lines and spaces in the line-space pattern is 20 μm or less, from the viewpoint of further exhibiting the effects of the present invention.
The method for producing a laminate according to the present invention is a method for producing a laminate having a resin pattern on a substrate using the photosensitive transfer material according to the present invention.
As a method for producing the laminate, a method including the protective film peeling step, the bonding step, the exposure step, and the development step in this order is preferable.
< bonding Process >
The method for producing the resin pattern or the method for producing the laminate preferably includes a lamination 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 lamination temperature is not particularly limited, and is preferably, for example, 70℃to 130 ℃.
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 or the method for producing a laminate 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 substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
A preferred embodiment of the substrate is described in paragraph 0140 of international publication No. 2018/155193, the contents of which are incorporated herein by reference.
Examples of the base material constituting the substrate include glass, silicon, and a 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, 2010-152809 and 2010-257492 can be used.
When a film substrate is used as the substrate, a 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 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), IZ0 (indium zinc oxide) and Si0 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.
A preferable embodiment of the conductive layer is described in paragraph 0141 of international publication No. 2018/155193, the contents of which are incorporated herein by reference.
The substrate having the conductive layer is preferably a substrate having at least one of a transparent electrode and a wiring. The substrate described above can be preferably used as a substrate for a touch panel.
The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal thin wire such as a metal mesh and silver nanowire.
The fine metal wire may be a fine wire of silver, copper, or the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.
As a material of the routing wiring, metal is preferable.
Examples of the metal used for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and an alloy composed of 2 or more of these metal elements. Copper, molybdenum, aluminum, or titanium is preferable as a material of the wiring, and copper is particularly preferable.
For the purpose of protecting the electrode or the like (i.e., at least one of the electrode for a touch panel and the wiring for a touch panel), the electrode protecting film for a touch panel formed using the photosensitive transfer material according to the present invention is preferably provided so as to cover the electrode or the like directly or via another layer.
< Exposure procedure >
The method for producing a resin pattern or the method for producing a laminate preferably includes a step of exposing the photosensitive resin layer to a pattern after the bonding step (exposure step).
Here, "pattern exposure" refers to exposure in a pattern-like manner, that is, exposure in which there are exposed portions and non-exposed portions.
The positional relationship between the exposed region and the unexposed region in the pattern exposure is not particularly limited, and may be appropriately adjusted.
The detailed arrangement and specific dimensions of the pattern in the pattern exposure are not particularly limited. For example, in order to improve the display quality of a display device (for example, 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 。
Preferable modes of the light source, the exposure amount, and the exposure method used for exposure include, for example, modes described in paragraphs 0146 to 0147 of International publication No. 2018/155193, which are incorporated herein by reference.
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.
< stripping Process >
The method for producing a resin pattern or the method for producing a laminate may include a peeling step of peeling off the temporary support between the bonding step and the exposure step or between the exposure step and the development step.
The method of peeling the temporary support is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP 2010-072589 can be used.
< 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.
Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyl trimethylammonium hydroxide).
The developer described in paragraph 0194 of International publication No. 2015/093271 is also preferably used. The development method preferably used is, for example, the development method described in paragraph 0195 of international publication No. 2015/093271.
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 includes a protective film, the method for producing the resin pattern or the method for producing the laminate 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.
< post-exposure Process and post-baking Process >
The method for producing a resin pattern or the method for producing a laminate may include a step of exposing the resin pattern obtained in the development step (post-exposure step) and/or a step of heating (post-baking step).
In the case where both the post-exposure step and the post-baking step are included, post-baking is preferably performed after post-exposure.
< other procedure >
The method for producing a resin pattern or the method for producing a laminate may include any step (other step) other than the above steps. 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.
< use >
The resin pattern produced by the method for producing a resin pattern according to the present invention and the laminate produced by the method for producing a laminate according to the present invention can be applied to various devices. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to a display device such as an organic electroluminescence display device or a liquid crystal display device.
In the case where the laminate is applied to a touch panel, the resin pattern formed is preferably used as a protective film for an electrode for a touch panel or a wiring for a touch panel. That is, the photosensitive transfer material according to the present invention is preferably used for forming an electrode protective film for a touch panel or a wiring for a touch panel.
(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 japanese patent application laid-open No. 2006-23696.
Examples of the other steps include, but are not limited to, a step of reducing the reflectance of visible light described in paragraph 0172 of international publication No. 2019/022089, a step of forming a new conductive layer on an insulating film described in paragraph 0172 of international publication No. 2019/022089, and the like.
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. 3 and 4 show an example of a pattern of a mask used for manufacturing a touch panel.
In the pattern a shown in fig. 3 and the pattern B shown in fig. 4, 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. 3, 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 one example of the manufactured touch panel, the central portion (pattern portion formed by connecting four corners) 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 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
The following examples are presented to more specifically describe embodiments of the present invention. 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.
Details of abbreviations for the compounds used in the examples and comparative examples are shown below.
< alkali-soluble resin >
A-1: styrene/methacrylic acid/methyl methacrylate=32/28/40 (mass%), mw=40,000
A-2: styrene/methacrylic acid/methyl methacrylate=52/29/19 (mass%), mw=60,000
A-3: benzyl methacrylate/methacrylic acid=81/19 (mass%), mw=40,000
A-4: propylene glycol monomethyl ether acetate solution of copolymer of benzyl methacrylate/methacrylic acid/acrylic acid=75/10/15 (solid content concentration 30.0%, mw=30,000, acid value 153 mgKOH/g)
A-5: kuraray Poval PVA-205 (polyvinyl alcohol, KURARAY co., ltd.)
A-6: polyvinylpyrrolidone K-30 (NIPPON SHOKUBIAI CO., LTD.)
< ethylenically unsaturated Compound >
B-1: NK ester BPE-500 (2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane, shin-Nakamura Chemical Co., ltd.
B-2: NK ester BPE-200 (2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane, shin-Nakamura chemical Co., ltd.
B-3: dimethacrylates of polyethylene glycol to which an average of 1 5 moles of ethylene oxide and an average of 2 moles of propylene oxide were added at both ends of bisphenol A, respectively
B-4: LIGHT ACRYLATE DPE-6A (dipentaerythritol hexaacrylate, KYOEISHA CHEMICAL CO., LTD.)
B-5: ARONIX M-270 (polypropylene glycol diacrylate, TOAGOSEI CO., LTD.)
B-6: NK ester A-TMPT (trimethylolpropane triacrylate, shin-Nakamura Chemical Co., ltd.)
B-7: sartomer SR-454 (ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema Co., ltd.)
B-8: sartomer SR-502 (ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema Co., ltd.)
B-9: NK ester A-9300-CL1 (epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, shin-Nakamura Chemical Co., ltd.
B-10: NK esters A-DCP (tricyclodecane dimethanol diacrylate, shin-Nakamura Chemical Co., ltd.)
B-11:8UX-015A (urethane acrylate, TAISEI FINE CHEMICAL CO, LTD. Manufactured by Mitsui.)
B-12: ARONIX TO-2349 (multifunctional olefinically unsaturated compounds with carboxylic acid groups, TOAGOSEI CO., LTD.)
< photopolymerization initiator >
C-1: B-CIM (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, KUROGANE KASEI Co., ltd.)
C-2: SB-PI 701 (4, 4' -bis (diethylamino) benzophenone, available from Sanyo tracking Co., ltd.)
C-3: omnifad 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by IGM Resins B.V.)
C-4: irgacure OXE02 (1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyl oxime), manufactured by BASF Co., ltd.),
C-5:4,4' -bis (diethylamino) benzophenone (manufactured by KANTO CHEMICAL co., inc.)
< polymerization inhibitor >
D-1: TDP-G (phenothiazine, kawaguchi ChemicalIndustry Co., LTD.)
D-2: phenoxazine (Tokyo ChemicalIndustry Co., ltd.)
D-3: irganox245 (hindered phenol polymerization inhibitor, manufactured by BASF corporation)
D-4: n-nitrosophenyl hydroxylamine aluminum salt (FUJIFILM Wako Pure Chemical Corporation system)
D-5: MQ (4-methoxyphenol, kawaguchi Chemical Industry Co., LTD.)
< other additives >
E-1: colorless crystal violet (developer, tokyo Chemical Industry co., ltd.)
E-2: N-phenylcarbamoylmethyl-N-carboxymethylaniline (developer, manufactured by FUJIFILM Wako Pure Chemical Corporation)
E-3: bright green (developer, tokyo Chemical Industry Co., ltd.)
E-4: CBT-1 (rust inhibitor, carboxybenzotriazole, JOHOKU CHEMICAL CO., LTD.)
E-5:1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole with 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole: 1 (mass ratio) mixture, rust inhibitor
E-6: phenanthrone (antioxidant, tokyo Chemical Industry Co., ltd.)
E-7: megafac F-552 (a fluorine-based surfactant, manufactured by DIC Corporation)
E-8: megafac F-444 (fluorine-based surfactant, DIC Corporation)
< solvent >
F-1: methyl ethyl ketone (SANKYO CHEMICAL Co., ltd.)
F-2: propylene glycol monomethyl ether acetate (SHOWA DENKO K.K.)
F-3: ion exchange water
F-4: methanol (Mitsubishi Gas Chemical Company, inc. made)
< preparation of thermoplastic resin composition >
The following components were mixed to prepare a thermoplastic resin composition.
A-4:42.85 parts
B-10:4.63 parts
B-11:2.31 parts
B-12:0.77 part
E-7:0.03 part
F-1:39.50 parts
F-2:9.51 parts
A compound having the structure shown below (photoacid generator, a compound synthesized by the method described in paragraph 0227 of japanese patent application laid-open No. 2013-47765): 0.32 part
[ chemical formula 25]
Figure BDA0004129129940001011
A compound having the structure shown below (a dye that develops color by an acid): 0.08 part
[ chemical formula 26]
Figure BDA0004129129940001012
< preparation of intermediate layer composition >
The following components were mixed to prepare an intermediate layer composition.
A-5:3.22 parts
A-6:1.49 parts
E-8:0.0015 part
F-3:38.12 parts
F-4:57.17 parts
< preparation of photosensitive resin composition >
Each of the photosensitive resin compositions used in examples and comparative examples was prepared with the compositions described in table 1 below.
Examples 1 to 16 and comparative examples 1 to 3
< preparation of photosensitive transfer Material >
As a temporary support, a polyethylene terephthalate (PET) film having a thickness of 30 μm was prepared. The thermoplastic resin composition was applied to the surface of the temporary support by using a slit nozzle so that the coating width became 1.0m and the layer thickness after drying became 4.0. Mu.m. The formed coating film of the thermoplastic resin composition was dried at 80℃for 40 seconds, thereby forming a thermoplastic resin layer.
The intermediate layer composition was applied to the surface of the formed thermoplastic resin layer by using a slit nozzle so that the coating width became 1.0m and the layer thickness after drying became 1.2. Mu.m. The coating film of the intermediate layer composition was dried at 80 ℃ for 40 seconds, thereby forming an intermediate layer.
The photosensitive resin compositions having the compositions shown in table 1 were applied to the surface of the intermediate layer formed using a slit nozzle so that the coating width became 1.0m and the layer thickness after drying became the layer thicknesses shown in table 1. The coated film of the photosensitive resin composition was dried at 80 ℃ for 40 seconds, thereby forming a photosensitive resin layer.
The photosensitive transfer materials of examples and comparative examples were produced by pressing a PET film (manufactured by tolay INDUSTRIES, INC., lumirror16QS 62) as a protective film on the surface of the formed photosensitive resin layer.
< evaluation of photosensitive transfer Material >
Lamination-
The protective film was peeled off from the obtained photosensitive transfer material, and the peeled photosensitive transfer material was laminated on a substrate (a copper layer having a thickness of 200nm was produced on a 100 μm pet film by sputtering) with a sheet laminator. The lamination conditions were set at a roll temperature of 100℃and a lamination speed of 2 m/min and a lamination pressure of 0.5MPa.
Eb measurement and sensitivity evaluation
Arranged on a temporary support of a laminated photosensitive transfer material15 step wedge (Fujifilm Corporation system), using 20mW/cm 2 180mJ/cm of high-pressure mercury lamp 2 Is a single-layer exposure. After exposure, the support was peeled off and developed in a 0.9 mass% aqueous sodium carbonate solution at 25℃for 30 seconds, and Eb was obtained from the residual film thickness in each step.
In addition, as the value of Eb, there is a preferable range of values from the viewpoint of adaptability to a general photolithography process. If Eb is 25mJ/cm 2 The sensitivity was moderate as above, the following performance of the device was excellent, and if Eb was 90mJ/cm 2 In the following, the exposure time can be shortened, and productivity is excellent.
For sensitivity, eb (mJ/cm based 2 ) Is evaluated according to the following criteria. The photosensitive transfer material is preferably a to C, more preferably a or B.
A：35≤Eb(mJ/cm 2 )≤70
B：25≤Eb(mJ/cm 2 ) Eb < 35 or 70 (mJ/cm) 2 )≤90
C：90＜Eb(mJ/cm 2 )
D：Eb(mJ/cm 2 )＜25
Determination of W3
The line was brought into contact with a photomask having a space=10 μm/10 μm and a temporary support, and the line was brought into contact with a photomask having a space of ep=2×fb (mJ/cm) 2 ) Exposing the photosensitive transfer material laminated on the substrate. After 3 hours from exposure, the temporary support, the thermoplastic resin layer and the intermediate layer were peeled off with an adhesive tape, 5mL of bromine water (0.2%) was separated in a 50mL container, and the sample was fixed in the container so as not to come into contact with the separated liquid, and left standing at room temperature (25 ℃) for 5 minutes. After that, the solution was stored under high vacuum for half a day to degas the residual bromine. Thus, a sample in which a carbon-carbon double bond was bromine-modified was produced.
The sample was analyzed by secondary ION mass spectrometry (SIMS 5 from ION-TOF Co., ltd., primary ION source: bi) 3+ (30 kV), measurement range: 50mm, area resolution: 512×512pixel, integration: 32 times, measurement mode: high spatial resolution mode (Fast Imaging: fast Imaging), charged correction: using electron gun), C was evaluated 2 HBr - Width of the region. C is C 2 HBr - The portion with the smaller strength is set as the width of the region where polymerization proceeds. The width of the region where polymerization proceeds was measured at 3, and the average value thereof was set to W 3 。
-W 24 Determination of-
Change the time elapsed after exposure to W 3 In the same manner as the measurement of (1), the polymerization progress area width W after 24 hours from the pattern exposure was obtained 24 . And calculate W 24 /W 3 Is a value of (2).
-W 72 Determination of-
Change the time elapsed after exposure to W 3 In the same manner as the measurement of (1), the polymerization progress area width W after 72 hours from the pattern exposure was obtained 72 . And calculate W 72 /W 3 Is a value of (2).
< line width Change at 24 hours after Exposure >
The line was brought into contact with a photomask having a space=10 μm/10 μm and a temporary support, and the line was brought into contact with a photomask having a space of ep=2×fb (mJ/cm) 2 ) Exposing the photosensitive transfer material laminated on the substrate. After exposure for 3 hours or 24 hours, the temporary support was peeled off, and a 25 ℃ aqueous solution of 1% sodium carbonate was sprayed to dissolve the unexposed portion to obtain a resist pattern. From a Scanning Electron Microscope (SEM) image of a cross section of the obtained resist pattern, a line width of a portion of the photosensitive resin layer in contact with the substrate was measured. The line width developed 3 hours after exposure was set as Wr 3 The line width developed after 24 hours was Wr 24 Wr was obtained 24 /Wr 3 . The closer the ratio is to 1, the smaller the line width variation upon placement after exposure, so to speak, the preferable performance. According to the following standard pair Wr 24 /Wr 3 Evaluation was performed. The photosensitive transfer material is preferably a or B.
A：Wr 24 /Wr 3 ＜1.03
B：1.03≤Wr 24 /Wr 3 ＜1.05
C：1.05≤Wr 24 /Wr 3 ＜1.1
D：1.1≤Wr 24 /Wr 3
< line width Change at development temperature Change >
The line was brought into contact with a photomask having a space=10 μm/10 μm and a temporary support, and the line was brought into contact with a photomask having a space of ep=2×eb (mJ/cm) 2 ) Exposing the photosensitive transfer material laminated on the substrate. After exposure for 3 hours, the temporary support was peeled off, and a 30 ℃ aqueous solution of 1% sodium carbonate was sprayed to dissolve the unexposed portion, thereby obtaining a resist pattern. Measuring line width Wr from cross-sectional SEM image of the obtained resist pattern 3b Wr was obtained 3b /Wr 3 . The closer the ratio is to 1, the smaller the line width variation at the time of development temperature variation, and the wider the process robustness, which can be said to be preferable. Wr is Wr 3b /Wr 3 The evaluation was performed on the basis of the following criteria. The photosensitive transfer material is preferably a or B.
A：Wr 3b /Wr 3 ＜1.03
B：1.03≤Wr 3b /Wr 3 ＜1.05
C：1.05≤Wr 3b /Wr 3
The measurement results and evaluation results are summarized in table 2.
TABLE 1
Figure BDA0004129129940001051
TABLE 2
Figure BDA0004129129940001061
As shown in tables 1 and 2, the photosensitive transfer materials of examples 1 to 16 showed less variation in line width of the resin pattern with the lapse of the exposure time than the photosensitive transfer materials of comparative examples 1 to 3.
In the photosensitive transfer materials of examples 1 to 16, the line width of the resin pattern was changed little with the change in the development temperature, and the sensitivity was also excellent.
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. 3, 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. 4, 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 wiring board was observed under a microscope, and was found to be a perfect pattern without peeling off, chipping, or the like.
In the pattern a shown in fig. 3, 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. 4, similarly to fig. 3, 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 disclosures of Japanese patent application Nos. 2020-156353, filed on even 17 at 9/2020, are incorporated herein by reference in their 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
1. 11-temporary support, 2, 12-transfer layer, 3, 17-photosensitive resin layer, 5-refractive index adjusting layer, 13-thermoplastic resin layer, 15-intermediate layer, 10, 20-photosensitive transfer material, GR-light shielding part (non-image part), EX-exposure part (image part), DL-alignment frame.

Claims (12)

1. A photosensitive transfer material, comprising:
a temporary support; and
a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator,
the photosensitive resin layer is used for mJ/cm 2 The width W of the double bond reaction region after exposure of the line and space pattern of 10 μm/10 μm with the exposure dose Ep of unit time of 3 hours 3 Width of double bond reaction region W after 24 hours 24 Satisfy W 24 /W 3 ≤1.05，
W 3 W and W 24 The width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material,
the Ep satisfies ep=2×eb,
The Eb is set to be 20mW/cm of illuminance passing through a 15-step wedge after the photosensitive resin layer is attached to a substrate 2 Is exposed to 180mJ/cm 2 Exposure is performed to give an exposure amount of an order of ±1% of the residual layer thickness of the developed photosensitive resin layer.
2. The photosensitive transfer material according to claim 1, wherein,
the double bond reaction area width W after 3 hours after exposing the photosensitive resin layer to the exposure Ep in a line and space pattern of 10 μm/10 μm 3 Width of double bond reaction region W at 72 hours 72 Satisfy W 72 /W 3 ≤1.10，
W 72 The width of the double bond reaction region obtained by the secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material was set.
3. The photosensitive transfer material according to claim 1 or 2, wherein,
the ethylenically unsaturated compound comprises an ethylenically unsaturated compound having a bisphenol structure.
4. The photosensitive transfer material according to any one of claims 1 to 3, wherein,
the photopolymerization initiator includes a biimidazole compound and a benzophenone compound.
5. The photosensitive transfer material according to any one of claims 1 to 4, wherein,
The photosensitive resin layer further comprises a polymerization inhibitor.
6. The photosensitive transfer material according to claim 5, wherein,
the polymerization inhibitor contains at least 1 compound selected from phenothiazine, phenoxazine and a compound having a hindered phenol structure.
7. The photosensitive transfer material according to claim 5 or 6, wherein,
when Rc is the content of the photopolymerization initiator and Rd is the content of the polymerization inhibitor in the photosensitive resin layer, the mass ratio Rd/Rc is 0.02 or more and 0.1 or less.
8. The photosensitive transfer material according to claim 7, wherein,
the mass ratio Rd/Rc is 0.03 or more and 0.05 or less.
9. A method for manufacturing a resin pattern, comprising, in order:
a step of bringing an outermost layer of the photosensitive transfer material according to any one of claims 1 to 8, 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; and
And developing the exposed photosensitive resin layer to form a resin pattern.
10. The method for producing a resin pattern according to claim 9, wherein,
At least a part of the resin pattern includes a line-and-space pattern, and at least 1 group of lines and spaces in the line-and-space pattern have a total width of 20 μm or less.
11. A method for manufacturing a circuit wiring includes, in order:
a step of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 8 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
And a step of etching the substrate in the region where the resin pattern is not arranged.
12. 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 8 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
And a step of etching the substrate in the region where the resin pattern is not arranged.
CN202180063610.4A 2020-09-17 2021-08-19 Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel Pending CN116235111A (en)

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