CN116635790A - Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, method for producing electronic device, and method for producing laminate - Google Patents

Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, method for producing electronic device, and method for producing laminate Download PDF

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Publication number
CN116635790A
CN116635790A CN202180085868.4A CN202180085868A CN116635790A CN 116635790 A CN116635790 A CN 116635790A CN 202180085868 A CN202180085868 A CN 202180085868A CN 116635790 A CN116635790 A CN 116635790A
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China
Prior art keywords
layer
photosensitive
transfer material
compound
photosensitive layer
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CN202180085868.4A
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Chinese (zh)
Inventor
两角一真
藤本进二
有富隆志
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN116635790A publication Critical patent/CN116635790A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention provides a photosensitive transfer material having a temporary support and a photosensitive layer containing an ethylenically unsaturated compound, wherein an ultra-high pressure mercury lamp is used to achieve an energy density of 100mJ/cm at a wavelength of 365nm, and a method for producing a laminate, a method for producing a resin pattern using the photosensitive transfer material, an etching method, and a method for producing an electronic device 2 When the photosensitive layer is exposed, the ratio of the disappearance rate of the ethylenic unsaturated bonds in the photosensitive layer exposed before and after the peeling of the temporary support is 70% to 100%.

Description

Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, method for producing electronic device, and method for producing laminate
Technical Field
The present invention relates to a photosensitive transfer material, a method for producing a resin pattern, a method for producing a circuit wiring, a method for producing an electronic device, and a method for producing a laminate.
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, since the number of steps for obtaining a desired pattern shape is small, a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate with a photosensitive transfer material through a mask having a desired pattern and then developing the exposed layer is widely used.
Further, as a conventional photosensitive resin laminate, a photosensitive resin laminate described in japanese patent application laid-open No. 2019-133143 is known.
Japanese patent application laid-open publication No. 2019-133143 discloses a photosensitive resin laminate for exposure after support film peeling, comprising: a support film; and a photosensitive resin composition layer disposed on the support film and containing a photosensitive resin composition, wherein the photosensitive resin composition layer comprises: an alkali-soluble polymer, (B) a compound reactive with a photoinitiator, and (C) a photoinitiator, wherein a copper-clad laminate (Copper Clad Laminate) of 0.4mm thickness on which 35 μm rolled copper foil is laminated is jet-milled with a polishing material of #400 and then preheated to 60 ℃, and the photosensitive resin laminate is laminated on the copper-clad laminate by a hot roll laminator at a roll temperature of 105 ℃ and a gas pressure of 0.35MPa at a lamination speed of 1.5m/min, and then exposed to light under any one of the following conditions (1) and (2):
(1) Exposing the support film with the focus position aligned with the surface of the support film by an exposing device, peeling the support film from the exposed photosensitive resin composition layer,
(2) The support film is peeled off, and then exposure is performed by an exposure device in a state that the focus position is aligned with the portion of the support film surface,
1% by mass of Na at 30℃in a time 2 times the minimum development time using a fine alkali developer 2 CO 3 Spraying an aqueous solution to remove the unexposed portion, washing with pure water for the same time as the development time, dehydrating with an air knife, and then drying with warm air to obtain a resist pattern, wherein the difference between the 1 st resist pattern obtained by the exposure under the above condition (1) and the 2 nd resist pattern obtained by the exposure under the above condition (2) is 5 μm or less in the patternable minimum individual thin line width,
the exposure device is any one of the following:
(a) An exposure device with a peak wavelength of exposure light of 350-370 nm;
(b) An exposure device with a peak wavelength of exposure light of 400-410 nm;
(c) An exposure device with a peak wavelength of 360-380 nm and 390-410 nm and a wavelength intensity ratio of 360-380 nm:390-410 nm=30:70; and
(d) Short arc mercury lamps.
Disclosure of Invention
Technical problem to be solved by the invention
An object of an embodiment of the present invention is to provide a photosensitive transfer material having excellent resolution even when a photosensitive layer is directly exposed without a temporary support.
Another object of another embodiment of the present invention is to provide a method for producing a laminate having excellent resolution.
Further, 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 an electronic device, 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 transfer layer comprising a photosensitive layer containing an ethylenically unsaturated compound, wherein a substrate having a metal layer on the surface thereof is bonded to the transfer layer in the photosensitive transfer material, and an ultra-high pressure mercury lamp is used to apply a radiation density of 100mJ/cm at a wavelength of 365nm in air at 23 ℃ and 1 atm 2 When the photosensitive layer is exposed, the ratio D2/D1 of the percentage D1 of the exposed ethylenic unsaturated bond without peeling the temporary support to the percentage D2 of the exposed ethylenic unsaturated bond after peeling the temporary support is 70% to 100%.
<2> the photosensitive transfer material according to <1>, wherein,
the oxygen permeability of the transfer layer was 1 mL/(m) 2 Day atm) to 100 mL/(m) 2 Day atm).
<3> the photosensitive transfer material according to <1> or <2>, wherein,
the photosensitive layer includes a photo radical polymerization initiator.
<4> the photosensitive transfer material according to <3>, wherein,
the photo radical polymerization initiator is a photo polymerization initiator which generates at least 1 kind of methyl radical or sulfur radical as a polymerization initiator.
<5> the photosensitive transfer material according to any one of <1> to <4>, wherein,
an intermediate layer is further provided between the temporary support and the photosensitive layer.
<6> the photosensitive transfer material according to <5>, wherein,
the intermediate layer contains a water-soluble compound.
<7> the photosensitive transfer material according to <6>, wherein,
the water-soluble compound is at least 1 compound selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives and amide compounds.
<8> the photosensitive transfer material according to <6> or <7>, wherein,
the water-soluble compound is polyvinyl alcohol.
<9> the photosensitive transfer material according to <8>, wherein,
the degree of hydrolysis of the polyvinyl alcohol is 73mol% to 99mol%.
<10> the photosensitive transfer material according to <8> or <9>, wherein,
the polyvinyl alcohol contains ethylene as a monomer unit.
<11> the photosensitive transfer material according to any one of <5> to <10>, wherein,
the intermediate layer contains an inorganic layered compound.
<12> the photosensitive transfer material according to any one of <1> to <11>, wherein,
the above-mentioned ethylenically unsaturated compound comprises a polyfunctional ethylenically unsaturated compound.
<13> the photosensitive transfer material according to any one of <1> to <12>, wherein,
the above-mentioned ethylenically unsaturated compound contains an ethylenically unsaturated compound having 3 functions or more.
<14> the photosensitive transfer material according to any one of <1> to <13>, wherein,
the above-mentioned ethylenically unsaturated compound contains an ethylenically unsaturated compound having a polyethylene oxide structure.
<15> a method for producing a resin pattern, comprising, in order:
a step of bonding the transfer layer of the photosensitive transfer material according to any one of <1> to <14> in contact with a substrate; and a step of forming a pattern by performing exposure treatment and development treatment on the exposed photosensitive layer.
<16> a method for manufacturing a circuit wiring, comprising, in order:
a step of bonding the transfer layer of the photosensitive transfer material according to any one of <1> to <14> by contacting the transfer layer with a substrate having a conductive layer; a step of forming a pattern by performing an exposure treatment and a development treatment on the exposed photosensitive layer; and etching the substrate in the region where the resin pattern is not arranged.
<17> a method of manufacturing an electronic device, comprising, in order:
a step of bonding the transfer layer of the photosensitive transfer material according to any one of <1> to <14> by contacting the transfer layer with a substrate having a conductive layer; a step of forming a pattern by performing an exposure treatment and a development treatment on the exposed photosensitive layer; and etching the substrate in the region where the resin pattern is not arranged.
<18> a method for producing a laminate, comprising, in order:
a bonding step of bonding a transfer layer of a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer containing an ethylenically unsaturated compound to a substrate to produce a laminate; a peeling step of peeling the temporary support from the laminate; and a patterning step of patterning the exposed photosensitive layer by exposure and development, wherein the exposed photosensitive layer is patterned by an ultra-high pressure mercury lamp with an energy density of 100mJ/cm at a wavelength of 365nm in air at 23 ℃ and 1 air pressure 2 When exposure is performed, the ratio D4/D3 of the rate D3 of eliminating ethylenic unsaturated bonds by exposing the photosensitive layer of the laminate produced in the lamination step through the temporary support to the rate D4 of eliminating ethylenic unsaturated bonds by exposing the photosensitive layer after the temporary support is peeled off in the peeling step is 80% to 100%.
Effects of the invention
According to an embodiment of the present invention, a photosensitive transfer material having excellent resolution can be provided even when the photosensitive layer is directly exposed without via a temporary support.
According to another embodiment of the present invention, a method for manufacturing a laminate having excellent resolution 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 an electronic device 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.
Fig. 2 is a schematic plan view showing a pattern a.
Fig. 3 is a schematic plan view showing a pattern B.
Detailed Description
The following describes the content of the present invention. Note that, although the description is given with reference to the drawings, the reference numerals may be omitted.
In the present specification, the numerical range indicated by the terms "to" means a range in which the numerical values before and after the term "to" are included as a lower limit value and an upper limit value.
In the present specification, "(meth) acrylic acid" means either or both of acrylic acid and methacrylic acid, "(meth) acrylic acid ester" means either or both of acrylic acid ester and methacrylic acid ester, "(meth) acryl" means either or both of acryl and methacryl.
In the present specification, the amount of each component in the composition refers to the total amount of the corresponding plurality of substances present in the composition unless otherwise specified, in the case where a plurality of substances corresponding to each component are present in the composition.
In the present specification, the term "process" refers not only to an independent process but also to a process that is not clearly distinguished from other processes, if the desired purpose of the process is achieved.
In the labeling of groups (atomic groups) in the present specification, the label that is not labeled with a substituent and is unsubstituted includes a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, in the present specification, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. The light used for exposure generally includes an open line spectrum of a mercury lamp, extreme ultraviolet rays (EUV light), active rays (active energy rays) such as X-rays and electron beams, which are represented by excimer laser light.
In addition, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.
In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights obtained as follows 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 transfer layer comprising a photosensitive layer containing an ethylenically unsaturated compound, wherein the photosensitive transfer material is prepared by reactingThe substrate having a metal layer on the surface is bonded to the transfer layer in the photosensitive transfer material, and the substrate is irradiated with an ultra-high pressure mercury lamp at an energy density of 100mJ/cm at a wavelength of 365nm in air at 23 ℃ and 1 atm 2 When the photosensitive layer is exposed, the ratio D2/D1 of the percentage D1 of the exposed ethylenic unsaturated bond without peeling the temporary support to the percentage D2 of the exposed ethylenic unsaturated bond after peeling the temporary support is 70% to 100%.
Examples of the layer included in the transfer layer include a photosensitive layer, an intermediate layer described later, and a thermoplastic resin layer described later. The temporary support and the transfer film described later are not included in the transfer layer.
The present inventors have found that, in a wiring formation process using a conventional photosensitive transfer material, when a temporary support is peeled off and a photosensitive layer attached to a substrate is exposed, oxygen present in the atmosphere permeates into the photosensitive layer, causing polymerization failure and lowering resolution.
As a result of intensive studies, the present inventors have found that the resolution is excellent even when the photosensitive layer is directly exposed without the temporary support by adopting the above-described method.
In the photosensitive transfer material according to the present invention, a substrate having a metal layer on the surface thereof is bonded to the transfer layer in the photosensitive transfer material in a photosensitive layer containing an ethylenically unsaturated compound, and an ultra-high pressure mercury lamp is used to apply a radiation density of 100mJ/cm at a wavelength of 365nm in air at 23℃and 1 atm 2 When the photosensitive layer is exposed, the ratio D2/D1 of the loss rate D1 of the ethylenic unsaturated bonds exposed without peeling the temporary support to the loss rate D2 of ethylenic unsaturated bonds exposed after peeling the temporary support is 70% to 100%, and thus, although the detailed mechanism is not clear, a photosensitive layer which is less likely to cause polymerization failure due to oxygen can be produced, and even when the photosensitive layer is directly exposed without passing through the temporary support, the resolution is excellent.
< ratio of the loss of ethylenically unsaturated bond D2/D1>
In the photosensitive transfer material according to the present invention, a substrate having a metal layer on the surface is bonded to the transfer layer in the photosensitive transfer material, and an ultra-high pressure mercury lamp is used to apply an energy density of 100mJ/cm at a wavelength of 365nm in air at 23 ℃ and 1 atm 2 When the photosensitive layer is exposed, the ratio D2/D1 of the disappearance of the ethylenic unsaturated bonds D1 exposed without peeling the temporary support to the disappearance of the ethylenic unsaturated bonds D2 exposed after peeling the temporary support is 70% to 100%, and from the viewpoints of resolution (hereinafter, simply referred to as "resolution") and patterning properties when the photosensitive layer is not directly exposed through the temporary support, it is preferably 80% to 100%, more preferably 85% to 100%, even more preferably 90% to 100%, and particularly preferably 95% to 100%.
The following methods are preferable as the measurement and calculation methods of the values of D1, D2 and D2/D1 in the present invention.
A PET substrate with a copper layer was used, which was prepared by sputtering a polyethylene terephthalate (PET) film having a thickness of 100 μm and a copper layer having a thickness of 200 nm.
The photosensitive transfer material thus produced was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4.0 m/min.
In the measurement of D1, the temporary support was not peeled off from the laminated substrate, but was placed on a substrate setting table of a projection exposure machine (Ushio inc. Manufactured by UX-2023 SM). A glass-chromium photomask having a line-space pattern (duty ratio 1:1, line width 1 μm-10 μm, stepwise changes every 1 μm) was set on a mask frame of an exposure machine, and exposure was performed at 100mJ/cm via a projection lens 2 Exposure is performed.
In the measurement of D2, the temporary support was peeled off from the laminated substrate and placed on the substrate setting table of a projection exposure machine (Ushio inc. Manufactured by UX-2023 SM). A glass-chromium photomask having a line-space pattern (duty ratio 1:1, line width 1 μm-10 μm and stepwise changing every 1 μm) is provided on a mask frame of an exposure machine, and exposure is performed by a projection lens at an exposure dose of 100mJ/cm 2 The temporary support was peeled off and then exposed to light for 10 minutes.
The measurement of the disappearance of the ethylenic unsaturated bond was performed after 3 hours of storage in the atmosphere of 1 air pressure 23℃and 55% RH after exposure.
The rate of disappearance of the ethylenic unsaturated bond (c=c rate) was measured by the following method.
In the measurement of the disappearance rate of the ethylenic unsaturated bonds in the sample with the intermediate layer, a photosensitive layer exposed after the intermediate layer was removed by wiping with water was used.
Using a LUMOS (full automatic Fourier transform infrared (FT-IR) microscope manufactured by Bruker Optics, inc.), MCT (mercury cadmium telluride) was used as a detector with a wave number resolution of 4cm -1 Total Reflection (ATR) measurement (Ge crystallization) was performed 32 times in total. C=C extension and contraction (1, 635 cm) -1 ) Peak height (after background treatment) of (2,900 cm) was scaled with C-H -1 ) The peak heights of (a) were normalized, and the ratio (exposed/unexposed) was defined as the ethylenically unsaturated bond disappearance (c=c residual ratio), and the c=c disappearance ratio was determined from 1- (c=c residual ratio).
In the case where the photosensitive transfer material has a protective film described later, the protective film is peeled off before the substrate is bonded during measurement of the loss rate of the ethylenic unsaturated bonds.
The method for increasing the value of D2/D1 is not particularly limited, and examples thereof include a method of forming a layer functioning as an oxygen barrier layer such as an intermediate layer, and a method of using a radical species (for example, a methyl radical, a sulfur-containing radical, etc.) which is hardly deactivated as a radical species of a polymerization initiator to be produced as a photo radical polymerization initiator.
< oxygen permeability of photosensitive layer ]
The oxygen permeability of the transfer layer in the photosensitive transfer material according to the present invention is preferably 20,000 mL/(m) from the viewpoints of resolution and pattern formation 2 Day atm) or less, more preferably 5,000 mL/(m) 2 Day atm) or less, more preferably 1,000 mL/(m) 2 Day atm) or less, particularly preferably 1 mL/(m) 2 Day atm) to 100 mL/(m) 2 Day atm).
The oxygen permeability was measured as follows.
A photosensitive transfer material was laminated on a cellulose Triacetate (TAC) substrate (40 μm thick) from the photosensitive layer side under lamination conditions of a roll temperature of 100 ℃, a line pressure of 1.0MPa, and a line speed of 4.0m/min, and the temporary support was peeled off to prepare a measurement sample. The measurement sample was attached to the electrode portion via silicone grease, and the measurement environment was adjusted to 23℃50% RH. The oxygen permeability coefficient (i.e., oxygen permeability) was determined from the amount of oxygen reaching the electrode in a steady state (apparatus: oxygen concentration meter, for example, MODEL Hach Ultra Analytics, inc. Oxygen concentration meter MODEL modem 3600).
The method of adjusting the oxygen permeability of the transfer layer to the above range is not particularly limited, and examples thereof include a method of forming an oxygen barrier layer by using a layer such as an intermediate layer in addition to the photosensitive layer, a method of adding an inorganic layered compound to the intermediate layer, a method of including a water-soluble compound having low oxygen permeability in the intermediate layer, and preferably a water-soluble resin.
The photosensitive transfer material according to the present invention preferably includes a temporary support, a photosensitive layer, and a protective film in this order.
The photosensitive transfer material according to the present invention may have other layers between the temporary support and the photosensitive layer, between the photosensitive layer and the protective film, and the like.
The photosensitive transfer material according to the present invention preferably further includes an intermediate layer between the temporary support and the photosensitive layer.
The photosensitive transfer material according to the present invention is preferably a roll-shaped photosensitive transfer material from the viewpoint of further exhibiting the effects of the present invention.
An example of the photosensitive transfer material according to the present invention is shown below, but is not limited thereto.
(1) "temporary support/photosensitive layer/refractive index adjustment layer/protective film"
(2) "temporary support/photosensitive layer/protective film"
(3) "temporary support/intermediate layer/photosensitive layer/protective film"
(4) "temporary support/thermoplastic resin layer/intermediate layer/photosensitive layer/protective film"
In each of the above structures, the photosensitive layer is preferably a negative photosensitive layer. The photosensitive layer is also preferably a colored resin layer. The photosensitive transfer material according to the present invention is preferably used as a photosensitive transfer material for an etching resist.
In the case of using the photosensitive transfer material for an etching resist, the photosensitive transfer material is preferably configured, for example, as described in (2) to (4) above.
In the case where the photosensitive transfer material has a structure in which the photosensitive layer further includes 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 layer is preferably 0.1% to 30%, more preferably 0.1% to 20%, with respect to the layer thickness of the photosensitive layer.
Hereinafter, a photosensitive transfer material according to the present invention will be described by taking a specific example of an embodiment.
Hereinafter, a photosensitive transfer material 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 layer 17, and a protective film 19.
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.
[ temporary support ]
The photosensitive transfer material used in the present invention has a temporary support.
The temporary support is a releasable support that supports the photosensitive layer or a laminate including the photosensitive layer.
The temporary support preferably has light transmittance from the viewpoint that exposure of the photosensitive layer via the temporary support can be performed when pattern exposure is performed on the photosensitive 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 layer, the transmittance of light of a wavelength (more preferably, 365 nm) used for pattern exposure of the temporary support is preferably 60% or more, more preferably 70% or more.
The transmittance of the layer included in the photosensitive transfer material is a ratio of the intensity of the light emitted from the layer when the light is incident in a direction perpendicular to the main surface of the layer (thickness direction) to the intensity of the incident light, and is measured using MCPD Series manufactured by Otsuka Elec tronics co.
Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and from the viewpoints of strength, flexibility, and light transmittance, the resin film is preferable.
Examples of the resin film include polyethylene terephthalate (PET: polyethylene 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, from the viewpoints of defect suppression, resolution, and linearity of the resin pattern, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, and particularly preferably 20 μm or less.
Further, it is preferable that the film used as the temporary support is free from deformation such as wrinkles, scratches, defects, and the like.
From the viewpoints of patterning property at the time of pattern exposure via the temporary support and 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 。
From the viewpoints of defect suppression of the resin pattern, resolution, and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, further preferably less than 1.0%, and particularly preferably 0.5% or less.
The haze value in the present invention is determined by the method according to JIS K7105: 1981, measured using a haze meter (NDH-2000, NIPPON DENSHOKU INDUSTRIES co., ltd.).
From the viewpoint of imparting handleability, a layer (lubricant layer) containing fine particles may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be set to (0.05 μm to 0.8 μm, for example) and the layer thickness of the lubricant layer can be set to 0.05 μm to 1.0 μm, for example.
From the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the arithmetic average roughness Ra of the surface of the temporary support on the side opposite to the photosensitive layer side is preferably equal to or greater than the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive layer side.
The arithmetic average roughness Ra of the surface of the temporary support on the side opposite to the photosensitive layer side is preferably 100nm or less, more preferably 50nm or less, further preferably 20nm or less, and particularly preferably 10nm or less, from the viewpoints of conveyability, defect suppression of the resin pattern, and resolution.
The arithmetic average roughness Ra of the surface of the temporary support on the photosensitive layer side is preferably 100nm or less, more preferably 50nm or less, further preferably 20nm or less, and particularly preferably 10nm or less, from the viewpoints of releasability of the temporary support, defect suppression of the resin pattern, and resolution.
Further, from the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the arithmetic average roughness Ra of the surface of the temporary support on the side opposite to the photosensitive layer side is preferably 0nm to 10nm, and more preferably 0nm to 5nm.
The arithmetic average roughness Ra of the surface of the temporary support or protective film in the present invention is measured by the following method.
The surface of the temporary support or protective film was measured using a three-dimensional optical profilometer (New View7300, manufactured by Zygo Corporation) under the following conditions to obtain the surface profile of the 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 to obtain an Ra value of the surface of the temporary support or protective film.
When the temporary support or the protective film is bonded to the photosensitive layer or the like, the temporary support or the protective film may be peeled off from the photosensitive layer, and the Ra value of the peeled surface may be measured.
In the case of conveying the wound laminate again by the roll-to-roll method, the peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive layer or the thermoplastic resin layer is preferably 0.5mN/mm or more, more preferably 0.5mN/mm to 2.0mN/mm, from the viewpoint of the peeling inhibition of the temporary support due to the adhesion of the laminate and the laminate stacked up and down.
The peel force of the temporary support in the present invention was measured as follows.
A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method, and a PET substrate with a copper layer was produced.
The protective film was peeled off from the photosensitive transfer material thus produced, and laminated on the copper-layer-equipped PET substrate under lamination conditions of a lamination roller temperature of 100℃and a linear pressure of 0.6MPa and a linear velocity (lamination speed) of 1.0 m/min. Next, after an adhesive tape (NITTO DENKO corporati0n. Manufactured by PRINTACK) was attached to the surface of the temporary support, a laminate having at least the temporary support and the photosensitive layer on the PET substrate with a copper layer was cut into 70mm×10mm pieces, and a sample was produced. The PET substrate side of the sample was fixed to a sample stage.
The adhesive tape was stretched at 5.5 mm/sec in a direction of 180 degrees using a tensile compression tester (manufactured by IMADA-SS Corporation, SV-55), and the adhesive tape was peeled off between the photosensitive layer or the thermoplastic resin layer and the temporary support, and the force required for peeling off (peeling force) was measured.
Preferable modes of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of International publication No. 2012/081680, paragraphs 0029 to 0040 of International publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese patent application laid-open No. 2019-101405, the contents of which are incorporated herein by reference.
[ photosensitive layer ]
The photosensitive transfer material according to the present invention has a photosensitive layer containing an ethylenically unsaturated compound.
The photosensitive layer is preferably a negative photosensitive layer.
The photosensitive layer preferably contains an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator, and more preferably contains an alkali-soluble resin based on the total mass of the photosensitive 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.
< ethylenically unsaturated Compound >
The photosensitive layer contains an ethylenically unsaturated compound.
The ethylenically unsaturated compound is a compound having 1 or more ethylenically unsaturated groups.
The ethylenically unsaturated group of the ethylenically unsaturated compound is not particularly limited, and examples thereof include a vinyl group, an acryl group, a methacryl group, an acrylamide group, a methacrylamide group, a styryl group, an allyl group, and a maleimide group.
The ethylenically unsaturated group is preferably an acryl group, a methacryl group, an acrylamide group, a methacrylamide group or a styryl group, and more preferably an acryl group or a methacryl group.
Further, the ethylenically unsaturated compound preferably contains a (meth) acrylate compound.
From the viewpoints of resolution and pattern formability, the photosensitive layer preferably contains an ethylenically unsaturated compound having 2 or more functions (polyfunctional ethylenically unsaturated compound), more preferably contains an ethylenically unsaturated compound having 3 or more functions.
Here, the ethylenically unsaturated compound having 2 or more functions means a compound having 2 or more ethylenically unsaturated groups in one molecule.
In addition, from the viewpoint of excellent resolution and releasability, the number of the ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less.
The photosensitive layer preferably contains a 2-functional or 3-functional ethylenically unsaturated compound, more preferably contains a 2-functional ethylenically unsaturated compound, from the viewpoint of more excellent balance of photosensitivity, resolution and releasability of the photosensitive layer.
The content of the 2-functional or 3-functional ethylenically unsaturated compound in the photosensitive layer is preferably 60 mass% or more, more preferably more than 70 mass%, and still more preferably 90 mass% or more, relative to the total content of the ethylenically unsaturated compounds, from the viewpoint of excellent releasability. The upper limit is not particularly limited, and may be 100 mass%. That is, all of the ethylenically unsaturated compounds contained in the photosensitive layer may be 2-functional ethylenically unsaturated compounds.
From the viewpoints of resolution and patterning, the photosensitive layer preferably contains an ethylenically unsaturated compound having a polyalkylene oxide structure, and more preferably contains an ethylenically unsaturated compound having a polyethylene oxide structure.
The ethylenically unsaturated compound having a polyalkylene oxide structure may preferably be a polyalkylene glycol di (meth) acrylate, an alkylene oxide modified product, or the like, which will be described later.
Olefinically unsaturated compounds B1-
The photosensitive layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and 2 ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in one molecule among the above ethylenically unsaturated compounds.
The mass ratio of the content of the ethylenically unsaturated compound B1 in the photosensitive layer to the content of the ethylenically unsaturated compound is preferably 40 mass% or more, more preferably 50 mass% or more, further preferably 55 mass% or more, and particularly preferably 60 mass% or more, from the viewpoint of more excellent resolution. 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 in terms of releasability.
Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferable, and benzene ring is more preferable. The aromatic ring may have a substituent.
The ethylenically unsaturated compound B1 may have only 1 aromatic ring or may have 2 or more aromatic rings.
The ethylenically unsaturated compound B1 preferably has a bisphenol structure in terms of improving resolution by suppressing swelling of the photosensitive layer due to the developer.
Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and a bisphenol a structure is preferable.
Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure.
The bisphenol structure may be directly bonded to both ends of 2 polymerizable groups, or may be bonded to each other through 1 or more alkylene oxide groups. As the alkylene oxide group added to both ends of the bisphenol structure, ethylene oxide group or propylene oxide group is preferable, and ethylene oxide group is more preferable. The number of alkylene oxide groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule.
The olefinically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated into the present specification.
The ethylenically unsaturated compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane.
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.
As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.
[ chemical formula 1]
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.
The content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10 mass% or more, more preferably 20 mass% or more, with respect to the total mass of the photosensitive layer, from the viewpoint of further excellent resolution. The upper limit is not particularly limited, but is preferably 70 mass% or less, more preferably 60 mass% or less, in terms of transferability and edge melting (a phenomenon in which components in the photosensitive layer bleed out from the end portion of the photosensitive transfer material).
The photosensitive layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1.
The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited, and may be appropriately selected from known compounds. Examples thereof include compounds having 1 ethylenically unsaturated group in one 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 layer preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 3 or more functional ethylenically unsaturated compounds, and more preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 2 or more ethylenically unsaturated compounds 3 or more functional ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the ethylenically unsaturated compound having 3 or more functions is preferably (the total mass of the ethylenically unsaturated compounds B1): (total mass of the ethylenically unsaturated compounds of 3 functions or more) =1:1 to 5:1, more preferably 1.2:1 to 4:1, still more preferably 1.5:1 to 3:1.
In one embodiment, the photosensitive layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and 2 or more kinds of 3-functional ethylenically unsaturated compounds.
Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical Co., ltd., A-9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD RP-1040, shin-Nakamura Chemical Co., ltd., ATM-35E and A-9300, DAICEL-ALLNEX LTD, EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., ltd., A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (AGOSEI CO., LTD. Etc.), ARONIX M-520 (AGOSEI CO., LTD. TOOSEI. 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 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 viewpoints of curability and resolution, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth) acryloxy compound.
Further, from the viewpoints of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive 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 layer.
The molecular weight (weight average molecular weight (Mw) in the case of having a distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.
The ethylenically unsaturated compound may be used alone or in combination of at least 2 kinds.
The content of the ethylenically unsaturated compound in the photosensitive 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 layer.
< photopolymerization initiator >
The photosensitive layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that starts polymerization of an ethylenically unsaturated compound upon receiving active light rays such as ultraviolet rays, visible rays, and X rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator.
Among them, the photosensitive layer is preferably a photo radical polymerization initiator from the viewpoints of resolution and patterning.
Further, from the viewpoints of resolution and patterning, the photo radical polymerization initiator preferably generates methyl radicals (. CH) as a polymerization initiator species 3 ) Or a photopolymerization initiator containing 1 or more of sulfur-containing radicals (s—r), more preferably a photopolymerization initiator generating methyl radicals as a polymerization initiator species from the viewpoint of reactivity, and still more preferably a photopolymerization initiator generating sulfur-containing radicals as a polymerization initiator species from the viewpoint of ease of production. The above-mentioned R forming a sulfur-containing radical is not particularly limited, but is preferably an alkyl group from the viewpoint of reactivity.
As the polymerization initiator, as a photopolymerization initiator generating a methyl radical, an oxime acetate compound is preferable.
Further, as a polymerization initiator, a combination of a photopolymerization initiator and a thiol compound is given as a photopolymerization initiator generating sulfur-containing radicals.
The thiol compound is not particularly limited, and a known thiol compound is preferably used as a chain transfer agent.
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.
As the photo radical polymerization initiator, for example, those described in paragraphs 0031 to 0042 of JP 2011-95716 and 0064 to 0081 of JP 2015-14783 can be used.
Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p ' -dimethoxybenzyl) anisyl ester, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF corporation), omnirad651 and 369 (trade name: IGM Resins B.V. Co., ltd.), and 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bisimidazole (Tokyo Chemical Industry Co., ltd.).
Examples of the commercially available photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (o-benzoyloxime) (trade name: IRGACURE (registered trademark) 0XE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG,IGM Resins B.V. Manufactured by Omni. Brand), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: 0mnirad 907,IGM Resins B.V. Manufactured by Omni-p-henyl), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropoyl) benzyl ] phenyl } -2-methylpropane-03 (trade name: IRGACURE-03 (manufactured by BASF corporation), 2- (dimethylamino) methyl-1- (4-morpholino) phenyl ] -1-butanone (trade name: omni 1-4-methylpropane-0 m-4-butanone (trade name: 3, manufactured by Omni-p-4-morpholino-1), IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: omnirad 1173,IGM Resins B.V), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184,IGM Resins B.V, manufactured) 2, 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651,IGM Resins B.V, manufactured), 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: made by emnirad 819,IGM Resins B.V), an oxime ester-based photopolymerization initiator (trade name: lunar 6,DKSH Holding Ltd), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, hampford 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 active light to generate an acid. The photo cation polymerization initiator is preferably a compound that generates an acid in response to an active light having a wavelength of 300nm or more, preferably 300 to 450nm, but the chemical structure thereof is not limited. The photo cation polymerization initiator which does not directly react with the active light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by reacting with the active 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 photosensitive 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 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 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 layer.
< alkali-soluble resin >
The photosensitive layer preferably contains an alkali-soluble resin.
In the present specification, "alkali-soluble" means that the solubility of sodium carbonate in 100g of a 1 mass% aqueous solution at a liquid temperature of 22 ℃ is 0.1g or more.
The alkali-soluble resin is not particularly limited, and for example, a known alkali-soluble resin used for etching resists 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 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, in view of more 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 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 ease of chipping in the case of cutting an unexposed film with a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, the chips are transferred to a mask in a subsequent exposure step or the like, and cause defective products. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, still more preferably 1.0 to 3.0. In the present invention, the molecular weight is a value measured by gel permeation chromatography. And the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).
From the viewpoint of suppressing the line width from becoming thicker or the resolution from deteriorating when the focus position is shifted during exposure, the photosensitive 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 in the case of containing a plurality of polymers a was determined as a weight average value.
Examples of the monomer having an aromatic hydrocarbon include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, a styrene dimer, a styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is styrene, the content of the styrene monomer component is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of the total monomer components.
Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.
Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.
Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group, for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like; vinyl monomers having a benzyl group, for example, vinylbenzyl chloride, vinylbenzyl alcohol, and the like. Among them, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is benzyl (meth) acrylate, the content of the benzyl (meth) acrylate monomer component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of the total monomer components.
The polymer a containing a monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon with at least 1 of the first monomers described later and/or at least 1 of the second monomers described later.
The polymer a containing no monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing at least 1 kind of a first monomer described later, more preferably by copolymerizing at least 1 kind of the first monomer with at least 1 kind of a second monomer described later.
The first monomer is a monomer having a carboxyl group in a molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is preferable.
The content of the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of the total monomer components.
The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of the total monomer components. The above-mentioned copolymerization ratio is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more from the viewpoint of exhibiting good developability, controlling edge meltability, and the like. The above-mentioned copolymerization ratio is preferably 50 mass% or less from the viewpoint of high resolution of the resist pattern and the curl shape, and more preferably 35 mass% or less, further preferably 30 mass% or less, particularly preferably 27 mass% or less from the viewpoint of chemical resistance of the resist pattern.
The second monomer is a non-acidic monomer having at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth) acrylonitrile, etc. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable.
The content of the second monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass, based on the total mass of the total monomer components.
From the viewpoint of suppressing the line width thickening or the deterioration of resolution at the time of focus position shift at the time of exposure, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.
In one embodiment, the polymer a preferably contains 25 to 40% by mass of a monomer component having an aromatic hydrocarbon, 20 to 35% by mass of a first monomer component, and 30 to 45% by mass of a second monomer component. In another embodiment, the polymer preferably contains 70 to 90 mass% of the monomer component having an aromatic hydrocarbon and 10 to 25 mass% of the first monomer component.
The polymer a may have a branched structure or an alicyclic structure in a side chain. The branched structure or alicyclic structure can be introduced into the side chain of the polymer a by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain.
Specific 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-isoamyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, tert-octyl (meth) acrylate, and the like. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.
Examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group, and examples of the monomer include (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (the number of carbon atoms (carbon atom number)). More specific examples thereof include (bicyclo [2.2.1] heptyl-2) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyl adamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) acrylate, 3, 5-triethyl-1-adamantyl (meth) acrylate, 7-octahydro-indene (meth) acrylate, 1-menthyl (meth) acrylate, 1-adamantyl (meth) acrylate, 1-2-adamantyl (meth) acrylate, 2-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methano-indene (meth) acrylate, and (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, cyclohexyl (meth) acrylate, and the like. Among these (meth) acrylic esters, cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecane (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is particularly preferable.
The polymer A may be used alone or in combination of at least 2 kinds. When 2 or more kinds of polymers a containing a monomer component having an aromatic hydrocarbon are mixed and used, it is preferable to mix and use 2 kinds of polymers a containing a monomer component having an aromatic hydrocarbon and polymers a not containing a monomer component having an aromatic hydrocarbon. In the latter case, the ratio of the polymer a containing the monomer component having an aromatic hydrocarbon to be used is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more, relative to the whole of the polymer a.
Regarding the synthesis of polymer a, it is preferable to proceed as follows: to a solution obtained by diluting one or more of the above-described monomers with a solvent such as acetone, methyl ethyl ketone, isopropyl alcohol, etc., a proper amount of a radical polymerization initiator such as benzoyl peroxide, azoisobutyronitrile, etc., is added, and heating and stirring are performed. In some cases, synthesis may be performed while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, in addition to the solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.
The glass transition temperature Tg of the polymer A is preferably 30℃or more and 135℃or less. By using the polymer a having a Tg of 135 ℃ or less in the photosensitive 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 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, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.
The alkali-soluble resin may be used alone or in combination of 1 or more than 2.
The proportion of the alkali-soluble resin to the total mass of the photosensitive 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 layer is preferably 90 mass% or less. On the other hand, from the viewpoint of improving the edge melting resistance, the proportion of the alkali-soluble resin to the photosensitive layer is preferably 10 mass% or more.
< pigment >
The photosensitive 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 the pigment N is contained, although the detailed mechanism is not clear, the adhesion to the adjacent layers (for example, the temporary support and the 1 st resin 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 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 color developing or decoloring state may be changed by generating an acid, an alkali or a radical in the photosensitive layer by exposure to light, or the color developing or decoloring state may be changed by changing the state (for example, pH) in the photosensitive 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 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 dye N is preferably a dye 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 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 of the dye N in the wavelength range of 400nm to 780nm at the time of color development 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 an atmosphere, 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 preferably has 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. The colorless compound is preferably a compound having a lactone ring, a sultone ring or a sultone ring, which develops color by free radical or acid ring opening, and more preferably a compound having a lactone ring, which develops color by free radical or acid ring opening.
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 (benzopurline) 4B, alpha-naphthalene red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), parapin red (parafuchsin), victoria pure blue (victoria pure blue) -naphthalene sulfonate, victoria pure blue (Hodogaya Chemical co., ltd, manufactured), oil blue #603 (0 rient Chemical Industries Co, ltd, manufactured), oil pink #312 (0 rient Chemical Industries Co, ltd, manufactured), oil red 5B (Orient Chemical Industries co, ltd, manufactured), oil scarlet (oil scarlet) #308 (0rient Chemical Industries C0, ltd, manufactured), oil red OG (OrientChem, industri es co, ltd, manufactured), oil red RR (Orient Chemical Industries co, ltd, manufactured), oil green #502 (Orient Chemical Industri es co, ltd, manufactured), shi Bilong red (spil 0N red) BEH special (Hodogaya Chemical C0., ltd, manufactured), metacresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, gold amine, 4-p-diethylaminophenyl iminonaphthaquinone, 2-carboxyanilino-4-p-diethylaminophenyl iminonaphthaquinone 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.
From the viewpoints of visibility of the exposed portion and the non-exposed portion, visibility of the pattern after development, and resolution, the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and more preferably a dye which develops by radicals.
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 dye is preferably 0.1 mass% or more, more preferably 0.1 to 10 mass%, even more preferably 0.1 to 5 mass%, and particularly preferably 0.1 to 1 mass% relative to the total mass of the photosensitive 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 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 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.) was added as a photo radical polymerization initiator, and light of 365nm was irradiated to generate radicals, thereby bringing all the pigments into a color-developed state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under an air atmosphere 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 layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive layer was calculated based on the calibration curve from the absorbance of the obtained solution containing the photosensitive layer.
< thermally crosslinkable Compound >
The photosensitive 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, which will be described later, is treated not as a polymerizable compound but 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, when the resin and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the formed film decreases, and the function tends to be enhanced when the film obtained by curing the photosensitive layer is used as a protective film.
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 brittleness of the film, improving adhesion to a 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 more preferable than a compound having no oxime structure in that the dissociation temperature is easily set within a preferable range and development residues are easily reduced.
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]
The thermally crosslinkable compound may be used alone or in combination of 1 or 2 or more.
When the photosensitive 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 layer.
< other ingredients >
The photosensitive layer may contain components other than the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, the pigment, and the thermally crosslinkable compound.
Surfactant-containing compositions
From the viewpoint of thickness uniformity, the photosensitive 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 catalyst 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, EXP.MFS-578, and the like R-41, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation, supra), fluorad (trade name) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, supra), surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc, supra), polyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solut ions Inc, supra), ftergent (trade name) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (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, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol octacosanate, and sorbitan fatty acid ester.
Specific examples thereof include Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (manufactured by BASF corporation), solsperse (trade name) 20000 (manufactured by Lubrizol Japan Limited, supra), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-1105, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., ltd., supra), olfine E1010, surfyn 104, 400, 440 (manufactured by Nissin Co., ltd., supra), 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 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-based 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 DC3PA, toray Silicone SH7PA, toray Silicone DC PA, toray Silicone SH 21 PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (Dow Corning Toray Co, supra), ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351 82348, L, KF-355, A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-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 is Et-su Co.) ltd), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials inc. Above), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (BYK Chemie Co., ltd.).
The photosensitive 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 layer.
Additive-
The photosensitive layer may contain a known additive as required in addition to the above components.
Examples of the additive include a polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide and the like), purine bases (adenine and the like) and solvents. The photosensitive layer may contain 1 kind of each additive alone or 2 or more kinds of additives.
The photosensitive layer may contain a polymerization inhibitor. The polymerization inhibitor is preferably a radical polymerization inhibitor.
Examples of the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenyl hydroxylamine aluminum salt, and diphenyl nitrosoamine. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenyl hydroxylamine aluminum salt is preferably used as a polymerization inhibitor.
Examples of the benzotriazoles include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.
Examples of carboxybenzotriazoles include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. As the carboxybenzotriazoles, for example, commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD. Product name) can be used.
The total content of the polymerization inhibitor, benzotriazole and carboxybenzotriazole is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, based on the total mass of the photosensitive layer. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.01 mass% or more. 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 layer may contain a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone (xanthone) compound, a thioxanthone (thioxanthone) compound, an acridone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (e.g., 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.
The photosensitive layer may contain 1 sensitizer alone or 2 or more sensitizers.
When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing speed by balancing the polymerization speed and chain transfer, the content is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% with respect to the total mass of the photosensitive layer.
The photosensitive 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 layer may contain a solvent. When the photosensitive layer is formed from the photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive layer.
The photosensitive 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 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 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 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 layer is produced, and a method for cleaning and removing the impurity. 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 P asa: inductively coupled plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.
The photosensitive layer preferably contains a small amount of compounds 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 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 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 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 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, with respect to the total mass of the alkali-soluble resin, from the viewpoints of pattern formability and reliability. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
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, with respect to the total mass of the photosensitive layer, from the viewpoints of pattern formability and reliability. 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 layer is preferably 0.1 μm to 300. Mu.m, more preferably 0.2 μm to 100. Mu.m, still more preferably 0.5 μm to 50. Mu.m, still more preferably 0.5 μm to 15. Mu.m, particularly preferably 0.5 μm to 10. Mu.m, and most preferably 0.5 μm to 8. Mu.m. This can improve the developability of the photosensitive layer and improve the resolution.
In one embodiment, the thickness is preferably 0.5 μm to 5. Mu.m, more preferably 0.5 μm to 4. Mu.m, and still more preferably 0.5 μm to 3. Mu.m.
The layer thickness of the photosensitive layer is preferably 10 μm or less, more preferably 8 μm or less, from the viewpoint of 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, the transmittance of the photosensitive layer for light having a wavelength of 365nm is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more, from the viewpoint of further excellent adhesion. The upper limit is not particularly limited, but is preferably 99.9% or less.
< method of Forming >
The method for forming the photosensitive layer is not particularly limited as long as the layer containing the above components can be formed.
Examples of the method for forming the photosensitive layer include the following methods: 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 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 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 can dissolve or disperse 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 them.
In the case of producing a photosensitive transfer material including a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive layer, and a protective film, the photosensitive resin composition preferably contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these, a mixed solvent containing at least 1 selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 selected from a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least 3 selected from at least 1 selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent is still more preferable.
Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.
Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
As the solvent, a solvent described in paragraphs 0092 to 0094 of international publication No. 2018/179640 and a solvent described in paragraph 0014 of japanese patent application laid-open No. 2018-177889, which are incorporated herein by reference, can be used.
The photosensitive resin composition may contain 1 kind of solvent alone or 2 or more kinds of solvents.
The content of the solvent in 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 examples thereof include the following methods: 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 layer, the photosensitive resin composition is preferably filtered using a filter having a pore diameter of 0.2 μm to 30 μm.
The method of applying the photosensitive resin composition is not particularly limited, and the photosensitive resin composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
The photosensitive layer may be formed by applying a photosensitive resin composition to a protective film described later and drying the same.
In the photosensitive transfer material of the present invention, it is preferable that another layer is provided between the temporary support and the photosensitive layer from the viewpoints of resolution and releasability of the temporary support.
Examples of the other layer include an intermediate layer, a thermoplastic resin layer, and a protective film.
Among these, the other layers are preferably provided with an intermediate layer, and more preferably provided with a thermoplastic resin layer and an intermediate layer.
[ intermediate layer ]
When the photosensitive transfer material has a thermoplastic resin layer described later between the temporary support and the photosensitive layer, it is preferable to have an intermediate layer between the thermoplastic resin layer and the photosensitive layer. According to the intermediate layer, mixing of components at the time of forming a plurality of layers and at the time of storage 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 invention, "water-soluble" means that the solubility in 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more.
Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. By using the intermediate layer as the oxygen barrier layer, the sensitivity at the time of exposure is improved, and the time load of the exposure machine is reduced, resulting in an improvement in productivity. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers. The oxygen barrier layer used as the intermediate layer is preferably an oxygen barrier layer that 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 ℃).
Further, the intermediate layer preferably contains an inorganic layered compound from the viewpoints of oxygen barrier property, resolution and patterning property.
Examples of the inorganic layered compound include particles having a thin plate-like shape, for example, mica compounds such as natural mica and synthetic mica, and the like, and the formula: 3MgO.4SiOH 2 Talc, taeniolite (taeniolite), montmorillonite, saponite, hectorite (Hectorite), zirconium phosphate, and the like, represented by O.
Examples of the mica compound include the formula: a (B, C) 2-5 D 4 O 10 (0H，F,O) 2 Wherein A is any one of K, na and Ca, B and C are any one of Fe (II), fe (III), mn, A1, mg and V, and D is Si or Al. Mica groups such as natural mica and synthetic mica are shown.
Among the mica groups, natural mica (Muscovite), sodium mica (Paragonite), phlogopite (Phlogopite), biotite (Biotite) and lepidolite (kepidolite) may be mentioned. As synthetic mica, fluorophlogopite KMg may be mentioned 3 (AlSi 3 O 10 )F 2 Potassium tetrasilicon mica KMg 2.5 Si 4 O 10 )F 2 Equal non-swelling mica and Na tetrasilicium mica NaMg 2.5 (Si 4 O 10 )F 2 Na or Li-carrying mica (Na, li) Mg 2 Li(Si 4 O 10 )F 2 Na or Li Hectorite (Na, li) 1/8 Mg 2/5 Li 1/8 (Si 4 O 10 )F 2 And swellable mica. In addition, synthetic montmorillonite is also useful.
As the shape of the inorganic layered compound, the thinner the thickness is, the larger the planar size is in a range that does not hinder the smoothness of the coated surface or the transmittance of the active light, and the better is from the viewpoint of diffusion control. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the major axis to the particle thickness, and can be measured, for example, from a projection view of a particle-based photomicrograph. The larger the aspect ratio, the greater the effect obtained.
The average long diameter of the particle diameter of the inorganic layered compound is preferably 0.3 μm to 20. Mu.m, more preferably 0.5 μm to 10. Mu.m, particularly preferably 1 μm to 5. Mu.m. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swellable synthetic mica as a representative compound, the thickness is preferably about 1nm to 50nm, and the surface size (major diameter) is about 1 μm to 20 μm.
The content of the inorganic lamellar compound is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass, relative to the total mass of the intermediate layer, from the viewpoints of oxygen barrier property, resolution and pattern formation.
The intermediate layer preferably comprises 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.
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 negative photosensitive layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.
Further, the intermediate layer preferably contains a water-soluble compound, more preferably contains a water-soluble resin, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation.
The water-soluble compound is not particularly limited, but is preferably at least one compound selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives and amide compounds, and more preferably at least 1 water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl methylcellulose, from the viewpoints of oxygen barrier property, developability, resolution and patterning property.
Examples of the water-soluble resin include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth) acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.
Among them, the water-soluble compound preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation.
The degree of hydrolysis of the polyvinyl alcohol is not particularly limited, but is preferably 73mol% to 99mol% from the viewpoints of oxygen barrier property, developability, resolution and pattern formability.
Further, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation property, the polyvinyl alcohol preferably contains ethylene as a monomer unit.
The method for measuring the degree of hydrolysis is not particularly limited, and can be determined by JIS K6726: the measurement was performed by the method described in 1994.
The intermediate layer preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoints of oxygen barrier property 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 or 2 or more resins alone.
The content of the water-soluble compound in the intermediate layer 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 the multilayer and at the time of storage after coating.
The intermediate layer may contain an additive as needed. Examples of the additive include surfactants.
Regarding the thickness of the intermediate layer, there is no limitation. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. By having the thickness of the intermediate layer in the above range, mixing of components at the time of forming a plurality of layers and at the time of storage can be suppressed without lowering the oxygen barrier property, and an increase in the removal time of the intermediate layer at the time of development can be suppressed.
The method for forming the intermediate layer is not limited as long as the layer containing the above components can be formed. Examples of the method for forming the intermediate layer include a method of coating the intermediate layer composition on the surface of the thermoplastic resin layer or the photosensitive layer, and then drying the coating film of the intermediate layer composition.
Examples of the intermediate layer composition include a composition containing a resin and any additives. 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 is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least 1 selected from the group consisting of water-miscible organic solvents (Water Miscibility), and more preferably water or a mixed solvent of water and a water-miscible organic solvent.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.
[ thermoplastic resin layer ]
The photosensitive transfer material according to the present invention may have a thermoplastic resin layer. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive layer. This is because, by providing the photosensitive transfer material with the thermoplastic resin layer between the temporary support and the photosensitive layer, the following property to the adherend is improved, and the mixing of air bubbles between the adherend and the photosensitive transfer material is suppressed, and as a result, the adhesion between layers is improved.
The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.
The alkali-soluble resin is preferably an acrylic resin from the viewpoints of developability and adhesion to a layer adjacent to the thermoplastic resin layer. The "acrylic resin" refers to a resin having at least 1 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.
In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, the ratio of 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 preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, 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 is not limited. The acid value of the alkali-soluble resin 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 limited, and can be suitably selected from known resins and used. Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-95716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of JP 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the binder polymers described in paragraphs 0053 to 0068 of JP 2016-224162.
The content of the structural unit having a carboxyl group in the acrylic resin having a carboxyl group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass, based on the total mass of the acrylic resin having a carboxyl group.
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 a layer adjacent to the thermoplastic resin layer.
The alkali-soluble resin may have a reactive group. The reactive group may be any group that can be addition-polymerized, for example. Examples of the reactive group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxyl group and a carboxyl group), and a polyaddition reactive group (e.g., an epoxy group and a (blocked) isocyanate group).
The alkali-soluble resin preferably has a weight average molecular weight (Mw) of 1,000 or more, more preferably 1 to 10 tens of thousands, particularly preferably 2 to 5 tens of thousands.
The thermoplastic resin layer may contain 1 or 2 or more alkali-soluble resins alone.
The content ratio of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass, relative to the total mass of the heat-relaxing resin layer, from the viewpoints of developability and adhesion to the layer adjacent to the thermoplastic resin layer.
The thermoplastic resin layer preferably contains a dye (hereinafter, sometimes referred to as "dye B") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm, which is a wavelength range at the time of color development, and the maximum absorption wavelength is changed by an acid, a base, or a radical. The preferred embodiment of the dye B is the same as that of the dye N described above, except for the points described below.
From the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, 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 of the exposed portion, visibility of the non-exposed portion, and resolution, the thermoplastic layer preferably contains a dye whose maximum absorption wavelength changes by an acid as a dye B, and a compound which generates an acid by light described later.
The thermoplastic resin layer may contain 1 or 2 or more pigments B alone.
The content of the dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, even more 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 viewpoints of visibility of the exposed portion and visibility of the non-exposed portion.
The content ratio of the dye B is the content ratio of the dye when all the dye B contained in the thermoplastic resin layer is 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. 2 solutions were prepared in which pigment (0.001 g) and pigment (0.01 g) were dissolved in methyl ethyl ketone (100 mL). After IRGACURE OXE-01 (BASF corporation) was added as a photo radical polymerization initiator to each of the obtained solutions, 365nm light was irradiated to generate radicals, and all the pigments were brought into a color-developed state. Next, the absorbance of each solution having a liquid temperature of 25 ℃ was measured under an atmosphere using a spectrophotometer (UV 3100, 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 the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone instead of the pigments. Based on the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the pigment contained in the thermoplastic resin layer was calculated based on the calibration curve.
The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, sometimes referred to as "compound C"). The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving active light rays (e.g., ultraviolet rays and visible rays). Examples of the compound C include a known photoacid generator, a photoacid generator, and a photoradical polymerization initiator (photoradical generator). Compound C is preferably a 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 layer, and the same is preferable except for the point described below.
The photoacid generator preferably contains at least 1 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 is also preferably one having the following structure.
[ chemical formula 3]
The thermoplastic resin layer may also contain photobase generators. Examples of the photobase generator 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) -butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine, and 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine.
The thermoplastic resin layer may also contain a photo radical polymerization initiator. The photo radical polymerization initiator may be, for example, a photo radical polymerization initiator that may be contained in the photosensitive layer, and the same is preferable.
The thermoplastic resin layer may contain 1 or 2 or more kinds of compound C alone.
The content ratio 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 of the exposed portion, visibility of the non-exposed portion, and resolution.
The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.
The molecular weight of the plasticizer (for the molecular weight of the oligomer or polymer, refer to the weight average molecular weight (Mw). Hereinafter, the same applies in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.
The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkylene oxide group in the molecule, more preferably a polyalkylene glycol compound. The alkylene oxide group contained in the plasticizer preferably has a polyethylene oxide structure or a polypropylene oxide structure.
From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth) acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to a layer adjacent to the thermoplastic resin 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, for example, the (meth) acrylate compounds described in the above-mentioned ethylenically unsaturated compounds. In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive layer are disposed in direct contact with each other, the thermoplastic resin layer and the photosensitive layer preferably contain the same (meth) acrylate compound. This is because the thermoplastic resin layer and the photosensitive 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 in the exposed portion after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer.
In one embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.
In one embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.
The thermoplastic resin layer may contain 1 or 2 or more kinds of plasticizers alone.
The content ratio 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 a layer adjacent to the thermoplastic resin layer, and developability.
From the viewpoint of uniformity of thickness, the thermoplastic resin layer preferably contains a surfactant. The surfactant may be, for example, a surfactant that may be contained in the photosensitive layer, and the same preferable embodiment is also adopted.
The thermoplastic resin layer may contain 1 or 2 or more surfactants alone.
The content ratio of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, based on the total mass of the thermoplastic resin layer.
The thermoplastic resin layer may also contain a sensitizer. Examples of the sensitizer include those that can be contained in the negative photosensitive layer.
The thermoplastic resin layer may contain 1 or 2 or more kinds of sensitizers alone.
The content ratio of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed portion, and the visibility of the non-exposed portion.
The thermoplastic resin layer may contain known additives as required in addition to the above components.
Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese unexamined patent publication No. 2014-85643. The contents of the above publications are incorporated into the present specification by reference.
There is no limitation regarding the thickness of the thermoplastic resin layer. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. There is no limitation as to the upper limit of the average thickness of the thermoplastic resin layer. The average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less from the viewpoints of developability and resolution.
The method for forming the thermoplastic resin layer is not limited as long as the layer containing the above components can be formed. As a method for forming the thermoplastic resin layer, for example, a method of coating a thermoplastic resin composition on the surface of a temporary support and drying a coating film of the thermoplastic resin composition is mentioned.
Examples of the thermoplastic resin composition include compositions containing the above components. 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.
The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. The solvent may be any solvent that the photosensitive resin composition may contain, and the same is preferable.
The thermoplastic resin composition may contain 1 or 2 or more solvents alone.
The content ratio of the solvent in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the thermoplastic resin composition.
The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the above-described method for preparing the photosensitive resin composition and method for forming the negative photosensitive layer. For example, a thermoplastic resin layer can be formed by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent, mixing the obtained solutions 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. After the negative photosensitive layer is formed on the protective film, a thermoplastic resin layer may be formed on the surface of the negative photosensitive layer.
[ protective film ]
The photosensitive transfer material has a protective film.
The photosensitive layer and the protective film are preferably in direct contact.
As a material constituting the protective film, a resin film and paper are exemplified, and from the viewpoints 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.
From the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive layer side is preferably equal to or less than the arithmetic average roughness Ra of the surface of the protective film on the photosensitive layer side, and more preferably smaller than the arithmetic average roughness Ra of the surface of the protective film on the photosensitive layer side.
From the viewpoint of transport property and windability, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive layer side is preferably 300nm or less, more preferably 100nm or less, still more preferably 70nm or less, and particularly preferably 50nm or less.
In addition, the arithmetic average roughness Ra of the surface of the protective film on the photosensitive layer side is preferably 300nm or less, more preferably 100nm or less, still more preferably 70nm or less, and particularly preferably 50nm or less, from the viewpoint of further excellent resolution. This is considered to be because the Ra value of the surface of the protective film falls within the above range, and the uniformity of the layer thickness of the photosensitive 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 1nm or more, more preferably 10nm or more, and particularly preferably 20nm or more on both surfaces.
The peeling force of the protective film is preferably smaller than the peeling force of the temporary support.
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.
The total thickness of the photosensitive transfer material is preferably 5 μm to 55. Mu.m, more preferably 10 μm to 50. Mu.m, particularly preferably 20 μm to 40. Mu.m. The total thickness of the photosensitive transfer material was measured by the method according to the method for measuring the thickness of each layer described above.
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 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.
[ method for producing photosensitive transfer Material ]
The method for producing the photosensitive transfer material according to 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, an intermediate layer 15, a photosensitive 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 12 by coating a thermoplastic resin composition on the surface of the temporary support 11 and then drying a coating film of the thermoplastic resin composition; a step of forming an intermediate layer 15 by applying an intermediate layer composition to the surface of the thermoplastic resin layer 13 and then drying a coating film of the intermediate layer composition; and a step of forming a photosensitive layer 16 by applying a photosensitive resin composition containing an ethylenically unsaturated compound to the surface of the intermediate 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 alkylene glycol ether solvents and alkylene glycol ether acetate solvents; an interlayer composition comprising at least 1 selected from water and water-miscible organic solvents; and a photosensitive resin composition containing a binder polymer, an ethylenically unsaturated compound, and at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This can suppress the application of the intermediate layer composition to the surface of the thermoplastic resin layer 13 and/or the mixing of the component contained in the thermoplastic resin layer 13 and the component contained in the intermediate layer 15 during the storage of the laminate having the coating film of the intermediate layer composition, and can suppress the application of the photosensitive resin composition to the surface of the intermediate layer 15 and/or the mixing of the component contained in the intermediate layer 15 and the component contained in the photosensitive layer 16 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 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 intermediate layer 15, the photosensitive 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 2 nd surface of the photosensitive layer 17.
After the photosensitive transfer material 20 is manufactured by the above-described manufacturing method, the photosensitive transfer material 20 may be wound up to manufacture and store the photosensitive transfer material in a roll 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 layer, the photosensitive 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 according to the present invention may preferably be one in which the photosensitive layer is a colored resin layer containing a pigment.
The colored resin layer may be used in addition to the above, and is suitable for the following applications: a colored pixel or a black matrix for a color filter or the like of a liquid crystal display device (LCD) and a solid-state imaging element (for example, a CCD (charge-coupled device)) and a CMOS (complementary metal oxide semiconductor: complementary metal oxide semiconductor) is formed.
The method for coloring the resin layer is the same as that described above except for the pigment.
< pigment >
The photosensitive 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, titanium 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 for any 100 particles and averaging the obtained 100 particle diameters, and the area of the pigment particles is calculated from a photographic image of the pigment particles taken by an electron microscope and the diameter of a circle having the same area as the area of the pigment particles is taken into consideration.
As the pigment other than the black pigment, the white pigments described in the () 015 and () 114 of japanese patent application laid-open No. 2005-007765 can be used as the white pigment. Specifically, among the white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon ink, 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 silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, 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.
In view of reducing the thickness of the heated photosensitive 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 layer is a colored resin layer, it is preferable that the photosensitive 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, in view of more 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 monastral fast 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 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 layer.
When the photosensitive 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 layer includes a black pigment and the photosensitive 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.
(method for producing resin Pattern, method for producing laminate, and method for producing Circuit Wiring)
The method for producing a resin pattern according to the present invention is a method for producing a resin pattern by forming a resin pattern on a substrate using the photosensitive transfer material according to the present invention.
As a method for producing the resin pattern, a method comprising the following steps in this order is preferable: a step of bonding the transfer layer in the photosensitive transfer material according to the present invention to a substrate, preferably a substrate having a conductive layer, by contacting the transfer layer with the substrate (hereinafter also referred to as a "bonding step"); and a step of forming a pattern by performing an exposure treatment and a development treatment on the exposed photosensitive layer (hereinafter also referred to as a "pattern forming step").
Further, as a method for producing a resin pattern, it is preferable that a step of peeling off the temporary support (hereinafter also referred to as a "temporary support peeling step") is included between the bonding step and the patterning step.
In addition, as a method for producing the resin pattern, a step of peeling the protective film (hereinafter also referred to as "protective film peeling step") is preferably included before the bonding step.
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 lamination step and the exposure and development step in this order is preferable.
Further, as a method for producing the laminate, a temporary support step is preferably included between the bonding step and the exposure and development step.
In addition, as a method for producing the laminate, a protective film peeling step is preferably included before the lamination step.
The method for producing a laminate according to the present invention preferably includes the following steps in order: a bonding step of bonding a transfer layer of a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer containing an ethylenically unsaturated compound to a substrate to produce a laminate; a peeling step of peeling the temporary support from the laminate; and a patterning step of patterning the exposed photosensitive layer by exposure and development, wherein the exposed photosensitive layer is patterned by an ultra-high pressure mercury lamp with an energy density of 100mJ/cm at a wavelength of 365nm in air at 23 ℃ and 1 air pressure 2 In the case of exposure, the exposure of the photosensitive layer of the laminate produced in the lamination step to the ethylenically unsaturated bond disappearance D3 through the temporary support and the peeling of the temporary support in the peeling step are followed by the exposure of the photosensitive layer to the photosensitive layerThe ratio D4/D3 of the extinction ratio D4 of the ethylenic unsaturated bonds when the sex layer is exposed is 80-100%.
In the method for producing a laminate according to the present invention, from the viewpoints of resolution and patterning, an ultra-high pressure mercury lamp is used to achieve an energy density of 100mJ/cm at a wavelength of 365nm in air at 23℃and 1 atm 2 In the case of exposure, the ratio D4/D3 of the loss rate D3 of the ethylenic unsaturated bonds exposing the photosensitive layer of the laminate in the bonding step through the temporary support to the loss rate D4 of ethylenic unsaturated bonds exposing the photosensitive layer after the temporary support is peeled off in the peeling step is preferably 70% to 100%, more preferably 80% to 100%, even more preferably 85% to 100%, even more preferably 90% to 100%, and most preferably 95% to 100%.
The values of D3, D4, and D4/D3 in the present invention can be measured and calculated by the same method as the method for measuring and calculating the values of D1, D2, and D2/D1, except for measuring the rate of disappearance of the ethylenic unsaturated bonds by exposing the photosensitive layer of the laminate in the bonding step via the temporary support and measuring the rate of disappearance of ethylenic unsaturated bonds by exposing the photosensitive layer after the temporary support is peeled off in the peeling step.
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, a method including the following steps in order is preferable: a step of bringing the transfer layer in the photosensitive transfer material according to the present invention into contact with and bonding to a substrate, preferably a substrate having a conductive layer; and a pattern forming step of performing exposure treatment and development treatment on the exposed photosensitive layer to form a pattern; and a step of etching the conductive layer in a region where the resin pattern is not arranged (hereinafter also referred to as "etching step").
Further, as a method for manufacturing the circuit wiring, a temporary support step is preferably included between the bonding step and the patterning step.
In addition, as a method for manufacturing the circuit wiring, a protective film peeling step is preferably included before the bonding step.
Hereinafter, each step included in the method for producing a resin pattern, the method for producing a laminate, and the method for producing a circuit wiring will be described, but unless otherwise mentioned, the description of each step included in the method for producing a resin pattern or the method for producing a laminate is applicable to each step included in the method for producing a circuit wiring.
< protective film peeling Process >
The method for producing a resin pattern or the method for producing a laminate preferably includes a step of peeling the protective film from the photosensitive transfer material according to the present invention. The method of peeling the protective film is not limited, and a known method can be applied.
< 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, the transfer layer in the photosensitive transfer material is preferably brought into contact with a substrate (in the case where a conductive layer is provided on the surface of the substrate, the conductive layer), and the photosensitive transfer material is preferably brought into pressure contact with the substrate. In the above-described aspect, since the adhesion between the transfer layer and the substrate in the photosensitive transfer material is improved, the patterned photosensitive layer after exposure and development can be preferably used as an etching resist in etching the conductive layer.
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 layer on the side not facing the temporary support, the surface of the photosensitive 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 having the photosensitive layer on the temporary support on the substrate, and pressing and heating the substrate 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 producing the resin pattern and the method for producing the laminate including the lamination 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: the substrate that can be wound and unwound is used as the substrate, and includes a step of winding out the substrate or a structure including the substrate before any step included in the method for producing a resin pattern or the method for etching (also referred to as "winding-out step") and a step of winding up the substrate or a structure including the substrate after any step (also referred to as "winding-up step"), and at least any step (preferably all steps or all steps except for the heating step) is performed while conveying the substrate or the structure including the substrate.
The winding-out method in the winding-out step and the winding-up method in the winding-up step are not particularly limited, and a known method may be used in a manufacturing method to which a roll-to-roll method is applied.
< substrate >
As the substrate used in the method for producing a resin pattern according to the present invention, a known substrate can be used, but a substrate having a conductive layer is preferable, and a conductive layer is more preferable on the surface of the substrate.
The substrate may have any layer other than the conductive layer as needed.
Examples of the 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 and 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 wire formability.
The substrate may have 1 conductive layer alone or 2 or more layers. In the case of having 2 or more conductive layers, conductive layers of different materials are preferable.
As a material of the conductive layer, a metal and a conductive metal oxide can be given.
As the metal, al, zn, cu, fe, ni, cr, mo, ag and Au are exemplified.
Examples of the conductive metal oxide include ITO (indium tin oxide), IZO (indium zinc oxide) and SiO 2 。
In the present specification, the term "conductivity" means that the volume resistivity is less than 1×10 6 Omega cm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 4 Ωcm。
In the case of manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.
The conductive layer is preferably an electrode pattern of a sensor corresponding to a visual recognition portion used in a capacitive touch panel or a wiring of a peripheral lead portion.
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.
< procedure of temporary support Release >
The method for producing a resin pattern or the method for producing a laminate preferably includes a temporary support peeling step of peeling off the temporary support between the bonding step and the exposure 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.
< patterning Process >
The method for producing a resin pattern or the method for producing a laminate preferably includes a step (pattern formation step) of forming a pattern by exposing the exposed photosensitive layer to light and developing the exposed photosensitive layer after the bonding step.
The exposure process is a pattern exposure process (also referred to as "pattern exposure"), that is, an exposure process in which there are an exposed portion and a non-exposed portion.
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 an etching 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 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 layer and then subjected to pattern exposure, or the temporary support may be removed after pattern exposure with the temporary support interposed therebetween before removal of the temporary support. In the case of peeling the temporary support before exposure, the mask may be exposed in contact with the photosensitive layer or may be exposed close to the photosensitive layer 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 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 layer may be directly drawn, or the photosensitive 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 with a liquid such as water interposed between the light source and the photosensitive layer.
In the pattern forming step, after exposure, the exposed photosensitive layer is subjected to a development treatment to form a pattern.
The development of the exposed photosensitive layer in the pattern forming step can be performed using a developer.
The developer is not particularly limited as long as the non-image portion of the photosensitive 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 any of spin-coating immersion development, spray and spin development, and immersion development may be used. The development by showering is a development process in which a developing solution is sprayed onto the photosensitive layer after exposure by showering to remove a non-image portion.
After the patterning step, the cleaning agent is sprayed and sprayed, and the development residues are preferably removed while wiping with a brush.
The liquid temperature of the developer is not particularly limited, but is preferably 20 to 40 ℃.
< 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, the resin pattern formed by the photosensitive layer is used as an etching resist, and 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 solution used in the wet etching may be an acidic or alkaline etching solution appropriately selected 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 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 producing a resin pattern, the method for producing a laminate, and the method for producing a circuit wiring may include any steps (other steps) other than the above steps. For example, the following steps may be mentioned, but the present invention is not limited to these steps.
Further, examples of the exposure step, the development step, and other steps which can be applied to the method for producing a circuit wiring include the steps described in paragraphs 0035 to 0051 of JP 2006-23696A.
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 >
The resin pattern produced by the method for producing a resin pattern according to the present invention, the laminate produced by the method for producing a laminate according to the present invention, and the circuit wiring produced by the method for producing a circuit wiring 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 electronic device)
The method for producing an electronic device according to the present invention is not particularly limited as long as it is a method using the photosensitive transfer material according to the present invention.
As a method for manufacturing an electronic device according to the present invention, it is preferable to sequentially include the steps of: a step of peeling the protective film from the photosensitive transfer material according to the present invention: a step of bringing an outermost layer of the photosensitive transfer material from which the protective film has been peeled, the outermost layer being on the side having the photosensitive layer with respect to the temporary support, into contact with a substrate having a conductive layer, and bonding the outermost layer; and a step of patterning the exposed photosensitive layer by exposure and development, wherein the manufactured electronic device has the resin pattern.
The electronic device manufactured by the method for manufacturing an electronic device according to the present invention preferably has the above-described resin pattern as a permanent film.
The specific modes of the steps in the method for manufacturing an electronic device, the order in which the steps are performed, and the like are preferably the same as those described in the above-described items of the "method for manufacturing a resin pattern" and the "etching method".
In the method of manufacturing an electronic device, the wiring for an electronic device may be formed by the method described above, but a known method of manufacturing an electronic device may be referred to.
The method for manufacturing an electronic device may include any step (other step) other than the above.
The electronic device is not particularly limited, but various wiring forming applications of a semiconductor package, a printed board, a sensor substrate, a touch panel, an electromagnetic shield material, a conductive film such as a film heater, a liquid crystal sealing material, and a structure in the micro-mechanical or micro-electronic field can be preferably given.
The resin pattern is preferably used as a permanent film in the electronic device, for example, an interlayer insulating film, a wiring protective film having an index matching layer, or the like.
Among them, a touch panel is particularly preferable as the electronic device.
Fig. 2 and 3 show an example of a pattern of a mask used for manufacturing a touch panel.
In the pattern a shown in fig. 2 and the pattern B shown in fig. 3, GR is a non-image portion (light shielding portion), EX is an image portion (exposure portion), and DL virtually represents an alignment frame. In the method for manufacturing a touch panel, for example, the photosensitive layer is exposed through a mask having a pattern a shown in fig. 2, whereby a touch panel having a circuit wiring having a pattern a corresponding to EX can be manufactured. Specifically, the method described in FIG. 1 of International publication No. 2016/190405 can be used. In an example of the manufactured touch panel, the central portion (pattern portion to be qualified for connection) of the exposure portion EX is a portion where a transparent electrode (electrode for touch panel) is formed, and the peripheral portion (thin line portion) of the exposure portion EX is a portion where wiring of the peripheral lead-out portion is formed.
By the above method for manufacturing an electronic device, an electronic device having at least wiring for an electronic device is manufactured, and for example, a touch panel having at least wiring for a touch panel is preferably manufactured.
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.
< Polymer >
In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
St: styrene (FUJIFILM Wako Pure Chemical Corporation system)
MAA: methacrylic acid (FUJIFILM Wako Pure Chemical Corporation system)
MMA: methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation)
PGMEA: propylene glycol monomethyl ether acetate (SHOWA DENKO K.K.)
V-601: dimethyl-2, 2' -azobis (2-methylpropionate) (FUJIFILM Wako Pure Chemical Corporat ion)
< Synthesis of Polymer A-1 >
PGMEA (116.5 parts) was added to a three-neck flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution to which St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts) and PGMEA (116.5 parts) were added was dropwise added over 2 hours to a three-necked flask solution maintained at 90.+ -. 2 ℃. After completion of the dropwise addition, the mixture was stirred at 90.+ -. 2 ℃ for 2 hours, whereby polymer A-1 (solid content: 30.0%) was obtained.
< ethylenically unsaturated Compound >
B-1: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd.)
B-2: ARONIX M-270 (polypropylene glycol diacrylate, TOAGOSEI CO., LTD.)
B-3: SR454 (3 mol ethoxylated trimethylolpropane triacrylate, manufactured by Sartomer Company, inc)
< photo radical polymerization initiator >
C-1: irgacure OXE02 (photo radical polymerization initiator, oxime ester photopolymerization initiator, methyl radical generator, BASF Co.)
C-2: BIMD (photo radical polymerization initiator, 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, manufactured by Hampford Co., ltd. B-CIM)
C-3: EAB-F (photo radical polymerization initiator (sensitizer), 4' -bis (diethylamino) benzophenone, tokyo Chemical Industry co., ltd.)
C-4: karenz MTBD1 (produced by combining a multifunctional thiol compound with a radical polymerization initiator to produce a sulfur-containing radical, SHOWA DENKO K.K.)
C-5 (N-phenylcarbamoylmethyl-N-carboxymethylaniline (FUJIF [ LM Wako Pure Chemical Corporation ]): 0.02 part
< additive >
D-1: CBT-1 (carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.)
D-2: LCV (colorless Crystal Violet, YAMADA CHEMICAL CO., LTD.)
D-3: phenothiazine (Seiko Chemical co., ltd.)
D-4: 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation)
D-5: kunipia F (inorganic lamellar compound (bentonite), KUNIMINE INDUSTRIES co., ltd.,) manufactured by ltd
< surfactant >
E-1: megafac F-552 (a fluorine-based surfactant, manufactured by DIC Corporation)
E-2: megafac F-444 (fluorine-based surfactant, DIC Corporation)
< Water-soluble resin >
F-1: kuraray EVALE105B (polyvinyl alcohol (ethylene-polyvinyl alcohol copolymer), hydrolysis degree 100mol%, kuraray C0., ltd. Product)
F-2: kuraray Poval PVA-4-88LA (polyvinyl alcohol, degree of saponification 88, degree of hydrolysis 88mol%, KURARAY CO., LTD.)
F-3: kuraray PovalPVA-L-8 (polyvinyl alcohol, saponification degree 71, hydrolysis degree 71mol%, kuraray C0., LTD. Co., ltd.)
F-4: polyvinylpyrrolidone K-30 (NIPPON SHOKUBIAI C0., LTD.)
F-5: metolose 60SH (hydroxypropyl methylcellulose, shin-Etsu Chemical Co., ltd.)
The degree of hydrolysis of the polyvinyl alcohols (F-1 to F-3) was determined in accordance with JIS K6726: the method described in 1994 was used for measurement.
< preparation of photosensitive resin composition 1 >
The following components were mixed to prepare a photosensitive resin composition 1. The unit of the amounts of the components is parts by mass.
Polymer A-1 (solid content: 30.0%): 25.2 parts of
B-1 (NK ester BPE-500, ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd.): 2.81 parts of
B-2 (ARONIX M-270, polypropylene glycol diacrylate, TOAGOSEI CO., LTD.): 0.58 part
B-3 (SR 454, 3 moles of ethoxylated trimethylolpropane triacrylate, manufactured by Sartomer Company, inc.): 2.81 parts of
C-1 (Irgacure OXE02, photo radical polymerization initiator, oxime ester photopolymerization initiator, BASF): 0.11 part
C-5 (N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)): 0.02 part
D1 (CBT-1 (JOHOKU CHEMICAL CO., LTD) 0.015 parts
D-2 (LCV, colorless crystal violet, YAMADA CHEMICAL CO., LTD. Manufactured, pigment developed by free radical): 0.06 part
D-3 (phenothiazine, seiko Chemical Co., ltd.): 0.04 part
D-4 (4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.002 parts
E-1 (Megafac F552, DIC Corporation): 0.048 part
Methyl ethyl ketone (SANKYO chemistry co., ltd.): 43.8 parts
PGMEA (SHOWA DENKO k.k.): 19.7 parts of
Propylene glycol monomethyl ether (MFG, nippon Nyukazai Co, manufactured by ltd): 3.89 parts
< preparation of intermediate layer composition 1 >
The following components were mixed to prepare an intermediate layer composition.
Ion exchange water: 38.12 parts
Methanol (Mitsubishi Gas Chemical Company, inc. Manufactured): 57.17 parts
F-2 (Kuraray PovalPVA-4-88LA, polyvinyl alcohol, KURARAY CO., LTD.): 3.22 parts
F-4 (polyvinylpyrrolidone K-30, NIPPON SHOKUBIAI CO., LTD.): 1.49 parts
F-5 (METOLOSE 60SH, shin-Etsu Chemical Co., ltd.): 0.04 part
D-5 (Kunipia G, KUNIMINE INDUSTRIES CO., LTD.): 0.08 part
E-2 (Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.001 part
After the above-mentioned mixed solution was pre-dispersed in high-speed stirring (3,000 rpm, peripheral speed=8.2 m/min), the mixture was stirred at a speed of 1,000kgf/cm using a high-pressure dispersing apparatus 1 (trade name: NANOMIZER NMII-2000AR, yoshida Kikai Co., manufactured by Ltd.) 2 Is treated under pressure to give an intermediate layer composition 1.
Example 1
< preparation of photosensitive transfer Material >
The intermediate layer composition 1 was applied to a polyethylene terephthalate film (manufactured by TORAY INDUSTRIES, INC., lumiror 16QS 62) having a thickness of 16 μm as a temporary support so as to have a structure shown in Table 1 below, using a slit nozzle, and passed through a drying zone at 80℃for 40 seconds so as to have a coating width of 1.0m and a layer thickness of 1.1. Mu.m, thereby forming an intermediate layer. Further, the photosensitive resin composition 1 was applied to the intermediate layer by using a slit nozzle so that the coating width became 1.0m and the layer thickness became 5.0 μm, and passed through a drying zone at 80℃for 40 seconds, thereby forming a photosensitive layer.
Determination of the oxygen permeability of the transfer layer
A photosensitive transfer material was laminated on a cellulose Triacetate (TAC) substrate (40 μm thick) from the photosensitive layer side under lamination conditions of a roll temperature l00 ℃, a line pressure of 1.0MPa and a line speed of 4.0m/min, and the temporary support was peeled off to prepare a measurement sample. The measurement sample was attached to the electrode portion via silicone grease, and the measurement environment was adjusted to 23℃50% RH. The oxygen permeability coefficient (i.e., oxygen permeability) was obtained from the amount of oxygen reaching the electrode in a steady state (apparatus: hach Ultra Analytics, inc. Oxygen production concentration meter MODEL MODEL 3600).
Ratio of the disappearance of ethylenic unsaturated bonds (c=c disappearance rate) by post-release exposure/pre-release exposure
The c=c disappearance rate at the time of exposure after the temporary support was peeled off without a mask and the c=c disappearance rate at the time of exposure without peeling off the temporary support were measured and compared with each other in the exposure amount used in the following resolution evaluation. After exposure to light, the film was stored in an atmosphere of 1 air pressure 23℃and 55% RH for 3 hours, and then measured. The c=c disappearance rate was measured by the following method. In the measurement of the disappearance rate of the sample with the intermediate layer, a photosensitive layer exposed by wiping the intermediate layer with water was used.
ATR measurements (Ge crystallization) were performed using LUMOS manufactured by Bruker Optics, MCT with a detector at a wave number resolution of 4cm and 32 times. C=C extension and contraction (1, 635 cm) -1 ) Peak height (after background treatment) of (2, 900 cm) with C-H stretching -1 ) The peak heights of (a) were normalized, and the ratio (exposed/unexposed) was defined as c=c residual ratio, and c=c vanishing ratio was determined by 1- (c=c residual ratio).
< evaluation of Performance >
A PET substrate with a copper layer was used, which was prepared by sputtering a polyethylene terephthalate (PET) film having a thickness of 100 μm and a copper layer having a thickness of 200 nm.
Resolution (resolution)
The photosensitive transfer material thus produced was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.OMPa and a linear velocity of 4.0 m/min. The temporary support was peeled off from the laminated substrate and placed on a substrate setting table of a projection exposure machine (Ushio inc. Manufactured by UX-2023 SM). A glass-chromium photomask having a line-space pattern (duty ratio 1:1, line width 1 μm-10 μm, stepwise changes every 1 μm) was set on a mask frame of an exposure machine, and exposure was performed at 100mJ/cm via a projection lens 2 After the temporary support was peeled off, exposure was performed for 10 minutes, and then development was performed.
For development, a 1.0% aqueous sodium carbonate solution at 25 ℃ was used, and development by spraying was performed for 30 seconds.
When a line and space pattern of 10 μm was formed by the above method, residues in the space were observed by a Scanning Electron Microscope (SEM), and when exposure was performed with an exposure amount at which the resist line width was just 10 μm, the minimum line width at which the resist pattern could be resolved without peeling and residues was evaluated as resolution.
A: resolution of less than 2 mu m
B: resolution is 3 μm or more and 4 μm or less
C: resolution is 5 μm or more and 6 μm or less
D: resolution of 7 μm or more
A to C are preferred.
Pattern shape-
The cross section of the minimum line width pattern on which the above resolution evaluation was performed was observed by a Scanning Electron Microscope (SEM), and the pattern shape was evaluated.
A: the pattern shape is rectangular
B: the pattern shape slightly shrinks
C: the top of the pattern is rounded and shrunk
D: pattern collapse and skirt widening
A to C are preferred.
(examples 2 to 11 and comparative example 1 and comparative example 2)
Photosensitive transfer materials of examples 2 to 11 and comparative examples 1 and 2 were produced in the same manner as in example 1 except that the compositions of the intermediate layer and the photosensitive layer were changed as described in table 1.
Further, performance evaluation was performed in the same manner as in example 1. The evaluation results are summarized in table 1.
TABLE 1
The values of D4/D3 in examples 1 to 11 and comparative examples 1 and 2 were the same as the values of D2/D1 shown in Table 1.
As shown in table 1, the photosensitive transfer materials of examples 1 to 11 were excellent in resolution as compared with the photosensitive transfer materials of comparative example 1 or comparative example 2 even when the photosensitive layer was directly exposed without the temporary support.
As shown in table 1, the photosensitive transfer materials of examples 1 to 11 also have excellent pattern formability.
Example 101 contact Exposure
The photosensitive transfer material produced in example 1 was laminated on the copper-layer-equipped PET substrate under lamination conditions of a roll temperature of l00 ℃, a line pressure of 1.0MPa, and a line speed of 4.0 m/min. The temporary support was peeled off, exposed to light by an ultra-high pressure mercury lamp through a line-space pattern mask (duty ratio 1:1, line width 1 μm to 10 μm, stepwise changes every 1 μm), and then developed.
For development, a 1.0% aqueous sodium carbonate solution at 25 ℃ was used, and development by spraying was performed for 30 seconds.
The obtained pattern substrate was observed by a microscope, and a pattern having a good resolution and pattern shape was obtained.
(example 102: laser direct painting)
The photosensitive transfer material produced in example 1 was laminated on the copper-layer-equipped PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4.0 m/min. The illuminance was 80mW/cm by direct plotting of an exposure machine (Via Mechanics, manufactured by Ltd., DE-1DH, light source: gaN blue-violet diode (dominant wavelength 405 nm.+ -. 5 nm)), using a Stuffer 21-level step exposure table (steptab) or a mask pattern for prescribed DI exposure 2 Exposure is performed under the condition of (2). The exposure was performed with an exposure amount at which the highest residual film level at the time of exposure and development was 6 steps using the Stuffer 21 step exposure table (stepablet) as a mask. For development, a 1.0% aqueous sodium carbonate solution at 25 ℃ was used, and development by spraying was performed for 30 seconds.
The obtained pattern substrate was observed by a microscope, and a pattern having a good resolution and pattern shape was obtained.
Example 103
An ITO film was formed as a conductive layer of layer 2 by sputtering on a PET substrate having a thickness of 100 μm, and a copper film was formed as a conductive layer of layer 1 by vacuum evaporation thereon by a thickness of 200nm, thereby producing a circuit-forming substrate.
The cover film was peeled off from the copper layer, and the photosensitive transfer material obtained in example 1 was bonded to a substrate (lamination roll temperature i00 ℃, line pressure 0.8MPa, line speed 3.0 m/min.) to prepare a laminate. The resulting laminate was subjected to contact pattern exposure using a photomask provided with a pattern a shown in fig. 2 having a structure in which the temporary support was peeled off and the conductive layer pad was connected in one direction. In the exposure, a high-pressure mercury lamp having an i-ray (365 nm) as an exposure main wavelength was used.
Thereafter, development and water washing were performed to obtain a pattern a. Next, after etching the copper layer using a copper etching solution (KANTOCHEMICAL co., inc. Cu-02), the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., inc. ITO-02), whereby a substrate in which both copper and ITO were depicted in pattern a was obtained.
Next, the cover film was peeled off, and the photosensitive transfer material obtained in example 1 was again bonded to the remaining resist (cured negative photosensitive layer) under the same conditions as in example 101. In the aligned state, the temporary support is peeled off, pattern exposure is performed using a photomask provided with a pattern B shown in fig. 3, and then development and water washing are performed to obtain a pattern B. Then, the copper wiring was etched with Cu-02, and the residual cured negative photosensitive layer was peeled off with a peeling liquid (KANTO CHEMICAL CO., INC. Product KP-301), to obtain a circuit wiring board.
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.
The disclosure of japanese patent application 2020-217789, filed on even 25 months of 2020, is incorporated by reference in its entirety into this specification. 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.

Claims (18)

1. A photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer containing an ethylenically unsaturated compound,
bonding a substrate having a metal layer on the surface thereof to the transfer layer in the photosensitive transfer material, and applying an ultra-high pressure mercury lamp to a substrate having an energy density of 100mJ/cm at a wavelength of 365nm in air at 23 ℃ and 1 atm 2 When the photosensitive layer is exposed, the ratio D2/D1 of the extinction ratio D1 of the ethylenic unsaturated bonds exposed without peeling the temporary support to the extinction ratio D2 of ethylenic unsaturated bonds exposed after peeling the temporary support is 70 to 100%.
2. The photosensitive transfer material according to claim 1, wherein,
the oxygen permeability of the transfer layer was 1 mL/(m) 2 Day atm) to 100 mL/(m) 2 Day atm).
3. The photosensitive transfer material according to claim 1 or 2, wherein,
the photosensitive layer includes a photo radical polymerization initiator.
4. The photosensitive transfer material according to claim 3, wherein,
the photo-radical polymerization initiator is a photo-polymerization initiator which generates at least 1 kind of methyl radical or sulfur radical as a polymerization initiator.
5. The photosensitive transfer material according to any one of claims 1 to 4, wherein,
an intermediate layer is further provided between the temporary support and the photosensitive layer.
6. The photosensitive transfer material according to claim 5, wherein,
the intermediate layer comprises a water-soluble compound.
7. The photosensitive transfer material according to claim 6, wherein,
the water-soluble compound is at least 1 compound selected from water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives and amide compounds.
8. The photosensitive transfer material according to claim 6 or 7, wherein,
The water-soluble compound is polyvinyl alcohol.
9. The photosensitive transfer material according to claim 8, wherein,
the hydrolysis degree of the polyvinyl alcohol is 73-99 mol%.
10. The photosensitive transfer material according to claim 8 or 9, wherein,
the polyvinyl alcohol contains ethylene as a monomer unit.
11. The photosensitive transfer material according to any one of claims 5 to 10, wherein,
the intermediate layer comprises an inorganic layered compound.
12. The photosensitive transfer material according to any one of claims 1 to 11, wherein,
the ethylenically unsaturated compound comprises a polyfunctional ethylenically unsaturated compound.
13. The photosensitive transfer material according to any one of claims 1 to 12, wherein,
the ethylenically unsaturated compound comprises an ethylenically unsaturated compound having 3 or more functionalities.
14. The photosensitive transfer material according to any one of claims 1 to 13, wherein,
the ethylenically unsaturated compound comprises an ethylenically unsaturated compound having a polyethylene oxide structure.
15. A method for manufacturing a resin pattern, comprising, in order:
a step of bringing the transfer layer in the photosensitive transfer material according to any one of claims 1 to 14 into contact with a substrate to bond the transfer layer; and
And forming a pattern by performing exposure treatment and development treatment on the exposed photosensitive layer.
16. A method for manufacturing a circuit wiring includes, in order:
a step of bonding the transfer layer in the photosensitive transfer material according to any one of claims 1 to 14 in contact with a substrate having a conductive layer;
a step of forming a pattern by performing exposure treatment and development treatment on the exposed photosensitive layer; and
And a step of etching the substrate in the region where the resin pattern is not arranged.
17. A method of manufacturing an electronic device, comprising, in order:
a step of bonding the transfer layer in the photosensitive transfer material according to any one of claims 1 to 14 in contact with a substrate having a conductive layer;
a step of forming a pattern by performing exposure treatment and development treatment on the exposed photosensitive layer; and
And a step of etching the substrate in the region where the resin pattern is not arranged.
18. A method for producing a laminate, which comprises, in order:
a bonding step of bonding a transfer layer of a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer containing an ethylenically unsaturated compound to a substrate to produce a laminate;
A peeling step of peeling the temporary support from the laminate; and
a pattern forming step of performing exposure treatment and development treatment on the exposed photosensitive layer to form a pattern,
in air at 23℃and 1 atm, an ultra-high pressure mercury lamp was used to obtain a power density of 100mJ/cm at a wavelength of 365nm 2 When exposure is performed, the ratio D4/D3 of the extinction ratio D3 of the ethylenic unsaturated bonds at which the photosensitive layer of the laminate produced in the lamination step is exposed through the temporary support to the extinction ratio D4 of the ethylenic unsaturated bonds at which the photosensitive layer is exposed after the temporary support is peeled off in the peeling step is 80% to 100%.
CN202180085868.4A 2020-12-25 2021-12-20 Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, method for producing electronic device, and method for producing laminate Pending CN116635790A (en)

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JP2020217789 2020-12-25
JP2020-217789 2020-12-25
PCT/JP2021/047065 WO2022138576A1 (en) 2020-12-25 2021-12-20 Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring line, method for producing electronic device, and method for producing multilayer body

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JP3241144B2 (en) * 1993-02-19 2001-12-25 日立化成工業株式会社 Photosensitive resin composition laminate, method for producing resist pattern, method for producing substrate, printed wiring board, printed wiring board and equipment
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