CN112740107A - Method for manufacturing patterned base material, method for manufacturing circuit board, and method for manufacturing touch panel - Google Patents

Method for manufacturing patterned base material, method for manufacturing circuit board, and method for manufacturing touch panel Download PDF

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Publication number
CN112740107A
CN112740107A CN201980059678.8A CN201980059678A CN112740107A CN 112740107 A CN112740107 A CN 112740107A CN 201980059678 A CN201980059678 A CN 201980059678A CN 112740107 A CN112740107 A CN 112740107A
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resin composition
photosensitive resin
composition layer
group
pattern
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石坂壮二
汉那慎一
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • 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)
  • Theoretical Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

A method for manufacturing a patterned substrate and the use thereof, wherein the method comprises the following steps in sequence: a step of bonding a substrate to the photosensitive resin composition layer side of a photosensitive transfer material having a photosensitive resin composition layer supported by a temporary support; a step of peeling off the temporary support; a step of pattern-exposing the photosensitive resin composition layer; a step of bonding a protective film to the outermost layer on the photosensitive resin composition layer side subjected to pattern exposure; winding a laminate in which a base material, a pattern-exposed photosensitive resin composition layer, and a protective film are sequentially laminated; unwinding the wound laminate and peeling the protective film; and a step of developing the photosensitive resin composition layer exposed by the pattern to form a pattern of the photosensitive resin composition layer.

Description

Method for manufacturing patterned base material, method for manufacturing circuit board, and method for manufacturing touch panel
Technical Field
The present invention relates to a method for manufacturing a patterned base material, a method for manufacturing a circuit board, and a method for manufacturing a touch panel.
Background
In a display device (such as an organic Electroluminescence (EL) display device and a liquid crystal display device) including a touch panel such as a capacitive input device, a conductive pattern such as an electrode pattern of a sensor corresponding to a visual recognition unit, a peripheral wiring portion, and a wiring of a pickup wiring portion is provided inside the touch panel.
In forming the patterned layer, for example, the following method is employed: the layer of the photosensitive resin composition (photosensitive resin composition layer) provided on the temporary support having light transmittance is exposed through the temporary support via a mask having a desired pattern, then wound in a state of being stuck to the temporary support and stored, and unwound at the time of development to peel off the temporary support, thereby developing the photosensitive resin composition layer subjected to pattern exposure.
On the other hand, patent document 1 discloses a method for forming a resist pattern including the steps of: a laminating step of forming a photosensitive resin composition layer on a substrate by using a photosensitive resin composition laminate including at least a support film, a photosensitive resin composition layer, and a specific protective film, and laminating the photosensitive resin composition layer on the substrate while peeling the protective film, for the purpose of improving sensitivity, storage stability, and the like; an exposure step of exposing the photosensitive resin composition layer formed on the substrate; and a developing step of developing the exposed photosensitive resin composition layer to form a resist pattern on the substrate.
Prior art documents
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-088386
Disclosure of Invention
Technical problem to be solved by the invention
In the method disclosed in patent document 1, a pattern with high resolution can be formed because the photosensitive resin composition layer formed on the substrate is not subjected to pattern exposure via the support, but the method does not take into consideration a case where the photosensitive resin composition layer is temporarily stored after exposure until development.
The invention provides a method for manufacturing a patterned substrate, a method for manufacturing a circuit board using a patterned substrate obtained by the method for manufacturing a patterned substrate, and a method for manufacturing a touch panel, wherein the method for manufacturing a patterned substrate can prevent the photosensitive resin composition layer after exposure from being peeled off from a photosensitive transfer material having the photosensitive resin composition layer supported by a temporary support, and the photosensitive resin composition layer is exposed and then wound before development.
Means for solving the technical problem
The means for solving the above problems include the following means.
< 1 > a method for producing a patterned substrate, which comprises the following steps in order: a step of bonding a substrate to the photosensitive resin composition layer side of a photosensitive transfer material having a temporary support and a photosensitive resin composition layer supported by the temporary support;
a step of peeling off the temporary support;
a step of pattern-exposing the photosensitive resin composition layer;
a step of bonding a protective film to the outermost layer on the photosensitive resin composition layer side to which the pattern exposure is performed, when viewed from the substrate side;
a step of winding a laminate in which the base material, the photosensitive resin composition layer exposed through the pattern, and the protective film are sequentially laminated;
unwinding the wound laminate and peeling the protective film; and
and a step of forming a pattern of the photosensitive resin composition layer by developing the photosensitive resin composition layer exposed to the pattern.
< 2 > the method for producing a patterned substrate according to < 1 >, wherein the photosensitive resin composition layer contains an acid-decomposable resin.
< 3 > the method for producing a patterned substrate according to < 2 >, wherein the acid-decomposable resin has a structural unit represented by the following formula A1, formula A2 or formula A3.
[ chemical formula 1]
Figure BDA0002969578740000031
In the formula A1, R11And R12Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R11And R12Any of which is alkyl or aryl, R13Represents alkyl or aryl, optionally R11Or R12And R13Linked to form a cyclic ether, R14Represents a hydrogen atom or a methyl group, X1Represents a single bond or a divalent linking group, R15Represents a substituent, and n represents an integer of 0 to 4.
In the formula A2, R21And R22Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R21And R22Any of which is alkyl or aryl, R23Represents alkyl or aryl, optionally R21Or R22And R23Linked to form a cyclic ether, R24Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyl groupAn alkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In the formula A3, R31And R32Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R31And R32Any of which is alkyl or aryl, R33Represents alkyl or aryl, optionally R31Or R32And R33Linked to form a cyclic ether, R34Represents a hydrogen atom or a methyl group, and X0 represents a single bond or a divalent linking group.
< 4 > the method for producing a patterned substrate according to any one of < 1 > to < 3 >, wherein the protective film is a protective film comprising a resin having a structural unit containing a phenolic hydroxyl group or a structural unit containing an alcoholic hydroxyl group not directly bonded to the main chain, or an acrylic resin.
< 5 > the method for producing a patterned substrate according to < 4 >, wherein the resin having the structural unit containing the phenolic hydroxyl group or the structural unit containing an alcoholic hydroxyl group not directly bonded to the main chain is at least 1 resin selected from the group consisting of a modified cellulose resin and a novolac resin.
< 6 > the method for producing a patterned substrate according to any one of < 1 > to < 5 >, wherein the photosensitive transfer material is a photosensitive transfer material having an intermediate layer between the temporary support and the photosensitive resin composition layer.
< 7 > A method for manufacturing a circuit board, which comprises the following steps in order: a step of producing the patterned substrate by using, as the substrate, a substrate having a conductive layer on a surface of the photosensitive transfer material on the photosensitive resin composition layer side, by the method for producing a patterned substrate according to any one of < 1 > -6 >;
etching the conductive layer exposed in a region of the patterned substrate where the pattern of the photosensitive resin composition layer is not formed; and
removing the pattern of the photosensitive resin composition layer;
< 8 > A method for manufacturing a touch panel, which comprises < 7 > the method for manufacturing a circuit substrate.
Effects of the invention
According to one embodiment of the present invention, it is possible to provide a method for manufacturing a patterned base material, a method for manufacturing a circuit board using a patterned base material obtained by the method for manufacturing a patterned base material, and a method for manufacturing a touch panel, in which even when a temporary support is peeled from a photosensitive transfer material having a photosensitive resin composition layer supported by the temporary support, the photosensitive resin composition layer is exposed, and then a winding step is performed before development, peeling of the photosensitive resin composition layer after exposure can be suppressed.
Drawings
Fig. 1 is a schematic view showing an example of a flow of manufacturing a circuit board as one embodiment of the method of manufacturing a patterned base material of the present invention.
Fig. 2 is a schematic view schematically showing a method of continuously performing the temporary support peeling step, the exposure step, the protective film sticking step, and the winding step as one embodiment of the method of manufacturing a patterned substrate of the present invention.
FIG. 3 is a schematic view showing an example of a structure of a laminate in which a photosensitive resin composition layer and a temporary support are provided on both surfaces of a base.
Fig. 4 is a schematic view showing an example of the structure of the photosensitive transfer material including the cover film.
Detailed Description
The present invention will be described below. Note that, although the description is made with reference to the drawings, the reference numerals may be omitted.
In the present specification, the numerical range represented by "to" means a range in which the numerical values before and after "to" are included as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acrylate" represents both or either of acrylate and methacrylate.
In addition, with respect to the amount of each component in the composition in the present specification, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition is indicated.
In the present specification, the term "step" includes not only an independent step but also a step that is not clearly distinguished from other steps, and is included in the term as long as the intended purpose of the step is achieved.
In the labeling of a group (atomic group) in the present specification, a label not recorded as substituted and unsubstituted includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl" means that an alkyl group having a substituent (substituted alkyl) is included as well as an alkyl group having no substituent (unsubstituted alkyl).
The chemical structural formula in this specification may be described as a simple structural formula in which a hydrogen atom is omitted.
In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.
In the present invention, unless otherwise specified, the weight average molecular weight and the number average molecular weight in the polymer component are weight average molecular weights in terms of polystyrene measured in Gel Permeation Chromatography (GPC) with Tetrahydrofuran (THF) as a solvent.
(method for producing patterned substrate)
The method for manufacturing a patterned substrate of the present invention sequentially performs the following steps: a step of bonding a substrate to the photosensitive resin composition layer side of a photosensitive transfer material having a temporary support and a photosensitive resin composition layer supported by the temporary support (substrate bonding step); a step of peeling off the temporary support (temporary support peeling step); a step (exposure step) of pattern-exposing the photosensitive resin composition layer; a step of bonding a protective film to the outermost layer on the photosensitive resin composition layer side exposed by the pattern when viewed from the substrate side (protective film bonding step); a step (winding step) of winding a laminate in which the base material, the pattern-exposed photosensitive resin composition layer, and the protective film are sequentially laminated; a step (protective film peeling step) of unwinding the wound laminate and peeling the protective film; and a step (developing step) of developing the photosensitive resin composition layer exposed to the pattern to form a pattern of the photosensitive resin composition layer.
In the method for producing a patterned substrate of the present invention, since the temporary support is peeled off and the photosensitive resin composition layer is exposed, the resolution of the pattern obtained can be improved as compared with the case where the photosensitive resin composition layer is exposed without peeling off the temporary support.
On the other hand, the present inventors have found that when the temporary support is peeled off and exposed, and then wound in a roll and stored for a predetermined time, the pattern of the photosensitive resin composition layer is easily peeled off when the temporary support is unwound and developed during development.
The reason why the pattern of the photosensitive resin composition layer is easily peeled is presumably that the pattern is peeled from the soft portion of the photosensitive resin composition layer as a starting point. This is presumably because the unexposed portion of the negative photosensitive resin composition layer contains a large amount of monomers, and the exposed portion of the positive photosensitive resin composition layer contains a large amount of low molecules resulting from photodecomposition, and therefore, the photosensitive resin composition layer in the unexposed portion, which is to remain as a pattern, is softened by the decomposition reaction during storage before development after exposure.
The present inventors have also found that when the temporary support is peeled off and exposed, and then wound into a roll and stored for a predetermined time, and development is performed by unwinding the roll during development, the pattern of the photosensitive resin composition layer formed after development is likely to change from the exposure pattern.
The reason why the pattern of the photosensitive resin composition layer formed after development fluctuates from the exposure pattern may be as follows: when the concentration of a decomposition product (for example, a deprotected product of a polymer in the case of a positive photosensitive resin composition layer, or a decomposition product of a polymerization initiator in the case of a negative photosensitive resin composition layer) in the photosensitive resin composition layer after exposure is increased, the low molecular weight component is increased, whereby plasticization of the photosensitive resin composition layer is promoted to cause a reaction, and a pattern such as a variation in line width is likely to be caused during a period from exposure to development.
As a result of intensive studies by the present inventors, it has been found that, in the step of peeling off the temporary support and performing pattern exposure, and then providing a protective film on the outermost layer on the photosensitive resin composition layer side and winding the protective film into a roll, peeling off of the photosensitive resin composition layer when the photosensitive resin composition layer is subsequently stored and the protective film is unwound from the roll and developed can be suppressed, and further, a change in the pattern during storage can be suppressed.
The reason is not clear, but it is presumed that the reason is that the protective film is provided on the photosensitive resin composition layer after exposure and wound, whereby absorption of the decomposition component of the photosensitive resin composition layer by the protective film and plasticization and reaction of the photosensitive resin composition layer after winding are suppressed, and peeling of the photosensitive resin composition layer and change in pattern can be suppressed.
Fig. 1 is a schematic view showing an example of a flow of manufacturing a circuit board as an embodiment of the method of manufacturing a patterned base material of the present invention.
In the example shown in fig. 1, a photosensitive transfer material 33 in which the temporary support 18, the intermediate layer 38, and the photosensitive resin composition layer 36 are sequentially stacked, and a substrate 35 provided with a resin film 32 and a conductive layer 34 are used, and as shown in fig. 1 a, the photosensitive resin composition layer 36 of the photosensitive transfer material 33 and the conductive layer 34 of the substrate 35 are bonded (substrate bonding step).
After the substrates are bonded, the temporary support 18 is peeled off (temporary support peeling step), and as shown in fig. 1B, the photosensitive resin composition layer 36 is pattern-exposed through the intermediate layer 38 using a mask 70 (exposure step). In the exposure step, pattern exposure is performed in a state where the temporary support 18 is peeled off, so that pattern exposure with high resolution can be performed.
After the exposure, as shown in fig. 1(C), a protective film 42 is bonded to the outermost intermediate layer 38 on the photosensitive resin composition layer 36 side which has been pattern-exposed, when viewed from the substrate side (protective film bonding step).
The laminate in which the substrate 35, the photosensitive resin composition layer 36 subjected to pattern exposure, the intermediate layer 38, and the protective film 42 are sequentially laminated is wound by the lamination of the protective film 42 (winding step).
After the winding, when the photosensitive resin composition layer 36 subjected to the pattern exposure is developed, the wound laminate is unwound, and the protective film 42 is peeled off (protective film peeling step), and as shown in fig. 1(D), the photosensitive resin composition layer 36 subjected to the pattern exposure is developed to form a pattern (in this specification, sometimes referred to as "patterned photosensitive resin composition layer", "resist pattern") 136 of the photosensitive resin composition layer 36 (developing step). When the developing step is performed, a patterned substrate having the pattern 136 of the photosensitive resin composition layer is produced, which suppresses peeling of the photosensitive resin composition layer 36 and the pattern 136 and also suppresses a change in the exposure pattern.
Next, as shown in fig. 1E, the conductive layer 34 exposed in the region of the patterned substrate where the pattern (resist pattern) 136 of the photosensitive resin composition layer is not formed is etched (etching step).
After the etching, as shown in fig. 1(F), the pattern 136 of the photosensitive resin composition layer is removed (pattern removal step).
Through the above steps, a circuit board having the circuit 134 formed from the conductive layer 34 can be manufactured on the resin film 32.
Hereinafter, each step will be specifically described.
< substrate bonding Process >
The method for manufacturing a patterned substrate of the present invention includes a step of bonding a substrate to a photosensitive resin composition layer side of a photosensitive transfer material having a temporary support and a photosensitive resin composition layer supported by the temporary support. In the photosensitive transfer material, the temporary support and the photosensitive resin composition layer may or may not be in direct contact.
For example, in the example shown in fig. 1, as shown in fig. 1(a), a photosensitive transfer material 33 having a temporary support 18, an intermediate layer 38, and a photosensitive resin composition layer 36, and a substrate 35 having a resin film 32 and a conductive layer 34 are used, and the photosensitive transfer material 33 is bonded to the conductive layer 34 side of the substrate 35 on the photosensitive resin composition layer 36 side.
Photosensitive transfer material
The photosensitive transfer material of the present invention includes a temporary support and a photosensitive resin composition layer supported by the temporary support.
The temporary support is preferably a support that supports the photosensitive resin composition layer and can be peeled from the photosensitive resin composition layer, and is a support that can be peeled from the intermediate layer 38 when the intermediate layer 38 is present.
The temporary support may be a resin film, paper, or the like, and is preferably a resin film in view of strength, flexibility, or the like. Examples of the resin film include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a polyethylene terephthalate film is preferable, and a biaxially stretched polyethylene terephthalate film is particularly preferable.
When the photosensitive resin composition layer supported by the temporary support is subjected to pattern exposure, the photosensitive resin composition layer is usually subjected to pattern exposure via the temporary support having light transmittance, but in the method for producing a patterned substrate of the present invention, the temporary support is peeled off before the exposure step described later, and the photosensitive resin composition layer is not subjected to pattern exposure via the temporary support. Therefore, in the method for producing a patterned substrate of the present invention, the temporary support does not need to have light-transmitting properties.
The term "having optical transparency" means that the transmittance of the dominant wavelength of light used for exposure in the exposure step described later is 50% or more.
The thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm from the viewpoints of easy handling, versatility, and the like.
The thickness of the temporary support may be selected according to the material, from the viewpoints of the strength of the temporary support, the flexibility required for bonding to the substrate, the light transmittance required in the exposure step, and the like.
A preferred embodiment of the temporary support is described in paragraphs 0017 to 0018 of japanese patent application laid-open No. 2014-085643, for example, and the contents of this publication are incorporated in the present specification.
In the method for producing a patterned substrate of the present invention, the photosensitive resin composition layer is supported by the temporary support until the exposure step.
The photosensitive resin composition layer may be a so-called positive photosensitive resin composition layer in which the removability in development is increased by exposure, or a so-called negative photosensitive resin composition layer in which the removability in development is decreased by exposure.
The thickness of the photosensitive resin composition layer is preferably 0.5 to 20 μm. When the thickness of the photosensitive resin composition layer is 20 μm or less, the pattern resolution is more excellent, and from the viewpoint of pattern linearity, it is preferably 0.5 μm or more.
The thickness of the photosensitive resin composition layer is more preferably 0.8 to 15 μm, and particularly preferably 1.0 to 10 μm.
The method for producing the photosensitive transfer material is not particularly limited, and can be produced by a known method.
Specifically, for example, a photosensitive transfer material having a photosensitive resin composition layer on a temporary support can be obtained by applying a photosensitive resin composition to the temporary support and drying the applied composition. The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
Further, the photosensitive resin composition layer may be applied to a laminate of the temporary support and another layer described later.
The photosensitive transfer material may have a layer other than the temporary support and the photosensitive resin composition layer (hereinafter, may be referred to as "other layer").
Examples of the other layers include a contrast-enhancing layer, an intermediate layer, a cover film, and a thermoplastic resin layer.
The material constituting the photosensitive resin composition layer (i.e., the photosensitive resin composition) and the layers other than the temporary support and the photosensitive resin composition layer in the photosensitive transfer material in the present invention will be described in detail later.
A substrate
The substrate used in the present invention is preferably a flexible substrate such as a resin film according to winding after exposure. In the case where the circuit wiring in the method for manufacturing a circuit board of the present invention to be described later is a circuit wiring for a touch panel, the base material is particularly preferably a base material including a conductive layer for forming a circuit.
The refractive index of the resin film is preferably 1.50 to 1.52.
The substrate may be composed of a light-transmitting substrate (transparent substrate).
The term "transparent" in the present invention means that the transmittance of all visible rays is 85% or more, preferably 90% or more, and more preferably 95% or more.
When a substrate including a resin film (in this specification, it may be referred to as a resin film substrate) is used as the substrate, it is preferable to use a substrate having high transparency without optical deformation. Specific examples of the material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, cellulose triacetate, and cycloolefin polymer.
In the method for manufacturing a circuit board of the present invention to be described later, the base preferably has a conductive layer for forming a circuit on one surface of the resin film. In the present invention, the term "conductivity" means a volume resistivity of less than 1X 107Ω·cm。
When a substrate having a conductive layer is used, in the substrate bonding step, the substrate and the photosensitive transfer material are preferably bonded so that the conductive layer is in contact with the photosensitive resin composition layer.
As the conductive layer, any conductive layer used for a general circuit wiring or touch panel wiring can be cited.
Examples of the material of the conductive layer include metals and metal oxides.
Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Au, Ag, Ti, W, Si, and Mo. Examples of the metal Oxide include ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide).
The conductive layer preferably contains a metal oxide.
The conductive layer may be formed of 1 layer or 2 or more layers, and the conductive layer on the surface of the base material may be formed of different materials. For example, a mode in which 2 or more conductive layers made of different materials are provided on one surface of the base material, a mode in which a1 st metal layer is formed on a part of one surface of the base material and a2 nd metal layer different from the 1 st metal layer is formed on the other surface, a mode in which a metal layer is formed on a part of 1 surface of the base material and a metal oxide layer is formed on the other surface of 1 surface, and the like can be illustrated.
The shape and thickness of each of the base material and the conductive layer are not particularly limited, and may be appropriately set according to the desired patterned base material or circuit board.
In the substrate bonding step, for example, the conductive layer of the substrate having the conductive layer is pressed so as to be in contact with the photosensitive resin composition layer of the photosensitive transfer material. In the above-described aspect, the pattern of the photosensitive resin composition layer after exposure and development (i.e., the patterned photosensitive resin composition layer) can be preferably used as an etching resist in etching the conductive layer.
The method for pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and a known transfer method or lamination method can be used.
Specifically, for example, it is preferable that the photosensitive resin composition layer side of the photosensitive transfer material is superimposed on the conductive layer of the substrate, and the lamination is performed by applying pressure by a roller or the like or by applying pressure and heat. For the bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving productivity can be used.
The pressure and temperature in the base material bonding step are not particularly limited, and can be appropriately set according to the material and the transfer speed of the conductive layer and the photosensitive resin composition layer, the pressure bonding machine used, and the like. For example, as shown in fig. 4, when the cover film 60 is provided on the photosensitive resin composition layer 36 side of the photosensitive transfer material, the cover film 60 may be removed from the photosensitive resin composition layer 36 and then pressure-bonded.
When the substrate is a substrate including a resin film, the substrate may be pressure-bonded using a roll-to-roll method.
< temporary support peeling Process >
The method for producing a patterned substrate of the present invention includes a step of peeling off the temporary support after the substrate bonding step.
The method for peeling off the temporary support is not particularly limited, and a known method can be employed, and a peeling roller is preferably mentioned. It is preferable that the temporary support is peeled after the nip is performed with the nip roller so that the peeling point does not change. Further, it is preferable to appropriately adjust the winding tension to stably peel.
The size of the peeling roller used in the temporary support peeling step is not particularly limited, and may be appropriately set according to the width, length, thickness, and the like of the substrate.
The material of the peeling roller is not particularly limited as long as it has sufficient strength, and a known material can be used.
< Exposure Process >
The method for producing a patterned substrate of the present invention comprises a step of pattern-exposing the photosensitive resin composition layer.
In the exposure step, the substrate on which the coating film of the photosensitive resin composition (photosensitive resin composition layer) is provided is preferably irradiated with actinic rays through a mask having a predetermined pattern. In this step, for example, when the photosensitive resin composition layer is a positive photosensitive resin composition layer, the photoacid generator is decomposed to generate an acid. The acid-decomposable group contained in the coating component is hydrolyzed by the action of the generated acid catalyst to generate an acid group such as a carboxyl group or a phenolic hydroxyl group.
In the present invention, the detailed arrangement and specific dimensions of the pattern 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 a circuit board manufactured by the method for manufacturing a patterned base material according to the present invention and to reduce the area occupied by the extraction wiring as much as possible, at least a part of the pattern (particularly, an electrode pattern of the touch panel and a part of the extraction wiring) is preferably a thin line of 100 μm or less, and more preferably a thin line of 70 μm or less.
The exposure in the exposure step may be exposure through a mask, or may be digital exposure using a laser or the like, and is preferably exposure through an exposure mask.
In the method for producing a patterned substrate according to the present invention, it is preferable that a step of bringing the photosensitive transfer material into contact with an exposure mask is provided between the substrate bonding step and the exposure step. In this manner, the resolution of the obtained pattern is more excellent.
The actinic ray includes visible light, ultraviolet light, and electron beam, and preferably visible light or ultraviolet light, and particularly preferably ultraviolet light.
As the exposure light source based on actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a Light Emitting Diode (LED) light source, an excimer laser generating apparatus, and the like can be used, and actinic rays having a wavelength of 300nm to 450nm such as g-ray (436nm), i-ray (365nm), h-ray (405nm), and the like can be preferably used. The irradiation light can also be adjusted by a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter, as necessary.
As the exposure device, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity detector, a contactor, a microlens, and laser exposure can be used.
The exposure amount is appropriately selected depending on the photosensitive resin composition layer to be usedNamely, it is preferably 5mJ/cm2～200mJ/cm2More preferably 10mJ/cm2～100mJ/cm2。
In the exposure step, it is preferable that the conveyance of the laminate including the photosensitive resin composition layer is stopped when the exposure in the exposure step is performed.
< protective film application Process >
The method for producing a patterned substrate of the present invention comprises a step of bonding a protective film to the outermost layer on the photosensitive resin composition layer side exposed to a pattern when viewed from the substrate side. If the outermost layer is a photosensitive resin composition layer, the protective film is attached to the photosensitive resin composition layer, and if the outermost layer on the photosensitive resin composition layer side is an intermediate layer 38, as shown in fig. 1(C), for example, a protective film 42 is attached to the intermediate layer 38.
The material of the protective film is not particularly limited as long as it can be adhered to and wound around the outermost layer on the photosensitive resin composition layer side subjected to pattern exposure, and a resin film is particularly preferable from the viewpoint of strength and flexibility. Examples of the resin that can be used as the protective film include cellulose triacetate, polyolefin, acrylic resin, polyvinyl alcohol, polypropylene, polyethylene terephthalate (PET), and polyethylene.
The protective film in the present invention is preferably a protective film of a resin or acrylic resin containing a structural unit having a phenolic hydroxyl group or a structural unit having an alcoholic hydroxyl group not directly bonded to the main chain.
In the case of the protective film containing a resin having a structural unit having a phenolic hydroxyl group or a structural unit having an alcoholic hydroxyl group not directly bonded to the main chain, for example, a vinyl ether which is a decomposition component of a resin having an acetal protection with an acid generated when the positive photosensitive resin composition layer is exposed to light is easily absorbed.
In addition, the protective film containing an acrylic resin also easily absorbs vinyl ether generated as a decomposition component when the positive photosensitive resin composition layer is exposed.
The resin having a structural unit having a phenolic hydroxyl group or a structural unit having an alcoholic hydroxyl group not directly bonded to the main chain is preferably at least 1 resin selected from the group consisting of modified cellulose resins and novolac resins. In particular, a protective film containing a modified cellulose resin or a novolac resin is likely to absorb a decomposition product (for example, vinyl ether).
The thickness of the protective film is not particularly limited, and is preferably 10 μm to 70 μm, for example. When the thickness of the protective film is 10 μm or more, the photosensitive resin composition layer after pattern exposure can be easily attached and detached before development, and the protective film can be prevented from being broken by tension. Further, if the thickness of the protective film is 70 μm or less, the winding of the protective film after the attachment becomes easy, and therefore, the weight of the roll after the winding can be suppressed from being increased, which is advantageous for transportation and storage.
As the protective film, commercially available products can be used, and examples thereof include materials, trade names, and manufacturers (marker) described below, but the protective film is not limited to these commercially available products.
Examples of the protective film containing cellulose triacetate include FUJITAC (registered trademark) TD40, FUJITAC TD60, KC8UX2M, and KC4UY, both of which are available from fujitlm Corporation, Konica Minolta mechanics co.
Examples of the protective film containing a polyolefin/acrylic resin include TORETEC (registered trademark) 7141, TORETEC7531, TORETEC7332, TORETEC7131, and TORETEC7312, available from toway ADVANCED FILM co.
Examples of the protective film containing polyvinyl alcohol include KURARAY co, POVAL (registered trademark) film VF-PS #7500, POVAL film VF-PE #3000, and EVAL (registered trademark) film EF-XL of ltd.
Examples of the polypropylene-containing protective film include ARUFAN (registered trademark) HS-101, ARUFAN PU-002, and ARUFAN of Oji F-Tex Co., Ltd.
Examples of the protective film containing polyethylene terephthalate include lumiror (registered trademark) FB50 of TORAY INDUSTRIES, inc, T788#50 of Daicel Corporation, and T788# 75.
The method for attaching the protective film to the outermost layer on the photosensitive resin composition layer side is not particularly limited. For example, as shown in fig. 2 described later, a method of unwinding the protective film 42 from a roll 40 for winding the protective film and attaching the protective film 42 to the outermost layer on the photosensitive resin composition layer side after pattern exposure via a nip roll 17 can be cited.
< winding Process >
The method for producing a patterned substrate of the present invention comprises a step of winding a laminate in which a substrate, a photosensitive resin composition layer subjected to pattern exposure, and a protective film are laminated in this order.
The method of winding the laminate into a roll is not particularly limited, and a known method can be employed, and a winding roll can be preferably used.
The winding core used for winding may be a conventionally known winding core made of paper, resin, metal, or the like, and is preferably a resin winding core in view of dust emission, weight, ease of handling, and the like.
The size of the winding roll used in the winding step, such as the diameter and width, is not particularly limited, and may be appropriately set according to the width, length, and thickness of the base material.
The material of the winding roll is not particularly limited as long as it has sufficient strength, and a known material can be used. Examples of the winding roll include paper, resin, and metal, and a winding roll made of resin is preferable from the viewpoint of dust emission, weight, and ease of handling.
In the winding step, it is preferable that the winding and the stopping are repeated in accordance with the conveyance stop at the time of exposure in the exposure step. When the winding and stopping are repeated without the conveyance stop at the time of exposure in the exposure step, it is preferable to have a gap mechanism such as a dancer roll.
In the method for producing a patterned substrate according to the present invention, the temporary support peeling step, the exposure step, the protective film sticking step, and the winding step may be continuously performed roll to roll. Fig. 2 schematically shows an example of the method for producing a patterned substrate according to the present invention, in which the step of peeling off the temporary support to the step of winding up are continuously performed. In the example shown in fig. 2, as shown in fig. 3, a laminate 14 in which copper layers (i.e., conductive layers) 34A and 34B, photosensitive resin composition layers 36A and 36B, and temporary supports 18A and 18B are laminated in this order on both sides of a resin film 32 from the resin film 32 side is used. As another layer, for example, an intermediate layer may be disposed between the photosensitive resin composition layers 36A and 36B and the temporary supports 18A and 18B, respectively.
In the example shown in fig. 2, as the temporary support peeling step, the laminate 14 is unwound by the unwinding roller 12 and conveyed by the conveying roller 16, and the temporary supports 18A and 18B are peeled from both surfaces of the laminate 14 in the rolling roller 15. The temporary support members 18A and 18B to be peeled are wound around the upper and lower peeling rollers 20A and 20B, respectively.
After the temporary supports 18A and 18B are peeled off, the photosensitive resin composition layers 36A and 36B of the laminate 22 from which the temporary supports 18A and 18B are peeled off are exposed in a pattern form by the upper and lower exposure light sources 26A and 26B in the exposure apparatus 24 as an exposure step. In addition, since the copper layers 34A and 34B provided as conductive layers on both surfaces of the resin film 32 of the laminate 22 from which the temporary supports 18A and 18B are peeled shield the light from the exposure light sources 26A and 26B, the photosensitive resin composition layers 36A and 36B can be pattern-exposed to a desired shape by the exposure light sources 26A and 26B without receiving the light from the exposure light sources 26B and 26A disposed on the opposite sides, respectively.
The laminated body 39 in which the photosensitive resin composition layers 36A and 36B on both sides are pattern-exposed is conveyed by the conveying rollers 16. Thereafter, as a protective film attaching step, the protective film 42 is unwound from the protective film roll 40, the protective film 42 and the pattern-exposed laminate 39 are joined at the nip roll 17, and the protective film 42 is attached to one photosensitive resin composition layer 36B of the photosensitive resin composition layers 36A and 36B which become the outermost layers.
The protective film 42 may be attached to the photosensitive resin composition layer 36A without being attached to the photosensitive resin composition layer 36B. Further, although the protective films may be attached to the photosensitive resin composition layers 36A and 36B on both sides, the protective film 42 is preferably attached to one of the photosensitive resin composition layers 36A and 36B on both sides from the viewpoint of the roll diameter after winding and cost reduction.
After the protective film 42 is attached, as a winding step, the laminate 52 having the protective film 42 attached to the photosensitive resin composition layer 36B is wound around a winding roll 50. As shown in fig. 2, when the protective film 42 is attached to one photosensitive resin composition layer 36B, the photosensitive resin composition layer 36A is also in contact with the protective film 42 attached to the photosensitive resin composition layer 36B of the laminate 52 wound before, and therefore, peeling of the photosensitive resin composition layers 36A and 36B on both sides after exposure and a change in pattern can be effectively suppressed.
< protective film peeling Process >
The method for manufacturing a patterned substrate of the present invention includes a step of unwinding the wound laminate and peeling the protective film.
The method of unwinding the wound laminate and peeling the protective film in the winding step is not particularly limited.
For example, when a winding roll is used in the winding step, the end of the laminate is stretched, the laminate is unwound and the protective film is peeled off while the winding roll is rotated in the opposite direction to that in the winding step, the laminate from which the protective film is peeled off is transported to the developing step, and the peeled protective film is wound around the winding roll. The unwinding speed of the laminate in the developing step may be appropriately set according to the conveyance speed of the laminate at the time of development.
For example, similarly to the peeling of the temporary support shown in fig. 2, the protective film-attached laminate is unwound from a roll of the protective film-attached laminate and conveyed by a conveying roll, and the protective film peeled from the laminate is wound around a winding roll, whereby the peeling of the protective film and the conveyance of the laminate can be continuously performed.
< developing Process >
The method for producing a patterned substrate of the present invention comprises a step (developing step) of forming a pattern of the photosensitive resin composition layer by developing the photosensitive resin composition layer exposed to the pattern after the protective film is peeled off.
The development of the exposed photosensitive resin composition layer in the development step can be performed using a developer.
The developing solution is not particularly limited as long as the exposed portion of the photosensitive resin composition layer can be removed, and a known developing solution such as that shown in japanese patent application laid-open No. 5-072724 can be used. The developing solution is preferably a developing solution which causes the exposed portion of the photosensitive resin composition layer to be soluble. The developer is preferably an aqueous alkaline solution, and more preferably an aqueous alkaline solution containing a compound having a pKa of 7 to 13 at a concentration of, for example, 0.05mol/L (liter) to 5 mol/L. The developer may further contain water and a miscible organic solvent, a surfactant, and the like. As the developer preferably used in the present invention, for example, the developer described in paragraph 0194 of international publication No. 2015/093271 can be cited.
The developing method is not particularly limited, and any of liquid immersion development, shower and spin development, immersion development, and the like may be used. Here, the shower development is explained, and the exposed portion can be removed by spraying a developing solution to the exposed photosensitive resin composition layer. After the development, it is preferable to remove the development residue by spraying and blowing a cleaning agent or the like while wiping with a brush or the like. The temperature of the developing solution is preferably 20 ℃ to 40 ℃.
The method for producing a patterned substrate of the present invention may include known steps such as a step of washing with water or the like after development and a step of drying the obtained patterned substrate.
Further, the method may further include a step of drying the pattern including the photosensitive resin composition layer obtained by the development after the heat treatment.
The temperature of the postbaking is preferably from 80 ℃ to 250 ℃, more preferably from 110 ℃ to 170 ℃, and particularly preferably from 130 ℃ to 150 ℃.
The post-drying time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
The post-drying can be carried out in an air environment or a nitrogen substitution environment.
The post-drying may be performed under atmospheric pressure or under reduced pressure.
The transfer speed of the laminate in each step in the method for producing a patterned substrate of the present invention is not particularly limited, but is preferably 0.5 to 10m/min except for exposure, and more preferably 2.0 to 8.0m/min except for exposure.
The method for producing a patterned substrate of the present invention may further include other steps such as a post-exposure step.
As examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of japanese patent application laid-open No. 2006-023696 can be preferably used.
As described above, the substrate bonding step, the temporary support peeling step, the exposure step, the protective film bonding step, the winding step, the protective film peeling step, and the developing step are sequentially performed, whereby a patterned substrate in which a pattern of the photosensitive resin composition layer is formed on the substrate can be manufactured.
(method of manufacturing Circuit Board)
The method for manufacturing a circuit board of the present invention sequentially performs the following steps: a step of producing a patterned substrate obtained by the method for producing a patterned substrate, using as a substrate having a conductive layer on the surface on the photosensitive resin composition layer side to be bonded to a photosensitive transfer material (patterned substrate production step);
a step (etching step) of etching the conductive layer exposed in a region of the patterned substrate where the photosensitive resin composition layer is not formed; and
and a step of removing the pattern of the photosensitive resin composition layer (pattern removal step).
The patterned substrate manufacturing process is as described above, and therefore, the description thereof is omitted here.
< etching Process >
In the etching step, the pattern formed by the photosensitive resin composition layer in the patterned substrate obtained by the method for producing a patterned substrate of the present invention (the pattern of the photosensitive resin composition layer) is used as an etching resist, and etching treatment of the conductive layer is performed.
The conductive layer can be etched by a known method such as the method described in paragraphs 0048 to 0054 of jp 2010-152155 a.
For example, as a method of etching, a wet etching method in which the substrate is immersed in an etching solution is generally performed. The etching solution used in the wet etching may be appropriately selected from an acidic type etching solution and an alkaline type etching solution according to an object to be etched.
Examples of the acidic etching solution include an aqueous solution of a single acidic component such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or phosphoric acid, and an aqueous solution of a mixture of an acidic component and a salt such as ferrous chloride, ammonium chloride, or potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.
Examples of the alkaline type etching solution include an aqueous solution having a single alkali component, such as a salt of an organic amine, such as sodium hydroxide, potassium hydroxide, ammonia, or 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.
The temperature of the etching solution is not particularly limited, but is preferably 45 ℃. In the present invention, the pattern used as the etching mask (i.e., the etching pattern) preferably exhibits particularly excellent resistance to an acidic and alkaline etching solution in a temperature range of 45 ℃. Therefore, the positive photosensitive resin composition layer is prevented from peeling off in the etching step, and a portion where the positive photosensitive resin composition layer is not present is selectively etched.
After the etching step, a step of cleaning the substrate (cleaning step) and a step of drying the substrate (drying step) may be performed as necessary in order to prevent contamination of the process line. The cleaning step may be carried out, for example, by cleaning the substrate with pure water at normal temperature (10 ℃ C. to 35 ℃ C.) for 10 seconds to 300 seconds. In the drying step, for example, the blowing pressure (0.1 kg/cm) is appropriately adjusted by a blower2～5kg/cm2Left and right) to be dried.
< Pattern removal Process >
The method for manufacturing a circuit board of the present invention preferably includes a pattern removal step of removing the pattern of the photosensitive resin composition layer after the etching step.
After the etching step is completed, the patterned photosensitive resin composition layer remains. If the photosensitive resin composition layer is not necessary, all the remaining photosensitive resin composition layer may be removed.
For example, as a method for peeling off the photosensitive resin composition layer using a peeling liquid, for example, a method of immersing a substrate having a photosensitive resin composition layer or the like in a peeling liquid stirred at preferably 30 to 80 ℃ and more preferably 50 to 80 ℃ for 5 to 30 minutes is cited.
Examples of the stripping solution include solutions of inorganic bases such as sodium hydroxide and potassium hydroxide, or organic bases such as tertiary amines and quaternary ammonium salts in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. The peeling can be performed by a spray method, a shower method, a spin-coating immersion method, or the like using a peeling liquid.
The method for manufacturing a circuit board of the present invention may include other arbitrary steps. For example, the following steps are mentioned, but the present invention is not limited to these steps.
< Process for reducing reflectance of visible ray >
The method for manufacturing a circuit board of the present invention may include a step of performing a treatment for reducing the visible light reflectance of a part or all of the conductive layer on the base material.
As the treatment for reducing the visible light reflectance, oxidation treatment and the like can be cited. For example, the visible light reflectance can be reduced by performing oxidation treatment of copper to convert the copper into copper oxide and blackening the copper.
Preferable modes of the treatment for reducing the reflectance of visible light are described in paragraphs 0017 to 0025 of jp 2014-150118 a and paragraphs 0041, 0042, 0048 and 0058 of jp 2013-206315 a, the contents of which are incorporated in the present specification.
< Process for Forming insulating film on etched conductive layer and Process for Forming New conductive layer on insulating film >
The method for manufacturing a circuit board of the present invention preferably includes a step of forming an insulating film on the formed circuit wiring (i.e., the etched conductive layer) and a step of forming a new conductive layer on the insulating film.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. 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. A photosensitive material having conductivity can be used to form a new conductive layer in a desired pattern by photolithography.
In the method for manufacturing a circuit board of the present invention, the new conductive layer may be etched by forming an etching resist by the same method as described above, or may be etched separately by a known method.
The circuit board obtained by the method for manufacturing a circuit board according to the present invention may have only 1 layer of circuit wiring formed of a conductive layer, or may have 2 or more layers of circuit wiring formed of a conductive layer.
In the method for manufacturing a circuit board according to the present invention, it is also preferable to form a circuit on both surfaces of the conductive layer one by one or simultaneously by using a base material having conductive layers on both surfaces, as shown in fig. 3, for example. With this configuration, a circuit wiring in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface can be formed, and preferably, a circuit wiring for a touch panel can be formed.
< Circuit Board >
The application of the circuit board manufactured by the method for manufacturing a circuit board of the present invention is not limited, and for example, a circuit board for a touch panel is preferable. A preferred embodiment of the circuit board for a touch panel will be described later in the description of the capacitive input device.
< input device and display apparatus >
An input device is an example of an apparatus including a circuit board manufactured by the method for manufacturing a circuit board according to the present invention.
The input device in the present invention is preferably an electrostatic capacitance type touch panel.
The display device of the present invention preferably includes the input device of the present invention. The display device in the present invention is preferably an image display device such as an organic EL display device or a liquid crystal display device.
< touch Panel and touch Panel display device >
The touch panel of the present invention is a touch panel including at least a circuit board manufactured by the method for manufacturing a circuit board of the present invention. Further, the touch panel of the present invention preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device of the present invention is preferably a touch panel display device having at least a circuit board manufactured by the method for manufacturing a circuit board of the present invention, and a touch panel display device having a touch panel of the present invention.
The touch panel of the present invention and the detection method of the touch panel display device of the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.
Examples of the Touch panel type include a so-called in-cell type (described in, for example, fig. 5, 6, 7, and 8 of jp 2012-a 517051), a so-called out-cell type (described in, for example, fig. 19 of jp 2013-a 168125, fig. 1 and 5 of jp 2012-a 089102), an OGS (One Glass Solution) type, a TOL (Touch-on-Lens) type (described in, for example, fig. 2 of jp 2013-a 054727), other structures (described in, for example, fig. 6 of jp 2013-a 164871), and various plug-in types (described in, for example, GG, G1-G2, GFF, GF2, GF1, G1F).
As the touch panel and the touch panel display device according to the present invention, the configurations disclosed in "latest touch panel technology" (published by technologies Times 6.7/2009), "least squares" major edition, "technology and development of touch panel", CMC publishing (2004, 12), FPD International 2009Forum T-11 lecture, and Cypress Semiconductor Corporation application note AN2292, etc. can be applied.
Here, the photosensitive resin composition layer will be described in detail.
< Positive photosensitive resin composition layer >
The positive photosensitive resin composition layer used in the present invention is not particularly limited, and a known positive photosensitive resin composition layer can be used. The positive photosensitive resin composition layer used in the present invention is preferably a chemically amplified positive photosensitive resin composition layer containing a polymer having a structural unit having an acid group protected by an acid-decomposable group, which is an acid-decomposable resin, and a photoacid generator, from the viewpoint of sensitivity, resolution, and removability.
Since an acid generated by induction of active radiation (actinic rays) in a photoacid generator such as an onium salt or an oxime sulfonate compound described later functions as a catalyst for deprotection of a protected acid group in the polymer, the acid generated by the action of 1 photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as a few powers of 10, and high sensitivity can be obtained as a result of so-called chemical amplification.
On the other hand, when a quinonediazide compound is used as a photoacid generator for sensitive active radiation, a carboxyl group is generated by a sequential photochemical reaction, but the quantum yield thereof is required to be 1 or less, and it is not in accordance with a chemical amplification type.
[ Polymer A1 containing a Polymer having a structural Unit containing an acid group protected with an acid-decomposable group ]
The positive photosensitive resin composition layer is preferably a polymer (also simply referred to as "polymer a 1") containing a structural unit (also referred to as "structural unit a") having an acid group protected by an acid-decomposable group.
The positive photosensitive resin composition layer may contain other polymers in addition to the polymer a1 having the structural unit a. In the present invention, the polymer a1 having the structural unit a and other polymers are blended, and are also referred to as "polymer components".
The polymer component is not intended to contain a surfactant described later.
Therefore, when the polymer component and the resin component other than the surfactant are not contained in the positive photosensitive resin composition layer, the resin component in the positive photosensitive resin composition layer refers to the polymer component.
The polymer a1 is subjected to deprotection reaction of the structural unit a having an acid group protected by an acid-decomposable group in the polymer a1 by the action of a catalyst amount of an acidic substance generated by exposure to light to form an acid group. The acid group can be dissolved in the developer.
Further, the polymer a1 preferably further has a structural unit containing an acid group.
Preferred embodiments of the structural unit a are described below.
The positive photosensitive resin composition layer may further contain a polymer other than the polymer a1 having a structural unit containing an acid group protected by an acid-decomposable group.
Further, all the polymers contained in the polymer component are preferably polymers each having at least a structural unit containing an acid group described later.
The positive photosensitive resin composition may further contain a polymer other than these. The polymer component in the present invention means that other polymers added as needed are contained unless otherwise specified. Further, even if the compound corresponding to a crosslinking agent and a dispersing agent described later is a polymer compound, the compound is not included in the polymer component.
The polymer a1 is preferably an addition polymerization type resin, more preferably (meth) acrylic acid or a polymer having a structural unit derived from the ester. Further, the (meth) acrylic acid ester may have a structural unit other than the structural unit derived from the (meth) acrylic acid ester, for example, a structural unit derived from styrene, a structural unit derived from an ethylene compound, or the like.
From the viewpoint of suppressing deformation of the pattern shape, solubility in a developer, and transferability, the positive photosensitive resin composition layer preferably contains, as the polymer component, a polymer having, as the structural unit a, at least 1 structural unit selected from the group consisting of structural units represented by any one of formulae a1 to A3 (i.e., an acid-decomposable resin), and more preferably contains, as the polymer component, a polymer having, as the structural unit a, at least 1 structural unit selected from the group consisting of structural units represented by any one of formulae a1 to A3, and an acid group.
The number of the polymers a1 contained in the positive photosensitive resin composition layer may be only 1, or 2 or more.
Structural unit A-
The polymer component is preferably a polymer a1 containing a structural unit a having at least an acid group protected by an acid-decomposable group. The polymer component contains a polymer having a structural unit a, and thus can be a chemically amplified positive photosensitive resin composition layer with extremely high sensitivity.
The "acid group protected by an acid-decomposable group" (hereinafter, the acid-decomposable group protecting the acid group may be referred to as a "protecting group") in the present invention is not particularly limited, and a known acid group and acid-decomposable group can be used. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. As the acid group protected by an acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester group protected by a group represented by formula a3, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group) or a group which is relatively hardly decomposed by an acid (for example, a tertiary alkyl carbonate such as a tertiary butyl ester group or a tertiary alkyl carbonate such as a tertiary butyl carbonate) can be used.
Among these, preferred is a group having a structure protected in the form of acetal as an acid-decomposable group.
Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in line width in the obtained circuit wiring.
The structural unit a having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula a1, formula a2 or formula A3, and more preferably a structural unit represented by the following formula A3-3, from the viewpoint of sensitivity and resolution.
[ chemical formula 2]
Figure BDA0002969578740000231
In the formula A1, R11And R12Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R11And R12Any of which is alkyl or aryl, R13Represents alkyl or aryl, R11Or R12And R13May be linked to form a cyclic ether, R14Represents a hydrogen atom or a methyl group, X1Represents a single bond or a divalent linking group, R15Represents a substituent, and n represents an integer of 0 to 4.
In the formula A2, R21And R22Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R21And R22Any of which is alkyl or aryl, R23Represents alkyl or aryl, R21Or R22And R23May be linked to form a cyclic ether, R24Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In the formula A3, R31And R32Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R31And R32Any of which is alkyl or aryl, R33Represents alkyl or aryl, R31Or R32And R33May be linked to form a cyclic ether, R34Represents a hydrogen atom or a methyl group, X0Represents a single bond or a divalent linking group.
When the protective group has an acetal structure, the specific protective film easily absorbs acetal decomposed products (mainly vinyl ethers). The acid-decomposable resin is preferably a carboxylic acetal protective group structure because acid decomposition is rapid and sensitivity is low.
< preferred mode of structural unit represented by the formula A1 >
In the formula A1, R11Or R12In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10. R11Or R12When aryl, phenyl is preferred. R11And R12Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A1, R13Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
And, R11～R13The alkyl group and the aryl group in (1) may have a substituent.
In the formula A1, R11Or R12And R13May be linked to form a cyclic ether, preferably R11Or R12And R13May be linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the formula A1, X1Represents a single bond or a divalent linking group, and is preferably a single bond or an alkylene group, -C (═ O) O-, -C (═ O) NRN-, -O-or a combination of these, more preferably a single bond. The alkylene group may have a branched chain even in a linear state, may have a cyclic structure, and may have a substituent. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 4. X1When it contains-C (═ O) O-, it is preferable that the carbon atom contained in-C (═ O) O-is bonded to R14The carbon atoms of (b) are directly bonded. X1containing-C (═ O) NRNwhen-O-is preferred, it is-C (═ O) NRNCarbon atom contained in (A) with R bonded thereto14The carbon atoms of (b) are directly bonded. RNRepresents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a hydrogen atom.
In the formula A1, R is preferably contained11～R13Group of (2) and X1Bonded in para position to each other.
In the formula A1, R15Represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.
In the formula A1, n represents an integer of 0 to 4, preferably 0 or 1, more preferably 0.
In the formula A1, R14Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of further lowering Tg (glass transition temperature) of the polymer a 1.
More specifically, R in the formula A1 is relative to the total content of the structural units A contained in the polymer A114The structural unit that is a hydrogen atom is preferably 20 mass% or more.
In addition, R in the formula A1 in the structural unit A14The content (content ratio: mass ratio) of the structural unit which is a hydrogen atom can be determined according to13The intensity ratio of the peak intensities determined by C-nuclear magnetic resonance spectroscopy (NMR) and calculated by a conventional method was confirmed.
Among the structural units represented by the formula a1, the structural unit represented by the following formula a1-2 is more preferable from the viewpoint of suppressing the deformation of the pattern shape.
[ chemical formula 3]
Figure BDA0002969578740000241
In the formula A1-2, RB4Represents a hydrogen atom or a methyl group, RB5～RB11Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, RB12Represents a substituent, and n represents an integer of 0 to 4.
In the formula A1-2, RB4Preferably a hydrogen atom.
In the formula A1-2, RB5～RB11Preferably a hydrogen atom.
Formula A1-2, RB12Represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.
In the formula A1-2, n represents an integer of 0 to 4, preferably 0 or 1, more preferably 0.
As a preferred specific example of the structural unit a1 represented by formula a1, the following structural units can be exemplified. In addition, RB4Represents a hydrogen atom or a methyl group.
[ chemical formula 4]
Figure BDA0002969578740000251
< preferred mode of structural unit represented by the formula A2 >
In the formula A2, R21And R22When the alkyl group is used, the alkyl group preferably has 1 to 10 carbon atoms. R21And R22When aryl, phenyl is preferred. R21And R22Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably at least one of which is a hydrogen atom.
In the general formula A2, R23Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
R21Or R22And R23May be linked to form a cyclic ether.
In the formula A2, R24Preferably, each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R24Can be prepared by reaction with R24The same groups are further substituted.
In formula a2, m is preferably 1 or 2, more preferably 1.
A preferred specific example of the structural unit A2 represented by the formula A2 is as follows.
[ chemical formula 5]
Figure BDA0002969578740000261
< preferred mode of structural unit represented by the formula A3 >
In the formula A3, R31Or R32In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10. R31Or R32When aryl, phenyl is preferred. R31And R32Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A3, R33Represents an alkyl or aryl groupThe alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.
And, R31～R33The alkyl group and the aryl group in (1) may have a substituent.
In the formula A3, R31Or R32And R33May be linked to form a cyclic ether, preferably R31Or R32And R33May be linked to form a cyclic ether. The number of cyclic elements of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the formula A3, X0Represents a single bond or an arylene group, preferably a single bond. The arylene group may have a substituent.
The structural unit represented by formula a3 is a structural unit having a carboxyl group protected by an acid-decomposable group. The polymer a1 contains a structural unit represented by formula A3, and thus sensitivity in forming a pattern is excellent and resolution is more excellent.
In the formula A3, R34Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of further lowering the Tg of the polymer a 1.
More specifically, R in the formula A3 is relative to the total amount of the structural unit represented by the formula A3 contained in the polymer A134The structural unit that is a hydrogen atom is preferably 20 mass% or more.
In addition, R in the formula A1 in the structural unit represented by the formula A334The content (content ratio: mass ratio) of the structural unit which is a hydrogen atom can be determined according to13The intensity ratio of the peak intensities determined by C-nuclear magnetic resonance spectroscopy (NMR) and calculated by a conventional method was confirmed.
Among the structural units represented by the formula A3, the structural unit represented by the following formula A3-3 is more preferable from the viewpoint of further improving the sensitivity in forming a pattern.
[ chemical formula 6]
Figure BDA0002969578740000271
In the formula A3-3, R34Represents hydrogenAtom or methyl radical, R35～R41Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A3-3, R34Preferably a hydrogen atom.
In the formula A3-3, R35～R41Preferably a hydrogen atom.
As a preferable specific example of the structural unit having a carboxyl group protected with an acid-decomposable group represented by formula a3, the following structural unit can be exemplified. In addition, R34Represents a hydrogen atom or a methyl group.
[ chemical formula 7]
Figure BDA0002969578740000272
The number of the structural unit a included in the polymer a1 may be 1, or 2 or more.
The content of the structural unit a in the polymer a1 is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and still more preferably 30% by mass to 70% by mass, based on the total mass of the polymer a 1.
The content (content ratio: mass ratio) of the structural unit A in the polymer A1 can be determined by13C-NMR measurement and confirmation of the intensity ratio of the peak intensities calculated by a conventional method.
Further, the proportion of the structural unit a is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 30 to 70% by mass, based on the total mass of the polymer components, in order to decompose all the polymer components into structural units (monomer units).
Structural unit B-
The polymer a1 preferably comprises structural units B having acid groups.
The structural unit B is, for example, a structural unit having an acid group which is not protected by an acid-decomposable group, that is, an acid group having no protecting group. Since the polymer a1 contains the structural unit B, the sensitivity in forming a pattern is improved, and the polymer a1 is easily dissolved in an alkaline developer in a developing step after pattern exposure, thereby shortening the developing time.
The acid group in the present specification represents a proton-dissociative group having a pKa of 12 or less. The acid group is usually incorporated in the polymer as a structural unit (structural unit B) having an acid group using a monomer capable of forming an acid group. From the viewpoint of improving the sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Also, the pKa of the acid group is preferably-5 or more.
Examples of the acid group include a carboxyl group, a sulfonamido group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonimide group. Among them, at least 1 kind of acid group selected from the group consisting of a carboxylic acid group and a phenolic hydroxyl group is preferable.
The introduction of the structural unit having an acid group into the polymer a1 can be performed by copolymerizing a monomer having an acid group or copolymerizing a monomer having an acid anhydride structure to hydrolyze the acid anhydride.
The structural unit having an acid group as the structural unit B is more preferably a structural unit obtained by substituting an acid group for a structural unit derived from a styrene compound or a structural unit derived from a vinyl compound or a structural unit derived from (meth) acrylic acid. Specifically, examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene, examples of the monomer having a phenolic hydroxyl group include p-hydroxystyrene and 4-hydroxyphenylmethacrylate, and examples of the monomer having an acid anhydride include maleic anhydride.
The structural unit B is preferably a structural unit having a carboxylic acid group or a structural unit having a phenolic hydroxyl group, from the viewpoint that the sensitivity in pattern formation is further improved.
The monomer capable of forming the acid group of the structural unit B is not limited to the above-described examples.
The number of the structural units B contained in the polymer a1 may be only 1, or may be 2 or more.
The polymer a1 preferably contains the structural unit having an acid group (structural unit B) in an amount of 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass, based on the total mass of the polymer a 1. When the amount is within the above range, the pattern formability is further improved.
The content (content ratio: mass ratio) of the structural unit B in the polymer A1 can be determined by13C-NMR measurement and confirmation of the intensity ratio of the peak intensities calculated by a conventional method.
Other structural units
The polymer a1 may contain structural units other than the structural unit a and the structural unit B (hereinafter, may be referred to as a structural unit C) within a range not impairing the effects of the photosensitive transfer material according to the present invention.
The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds.
The structural unit C can be used to adjust at least any one of the type and the content, thereby adjusting various properties of the polymer a 1. In particular, the Tg of the polymer a1 can be easily adjusted by appropriately using the structural unit C.
When the glass transition temperature is 120 ℃ or lower, the positive photosensitive resin composition layer containing the polymer a1 maintains transferability and removability from the temporary support at good levels, and improves resolution and sensitivity in pattern formation.
The polymer a1 may contain only 1 kind of the structural unit C, or may contain 2 or more kinds.
Specific examples of the structural unit C include structural units obtained by polymerizing styrene, t-butoxystyrene, methylstyrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, ethylene methyl benzoate, ethylene ethyl benzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, and the like. Further, compounds described in paragraphs 0021 to 0024 of Japanese patent laid-open No. 2004-264623 can be mentioned.
In addition, the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton, from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specific examples of the monomer forming these structural units include styrene, tert-butoxystyrene, methylstyrene, α -methylstyrene, dicyclopentadienyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Among them, as the structural unit C, a structural unit derived from cyclohexyl (meth) acrylate can be preferably cited.
The monomer forming the structural unit C is preferably an alkyl (meth) acrylate, for example, from the viewpoint of adhesion. Among these, alkyl (meth) acrylates having an alkyl group having 4 to 12 carbon atoms are more preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
The content of the structural unit C is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less, based on the total mass of the polymer a 1. The lower limit may be 0 mass%, but is preferably 1 mass% or more, and more preferably 5 mass% or more. When the content is within the above range, the resolution and the adhesion are further improved.
From the viewpoint of optimum solubility in a developer and physical properties of the positive photosensitive resin composition layer, the polymer a1 is also preferable as the structural unit C to include a structural unit of an ester having an acid group in the structural unit B.
Among these, the polymer a1 is preferably a polymer containing a structural unit having a carboxylic acid group as a structural unit B and a structural unit C having a carboxylic acid ester group as a copolymerization component, and is more preferably a polymer containing a structural unit B derived from (meth) acrylic acid, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or a structural unit (C) derived from n-butyl (meth) acrylate, for example.
Preferred examples of the polymer a1 in the present invention will be described below, but the present invention is not limited to the examples below. In order to obtain preferable physical properties, the ratio of the structural units in the following exemplary compounds and the weight average molecular weight are appropriately selected.
[ chemical formula 8]
Figure BDA0002969578740000311
Average value of I/O values of polymer components-average value of I/O values of inorganic value I divided by organic value O based on an organic conceptual diagram is preferably 0.55 to 0.65, more preferably 0.57 to 0.63, from the viewpoint of removability of the polymer component used in the present invention.
The I/O value of the specific polymer used in the present invention may be appropriately set so that the average value of the I/O values falls within the above range, and is preferably 0.55 to 0.65, and more preferably 0.57 to 0.63.
Regarding I/O values, organic concept maps (hind farmed, SANKYO SHUPPAN co., Ltd. (1984)); kumamoto Pharmaceutical Bulletin, No. 1, pages 1-16 (1954); chemical field, volume 11, No. 10, pages 719-725 (1957); FRAGRANCE JOURNAL, No. 34, pp.97 to 111 (1979); FRAGRANCE JOURNAL, No. 50, pages 79 to 82 (1981); etc. are described in detail in the literature. The concept of I/O value is to divide the properties of a compound into organic groups representing covalent bonding and inorganic groups representing ionic bonding, and to locate each point on an orthogonal coordinate that names all organic compounds as organic and inorganic axes.
The I/O value when the polymer component contains 2 or more polymers can be considered as follows. For example, when the polymer component contains 3 kinds of polymers (polymer 1 to polymer 3), the I/O value Am of the mixed component can be estimated as follows when the I/O value of polymer 1 is a1, the mass fraction is M1, the I/O value of polymer 2 is a2, the mass fraction is M2, the I/O value of polymer 3 is A3, and the mass fraction is M3.
Am＝A1×M1+A2×M2+A3×M3
When the polymer component contains only 1 polymer alone, the I/O value of only 1 polymer contained is the average value of the I/O values in the polymer component.
Glass transition temperature of polymer a 1: tg-
The glass transition temperature (Tg) of the polymer a1 in the present invention is preferably 90 ℃ or lower, more preferably 20 ℃ to 60 ℃ inclusive, and further preferably 30 ℃ to 50 ℃ inclusive, from the viewpoint of transferability and from the viewpoint of adjusting the heating temperature in the heating step.
As a method for adjusting Tg of the polymer to the above-described preferable range, Tg of the target polymer a1 can be controlled, for example, by using FOX formula as a guideline based on a mass ratio of Tg of each individual polymer of each constituent unit of the target polymer to each constituent unit.
With respect to the formula FOX,
when Tg of the polymer alone of the 1 st structural unit contained in the polymer is Tg1, mass fraction in the copolymer of the 1 st structural unit is W1, Tg of the polymer alone of the 2 nd structural unit is Tg2, and mass fraction in the copolymer of the 2 nd structural unit is W2, Tg0(K) of the copolymer containing the 1 st structural unit and the 2 nd structural unit can be estimated according to the following formula.
FOX formula: 1/Tg0 ═ W1/Tg1) + (W2/Tg2)
The kind and mass fraction of each structural unit contained in the copolymer can be adjusted by the formula FOX already described to obtain a copolymer having a desired Tg.
Further, the Tg of the polymer can also be adjusted by adjusting the weight average molecular weight of the polymer.
Acid number of Polymer A1-
The acid value of the polymer A1 is preferably from 0mgKOH/g to 200mgKOH/g, more preferably from 5mgKOH/g to 100mgKOH/g, from the viewpoint of developability and transferability.
The acid value of the polymer in the present invention represents the mass of potassium hydroxide required for neutralizing 1g of the acidic component of the polymer. Specifically, a measurement sample was dissolved in a tetrahydrofuran/water 9/1 mixed solvent, and the obtained solution was subjected to neutralization titration with a 0.1M aqueous sodium hydroxide solution AT 25 ℃ using a potential difference titration apparatus (trade name: AT-510, KYOTO electroinc. The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated by the following formula.
A＝56.11×Vs×0.1×f/w
A: acid value (mgKOH/g)
Vs: amount of 0.1mol/l aqueous sodium hydroxide solution (mL) required for titration
f: titration amount of 0.1mol/l aqueous solution of sodium hydroxide
w: the mass (g) of the sample was measured (in terms of solid content)
Molecular weight of polymer a 1: mw-
The molecular weight of the polymer a1 is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. The weight average molecular weight of the polymer a1 is 60,000 or less, whereby the melt viscosity of the positive photosensitive resin composition layer is suppressed to be low, and bonding at a low temperature (for example, 130 ℃ or less) can be achieved when bonding to the substrate.
The weight average molecular weight of the polymer A1 is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
The weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatuses and the measuring techniques are known to those skilled in the art.
In the measurement of the weight average molecular weight by Gel Permeation Chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used as a measurement device, and TSKgel (registered trademark), Super HZM-M (4.6mmID × 15cm, manufactured by Tosoh Corporation), Super HZ4000(4.6mmID × 15cm, manufactured by Tosoh Corporation), Super HZ3000(4.6mmID × 15cm, manufactured by Tosoh Corporation), Super HZ2000(4.6mmID × 15cm, manufactured by Tosoh Corporation), and THF (tetrahydrofuran) were used as eluents, wherein 1 column was serially connected to each other.
The measurement conditions were 0.2 mass% of the sample concentration, 0.35ml/min of the flow rate, 10. mu.L of the sample injection amount, and 40 ℃ of the measurement temperature, and a differential Refractive Index (RI) detector was used.
The calibration curve can be obtained using a "standard TSK standard, polystyrene" manufactured by Tosoh Corporation: any of 7 samples of "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" was prepared.
The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer A1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
Process for the preparation of Polymer A1
The method for producing the polymer a1 (synthesis method) is not particularly limited, and for example, the polymer a1 can be synthesized by polymerizing a polymerizable monomer for forming the structural unit a represented by the formula a, a polymerizable monomer for forming the structural unit B having an acid group, and, if necessary, a polymerizable monomer for forming another structural unit C in an organic solvent using a polymerization initiator. Further, the synthesis can also be performed by a so-called polymer reaction.
The positive photosensitive resin composition layer in the present invention preferably contains the polymer component at a ratio of 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total solid content of the positive photosensitive resin composition layer, from the viewpoint of exhibiting good adhesion to the substrate.
In addition, the positive photosensitive resin composition layer preferably contains the polymer a1 in a proportion of 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total solid content of the positive photosensitive resin composition layer, from the viewpoint of exhibiting good adhesion to the substrate.
[ other polymers ]
The positive photosensitive resin composition layer may further contain, as a polymer component, a polymer (sometimes referred to as "other polymer") that does not contain a structural unit having an acid group protected by an acid-decomposable group, within a range that does not impair the effect of the photosensitive transfer material according to the present invention, in addition to the polymer a 1. When the positive photosensitive resin composition layer contains another polymer, the amount of the other polymer blended is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less of the total polymer components.
The positive photosensitive resin composition layer may contain only 1 kind of other polymer, or 2 or more kinds of other polymers, in addition to the polymer a 1.
As the other polymer, for example, polyhydroxystyrene can be used, and commercially available SMA1000P, SMA 2000P, SMA 391440F, SMA 17352P, SMA P, and SMA3840F (made by Sartomer Company, supra), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARON UC-3080 (made by TOAGOSEI CO., LTD., supra), Joncryl 690, Joncryl 678, Joncryl 67, and Joncryl 586 (made by BASF UFSE, supra), and the like can be used.
[ photoacid generators ]
The positive photosensitive resin composition layer preferably contains a photoacid generator.
The photoacid generator used in the present invention is a compound capable of generating an acid by irradiation with radiation such as ultraviolet light, far ultraviolet light, X-rays, and charged particle rays.
The photoacid generator used in the present invention is preferably a compound that generates an acid by sensing an actinic ray having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure thereof is not limited. Further, as the photoacid generator which does not directly sense actinic rays having a wavelength of 300nm or more, a compound which generates an acid by sensing actinic rays having a wavelength of 300nm or more is used together with a sensitizer, and can be preferably used in combination with a sensitizer.
The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of the pKa is not particularly limited, but is preferably at least-10.0, for example.
Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
The photoacid generator preferably contains at least 1 compound selected from the group consisting of an onium salt compound described below and an oxime sulfonate compound described below, and more preferably contains an oxime sulfonate compound, from the viewpoint of sensitivity and resolution.
Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion. These photoacid generators can be used alone in 1 kind or in combination of 2 or more kinds. Specific examples of trichloromethyl s-triazine and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.
The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure is preferably a compound having an oxime sulfonate structure represented by the following formula (B1).
[ chemical formula 9]
Figure BDA0002969578740000361
In the formula (B1), R21Represents an alkyl group or an aryl group, and represents a bonding site with other atoms or other groups.
With respect to the compound having an oxime sulfonate structure represented by the formula (B1), any of the groups may be substituted, and R21The alkyl group in (1) may be a straight chainThe compound may have a branched structure or a cyclic structure. The following describes the permissible substituents.
As R21The alkyl group of (3) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. R21The alkyl group (C) may be substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (including a bridged alicyclic group such as 7, 7-dimethyl-2-hydroxynorbornane, preferably a bicycloalkyl group) or a halogen atom.
As R21The aryl group of (1) is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. R21The aryl group (C) may be substituted with 1 or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group and a halogen atom.
The compound having an oxime sulfonate structure represented by the formula (B1) is preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of Japanese patent application laid-open No. 2014-085643.
Examples of a preferable photoacid generator include those having the following structures.
[ chemical formula 10]
Figure BDA0002969578740000362
[ chemical formula 11]
Figure BDA0002969578740000371
[ chemical formula 12]
Figure BDA0002969578740000372
Further, "OTs" represents p-toluenesulfonyl.
Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Among these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of Japanese patent application laid-open No. 2014-085643 can be preferably used.
The photoacid generator may be used alone or in combination of 2 or more.
The content of the photoacid generator in the positive photosensitive resin composition layer is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, with respect to the total mass of the positive photosensitive resin composition layer, from the viewpoint of sensitivity and resolution.
[ solvent ]
The positive photosensitive resin composition layer may contain a solvent.
In order to easily form the positive photosensitive resin composition layer, the positive photosensitive resin composition layer can be preferably formed by first containing a solvent to adjust the viscosity of the positive photosensitive resin composition, and then coating and drying the positive photosensitive resin composition containing the solvent.
As the solvent used in the present invention, a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. Specific examples of the solvent include those described in paragraphs 0174 to 0178 of Japanese patent application laid-open No. 2011-221494, and these are incorporated herein.
Further, a solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate may be added to the above-described solvent as necessary.
The solvent may be used in 1 kind or 2 or more kinds.
The solvent used in the present invention may be used alone in 1 kind, and preferably used in combination in 2 kinds. When 2 or more solvents are used, it is preferable to use propylene glycol monoalkyl ether acetates and dialkyl ethers simultaneously, diacetates and diethylene glycol dialkyl ethers simultaneously, or esters and butanediol alkyl ether acetates simultaneously, for example.
The solvent is preferably a solvent having a boiling point of 130 ℃ or higher and lower than 160 ℃, a solvent having a boiling point of 160 ℃ or higher, or a mixture of these solvents.
Examples of the solvent having a boiling point of 130 ℃ or higher and lower than 160 ℃ include propylene glycol monomethyl ether acetate (boiling point 146 ℃), propylene glycol monoethyl ether acetate (boiling point 158 ℃), propylene glycol methyl-n-butyl ether (boiling point 155 ℃) and propylene glycol methyl-n-propyl ether (boiling point 131 ℃).
As the solvent having a boiling point of 160 ℃ or higher, ethyl 3-ethoxypropionate (boiling point 170 ℃), diethylene glycol methylethylether (boiling point 176 ℃), propylene glycol monomethyl ether propionate (boiling point 160 ℃), dipropylene glycol methyl ether acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol diacetate (boiling point 190 ℃), diethylene glycol monoethylether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃) and 1, 3-butanediol diacetate (boiling point 232 ℃).
The content of the solvent in coating the positive photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass per 100 parts by mass of the total solid content in the positive photosensitive resin composition.
The content of the solvent in the positive photosensitive resin composition layer is preferably 2 mass% or less, more preferably 1 mass% or less, and still more preferably 0.5 mass% or less, based on the total mass of the positive photosensitive resin composition layer.
[ other additives ]
The positive photosensitive resin composition layer in the present invention may contain known additives as needed, in addition to the polymer a1 and the photoacid generator.
Plasticizer-
The positive photosensitive resin composition layer may contain a plasticizer for the purpose of improving plasticity.
The weight average molecular weight of the plasticizer is preferably less than that of polymer a 1.
The weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and further preferably 800 or more and less than 4,000, from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the polymer a1 and exhibits plasticity, and from the viewpoint of imparting plasticity, it is preferable that the plasticizer has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.
[ chemical formula 13]
Figure BDA0002969578740000391
In the formula, R is an alkyl group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and x represents a bonding site with other atoms.
Even if the compound is, for example, a compound having an alkyleneoxy group of the above structure (referred to as "compound X"), the plasticizer of the present invention is not included in the case where the plasticity of the chemically amplified positive photosensitive resin composition obtained by mixing the compound X, the polymer a1, and the photoacid generator is not improved as compared with the chemically amplified positive photosensitive resin composition formed without the compound X. For example, the surfactant to be added arbitrarily is not included in the plasticizer in the present specification because it is not generally used in an amount that imparts plasticity to the positive photosensitive resin composition.
Examples of the plasticizer include compounds having the following structures, but are not limited thereto.
[ chemical formula 14]
Figure BDA0002969578740000392
From the viewpoint of adhesion, the content of the plasticizer is preferably 1 to 50% by mass, and more preferably 2 to 20% by mass, based on the total mass of the positive photosensitive resin composition layer.
The positive photosensitive resin composition layer may contain only 1 kind of plasticizer, or may contain 2 or more kinds.
Sensitizers-
The positive photosensitive resin composition layer can further contain a sensitizer.
The sensitizer absorbs actinic rays to become an electron excited state. The sensitizer in the electron-excited state is brought into contact with the photoacid generator to cause electron movement, energy movement, heat generation, and the like. This causes the photoacid generator to chemically change and decompose, thereby generating an acid.
By containing a sensitizer, exposure sensitivity can be improved.
The sensitizer is preferably a compound selected from the group consisting of anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, basic styrene derivatives, and stilbene styrene derivatives, and more preferably an anthracene derivative.
As the anthracene derivative, preferred is anthracene, 9, 10-dibutoxyanthracene, 9, 10-dichloroanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9, 10-dibromoanthracene, 2-ethylanthracene or 9, 10-dimethoxyanthracene.
Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International publication No. 2015/093271.
The content of the sensitizer is preferably 0 to 10% by mass, more preferably 0.1 to 10% by mass, relative to the total mass of the positive photosensitive resin composition layer.
Basic compounds-
The positive photosensitive resin composition layer preferably further contains a basic compound.
The basic compound can be arbitrarily selected from basic compounds used for chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of these compounds include the compounds described in paragraphs 0204 to 0207 of Japanese patent application laid-open publication No. 2011-221494, and the contents thereof are incorporated in the present specification.
Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline and diphenylamine.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4, 5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxoquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1, 5-dioxaazabicyclo [4.3.0] -5-nonene, and 1, 8-dioxazabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, and the like.
The basic compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the basic compound is preferably 0.001 to 5% by mass, and more preferably 0.005 to 3% by mass, based on the total mass of the positive photosensitive resin composition layer.
Heterocyclic compounds
The positive photosensitive resin composition layer in the present invention may contain a heterocyclic compound.
The heterocyclic compound in the present invention is not particularly limited. Examples of the compound include compounds having an epoxy group or an oxetanyl group in the molecule, heterocyclic compounds having an alkoxymethyl group, oxygen-containing monomers such as various cyclic ethers and cyclic esters (lactones), nitrogen-containing monomers such as cyclic amines and oxazolines, and d-electron-carrying heterocyclic monomers such as silicon, sulfur and phosphorus.
When the heterocyclic compound is added, the amount of the heterocyclic compound added to the positive photosensitive resin composition layer is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and still more preferably 1 to 5% by mass, based on the total mass of the positive photosensitive resin composition layer. The above range is preferable from the viewpoint of adhesion and etching resistance. The heterocyclic compounds may be used in only 1 kind, or 2 or more kinds may be used simultaneously.
Specific examples of the compound having an epoxy group in the molecule include bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like.
The compound having an epoxy group in the molecule can be obtained as a commercially available product. Examples thereof include commercially available products described in paragraph 0189 of Japanese patent laid-open publication No. 2011-221494, such as JER828, JER1007, JER157, 39157S 70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and the like.
Other commercially available products include ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA CORPORATION), DENACOL EX-611, EX-612, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-220, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-941, EX-920, EX, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (manufactured by Nagase ChemteX Corporation above), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical (Co.) above) CELLOXIDE2021P, 2081, 2000, 3000, EHPE3150, EPOLEDADGT 400, Serubimasu B0134, B0177 (manufactured by Dal Corporation) and the like.
The compound having an epoxy group in the molecule may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among the compounds having an epoxy group in the molecule, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and aliphatic epoxy resins are more preferable, and aliphatic epoxy resins are particularly preferable.
Specific examples of the compound having an oxetanyl group in the molecule include ARONE OXETANE OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ and PNOX (TOAGOSEI CO., LTD.).
Also, it is preferable that the oxetanyl group-containing compound is used alone or in a mixture with the epoxy group-containing compound.
In the positive photosensitive resin composition layer of the present invention, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.
An alkoxysilane compound
The positive photosensitive resin composition layer may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound can be preferably cited.
Examples of the alkoxysilane compound include γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrialkoxysilane, γ -glycidoxypropylalkyldialkoxysilane, γ -methacryloxypropyltrialkoxysilane, γ -methacryloxypropylalkyldialkoxysilane, γ -chloropropyltrialkoxysilane, γ -mercaptopropyltrialkoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrialkoxysilane, and ethylenetrialkoxysilane. Of these, gamma-glycidoxypropyltrialkoxysilane and gamma-methacryloxypropyltrialkoxysilane are more preferable, gamma-glycidoxypropyltrialkoxysilane is further preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. These can be used alone in 1 or a combination of 2 or more.
Surfactants-
From the viewpoint of film thickness uniformity, the positive photosensitive resin composition layer preferably contains a surfactant. As the surfactant, any of anionic, cationic, nonionic (non-ion) and amphoteric can be used, and a preferable surfactant is a nonionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. Further, the following trade names include KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (KYOEISHA CHEMICAL Co., Ltd., LTD. manufactured), Eftop (JEMCO Co., Ltd.), MEGAFACE (DIC CORPORATION), FLUORAD (Sumitomo 3M Limited), Asahiguard, Surflon (ASAHI GLASS CO., LTD. manufactured), PolyFox (OMNOVA Solutions Inc.) and SH-8400(Dow Corning Toray Co., Ltd.).
Further, as a preferable example of the surfactant, a copolymer containing a structural unit SA and a structural unit SB represented by the following formula I-1 and having a weight average molecular weight (Mw) as measured by gel permeation chromatography in terms of polystyrene when Tetrahydrofuran (THF) is used as a solvent, of 1,000 to 10,000 can be cited.
[ chemical formula 15]
Figure BDA0002969578740000431
In the formula (I-1), R401And R403Each independently represents a hydrogen atom or a methyl group, R402Represents a linear alkylene group having 1 to 4 carbon atoms, R404Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q represent mass percentages representing a polymerization ratio, p represents a numerical value of 10 to 80 mass%, q represents a numerical value of 20 to 90 mass%, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and a bonding site with another structure.
L is preferably a branched alkylene group represented by the following formula (I-2). R in the formula (I-2)405An alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 2 or 3 carbon atoms is even more preferable, from the viewpoint of compatibility and wettability with the surface to be coated. The sum of p and q (p + q) is p + q 100, i.e., preferably 100 mass%.
[ chemical formula 16]
Figure BDA0002969578740000441
The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 to 5,000.
The surfactants described in paragraphs 0017 of Japanese patent No. 4502784 and 0060 to 0071 of Japanese patent application laid-open No. 2009-237362 may also be used.
The surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The amount of the surfactant added is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 3% by mass, based on the total mass of the positive photosensitive resin composition layer.
Other ingredients-
The positive photosensitive resin composition layer of the present invention may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors.
Preferable embodiments of the other components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present specification.
< negative photosensitive resin composition layer >
In the case where the photosensitive resin composition layer in the present invention is a negative photosensitive resin composition layer, it is preferable that the negative photosensitive resin composition layer contains a binder polymer having an acid group, a polymerizable compound, and a photopolymerization initiator, from the viewpoint of pattern formability.
When the photosensitive resin composition layer is a negative photosensitive resin composition layer, the photosensitive resin composition layer described in, for example, japanese patent application laid-open No. 2016-224162 can be used as the negative photosensitive resin composition layer.
[ polymerizable Compound ]
When the photosensitive resin composition layer in the present invention is a negative photosensitive resin composition layer, the negative photosensitive resin composition layer preferably contains a polymerizable compound.
The polymerizable compound is preferably an ethylenically unsaturated compound.
The ethylenically unsaturated compound is a component contributing to the photosensitivity (i.e., photocurability) of the negative photosensitive resin composition layer and the strength of the cured film.
The ethylenically unsaturated compound is a compound having 1 or more ethylenically unsaturated groups.
The negative photosensitive resin composition layer preferably contains an ethylenically unsaturated compound having 2 or more functions as an ethylenically unsaturated compound.
Here, the ethylenically unsaturated compound having 2 or more functions means a compound having 2 or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.
The 2-functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
Examples of the 2-functional ethylenically unsaturated compound include tricyclodecanedimethanol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate.
More specifically, tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-NaKamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-NaKamura Chemical Co., Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, Shin-NaKamura Chemical Co., Ltd.), 1, 6-hexanediol diacrylate (A-HD-N, Shin-NaKamura Chemical Co., Ltd.) and the like are mentioned as the 2-functional ethylenically unsaturated compound.
Also, as the 2-functional ethylenically unsaturated compound, it is also preferable to use a 2-functional ethylenically unsaturated compound having a bisphenol structure.
Examples of the 2-functional ethylenically unsaturated compound having a bisphenol structure include those described in paragraphs 0072 to 0080 of Japanese patent laid-open publication No. 2016-224162.
Specifically, alkylene oxide-modified bisphenol A di (meth) acrylate is exemplified, and 2, 2-bis (4- (methacryloyldiethoxy) phenyl) propane, 2-bis (4- (methacryloyloxyethoxy) phenyl) propane, and dimethacrylate (BPE-500, Shin-NaKamura Chemical Co., Ltd.) of polyethylene glycol in which ethylene oxide is added to both ends of bisphenol A in an average amount of 5 moles, respectively, are preferably exemplified.
The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and can be appropriately selected from known compounds.
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, bis-trimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compounds having a glycerol tri (meth) acrylate skeleton.
Here, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., Kayarad (registered trademark) DPCA-20 manufactured by Ltd., Shin Nakamura Chemical Co., Ltd., A-9300-1CL manufactured by Ltd.), alkylene oxide-modified compounds of (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., KAYARAD RP-1040 manufactured by Ltd., Shin Nakamura Chemical Co., ATM-35E, A-9300 manufactured by Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., Ltd.), and ethoxylated glycerol triacrylate (e.g., Shin Nakamura Chemical Co., Ltd., A-GLY-9E manufactured by Ltd.).
The ethylenically unsaturated compound may also be a urethane (meth) acrylate compound (preferably a 3-or more-functional urethane (meth) acrylate compound).
Examples of the 3-or more-functional urethane (meth) acrylate compound include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin Nakamura Chemical Co., Ltd.), and the like.
The ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group is preferable.
Examples of the ethylenically unsaturated compound having an acid group include 3 to 4-functional ethylenically unsaturated compounds having an acid group (a compound having a carboxyl group introduced into a pentaerythritol tri-and tetraacrylate (PETA) skeleton (acid value: 80mgKOH/g to 120mgKOH/g)), 5 to 6-functional ethylenically unsaturated compounds having an acid group (a compound having a carboxyl group introduced into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton (acid value: 25mgKOH/g to 70mgKOH/g)), and the like.
These ethylenically unsaturated compounds having 3 or more functions of the acid group can be used together with the ethylenically unsaturated compounds having 2 functions of the acid group as required.
The ethylenically unsaturated compound having an acid group is preferably at least 1 selected from the group consisting of an ethylenically unsaturated compound having 2 or more functions of a carboxyl group and a carboxylic anhydride thereof.
The carboxyl group-containing 2-or more-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.
As the carboxyl group-containing 2-or more-functional ethylenically unsaturated compound, for example, ARONIX (registered trademark) TO-2349(TOAGOSEI CO., LTD., manufactured by LTD.), ARONIX M-520(TOAGOSEI CO., LTD., manufactured by LTD.), or ARONIX M-510(TOAGOSEI CO., LTD., manufactured by LTD.), can be preferably used.
The ethylenically unsaturated compound having an acid group is also preferably a polymerizable compound having an acid group as described in paragraphs 0025 to 0030 of Japanese patent application laid-open No. 2004-239942. The content of this publication is incorporated in the present specification.
The polymerizable compound used in the present invention has a weight average molecular weight (Mw) of preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
In the polymerizable compound used in the negative photosensitive resin composition layer, the content of the polymerizable compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on all the ethylenically unsaturated compounds contained in the negative photosensitive resin composition layer.
The polymerizable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the polymerizable compound in the negative photosensitive resin composition layer is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the negative photosensitive resin composition layer.
When the negative photosensitive resin composition layer contains a 2-functional ethylenically unsaturated compound and an ethylenically unsaturated compound having a functionality of 3 or more, the content of the 2-functional ethylenically unsaturated compound is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and still more preferably 30 to 80% by mass, based on all the ethylenically unsaturated compounds contained in the negative photosensitive resin composition layer.
In this case, the content of the 3-or more-functional ethylenically unsaturated compound is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and still more preferably 20 to 70% by mass, based on the total ethylenically unsaturated compounds contained in the negative photosensitive resin composition layer.
In this case, the content of the 2-or more-functional ethylenically unsaturated compound is preferably 40% by mass or more and less than 100% by mass, more preferably 40% by mass to 90% by mass, still more preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, based on the total content of the 2-or more-functional ethylenically unsaturated compound and the 3-or more-functional ethylenically unsaturated compound.
When the negative photosensitive resin composition layer contains an ethylenically unsaturated compound having 2 or more functions, the negative photosensitive resin composition layer may further contain a monofunctional ethylenically unsaturated compound.
When the negative photosensitive resin composition layer contains an ethylenically unsaturated compound having 2 or more functions, it is preferable that the ethylenically unsaturated compound contained in the negative photosensitive resin composition layer contains an ethylenically unsaturated compound having 2 or more functions as a main component.
Specifically, when the negative photosensitive resin composition layer contains an ethylenically unsaturated compound having 2 or more functions, the content of the ethylenically unsaturated compound having 2 or more functions is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, based on the total content of the ethylenically unsaturated compounds contained in the negative photosensitive resin composition layer.
When the negative photosensitive resin composition layer contains an ethylenically unsaturated compound having an acid group (preferably, an ethylenically unsaturated compound having a carboxyl group and a 2-or more-functional group or a carboxylic anhydride thereof), the content of the ethylenically unsaturated compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 10% by mass, relative to the negative photosensitive resin composition layer.
[ adhesive Polymer having acid group ]
When the photosensitive resin composition layer in the present invention is a negative photosensitive resin composition layer, the photosensitive resin composition layer preferably contains a binder polymer having an acid group.
As the binder polymer having an acid group, an alkali-soluble resin is preferable.
Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group.
Among them, as the acid group, a carboxyl group can be preferably cited.
The acid value of the binder polymer having an acid group is not particularly limited, and from the viewpoint of alkali developability, an alkali-soluble resin having an acid value of 60mgKOH/g or more is preferable, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is particularly preferable.
The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more (hereinafter, may be referred to as a specific polymer a.) is not particularly limited as long as the above-mentioned conditions for the acid value are satisfied, and can be appropriately selected from known resins and used.
For example, as the specific polymer a in the present invention, an alkali-soluble resin which is a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of jp 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of jp 2010-237589, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the binder polymer described in paragraphs 0053 to 0068 of jp 2016-224162, and the like can be preferably used.
Here, the (meth) acrylic resin refers to a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from a (meth) acrylate ester.
The total ratio of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the (meth) acrylic resin is preferably 30 mol% or more, and more preferably 50 mol% or more.
The copolymerization ratio of the monomer having a carboxyl group in the specific polymer a is preferably in the range of 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass, based on 100% by mass of the polymer.
The specific polymer a may have a reactive group, and examples of a method for introducing a reactive group into the specific polymer a include a method in which an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride, and the like are reacted with a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, and the like.
The specific polymer a is preferably a compound a shown below. The content ratio of each structural unit shown below can be appropriately changed according to the purpose.
[ chemical formula 17]
Compound A
Figure BDA0002969578740000501
The acid value of the binder polymer having an acid group used in the present invention is preferably 60mgKOH/g to 200mgKOH/g, more preferably 60mgKOH/g to 150mgKOH/g, and still more preferably 60mgKOH/g to 110mgKOH/g, from the viewpoint of alkali developability.
In the present invention, the acid value is a value measured according to the method described in JIS K0070 (1992).
The weight average molecular weight of the binder polymer having an acid group is preferably 1,000 or more, more preferably 1 ten thousand or more, and further preferably 2 to 10 ten thousand.
In addition to the specific polymer a, the binder polymer having an acid group can be used by appropriately selecting an arbitrary film-forming resin according to the purpose. For example, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin and the like can be preferably cited.
The binder polymer having an acid group may be used alone in 1 kind, or may contain 2 or more kinds.
The content of the binder polymer having an acid group in the negative photosensitive resin composition layer is preferably 10 mass% or more and 90 mass% or less, more preferably 20 mass% or more and 80 mass% or less, and further preferably 30 mass% or more and 70 mass% or less with respect to the total mass of the negative photosensitive resin composition layer, from the viewpoint of photosensitivity.
[ photopolymerization initiator ]
When the photosensitive resin composition layer in the present invention is a negative photosensitive resin composition layer, the photosensitive resin composition layer preferably contains a photopolymerization initiator. The photopolymerization initiator receives actinic rays such as ultraviolet rays and visible rays to start polymerization of the polymerizable compound (ethylenically unsaturated compound).
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkylphenone structure (hereinafter, also referred to as an "α -aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkylphenone structure (hereinafter, also referred to as an "α -hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").
The photopolymerization initiator preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, α -hydroxyalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.
Further, it is also preferable that at least 1 selected from the group consisting of 2,4, 5-triarylimidazole dimers and derivatives thereof is contained as the photopolymerization initiator. The 2,4, 5-triarylimidazole dimer and its derivative may be a compound represented by the following formula PI.
[ chemical formula 18]
Figure BDA0002969578740000511
In the formula PI, X is preferred1And X2At least 1 of which is a chlorine atom. Ar (Ar)1、Ar2、Ar3And Ar4When the substituents are independent from each other, the number of the substituents is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. And, Ar1、Ar2、Ar3And Ar4When each of the substituents independently has a substituent, the substitution position is not particularly limited, and is preferably an ortho-position or a para-position. p and q are each independently an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.
Examples of the compound represented by the formula PI include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer. Further, the substituents of the aryl groups of 2,4, 5-triarylimidazoles may be the same to give a symmetric compound, or may be different to give an asymmetric compound.
Further, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-095716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-014783 may be used.
Commercially available photopolymerization initiators include 1- [4- (phenylthio) ] -1, 2-octanedione-2- (o-benzoyloxime) (trade name: IRGACURE (registered trade name) OXE-01, manufactured by BASF SE), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF SE), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF SE), 2-methyl-1- (4-methylphenylsulfanyl) -2-orinylpropane-1- Ketones (trade name: IRGACURE 907, manufactured by BASF SE), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF SE), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: IRGACURE 369, manufactured by BASF SE), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: IRGACURE 1173, manufactured by BASF SE), 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184, manufactured by BASF SE), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF SE), Manufactured by BASF SE), oxime ester type photopolymerization initiator (trade name: lunar 6, manufactured by DKSH Japan k.k., ltd.), 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Company), 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry co., ltd).
The photopolymerization initiator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the photopolymerization initiator in the negative photosensitive resin composition layer is not particularly limited, and is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and further preferably 1.0 mass% or more with respect to the total mass of the negative photosensitive resin composition layer.
The content of the photopolymerization initiator is preferably 10 mass% or less, and more preferably 5 mass% or less, based on the total mass of the negative photosensitive resin composition layer.
[ other additives ]
The negative photosensitive resin composition layer in the present invention may contain known additives, if necessary, in addition to the above components.
Polymerization inhibitors
When the photosensitive resin composition layer in the present invention is a negative photosensitive resin composition layer, the photosensitive resin composition layer contains at least 1 polymerization inhibitor.
As the polymerization inhibitor, for example, an anti-thermal polymerization agent described in paragraph 0018 of Japanese patent No. 4502784 can be used.
Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
When the negative photosensitive resin composition layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 3 mass%, more preferably 0.01 to 1 mass%, and still more preferably 0.01 to 0.8 mass% with respect to the total mass of the negative photosensitive resin composition layer.
-solvent-
The negative photosensitive resin composition layer may contain a solvent. The kind and content of the solvent contained in the composition for forming the negative photosensitive resin composition layer are the same as those of the positive photosensitive resin composition layer, and the description thereof will be omitted.
Plasticizer-
The negative photosensitive resin composition layer in the present invention may contain a plasticizer for the purpose of improving plasticity. The kind and content of the plasticizer are the same as those of the positive photosensitive resin composition layer, and the description thereof will be omitted.
Sensitizer for negative type
When the photosensitive resin composition layer in the present invention is a negative photosensitive resin composition layer, the photosensitive resin composition layer may further contain a negative sensitizer.
Examples of the negative-type sensitizer include known sensitizing dyes, and pigments. The negative type sensitizer may be 1 type alone or 2 or more types.
Examples of the sensitizing dye include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone compound, a thioxanthone 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.
Examples of the dye or pigment include magenta, phthalocyanine GREEN, auramine (auramine) base, alkoxide GREEN (calcoxide GREEN) S, paracanthine, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (Hodogaya Chemical co., ltd., Aizen (registered trademark) MALACHITE GREEN), basic blue 20, and DIAMOND GREEN (Hodogaya Chemical co., ltd., Aizen (registered trademark) DIAMOND GREEN GH).
As the dye, a color-developing dye can be used. The color-developing dye is a compound having a function of developing color by light irradiation. Examples thereof include leuco dyes and fluoran dyes. Among these, leuco dyes are preferred.
The content of the negative-type sensitizer can be appropriately selected according to the purpose, and is preferably in the range of 0.01 to 5 mass%, more preferably in the range of 0.05 to 1 mass% with respect to the total mass of the negative-type photosensitive resin composition layer, from the viewpoints of improving sensitivity to a light source, improving a polymerization rate and a curing rate balanced with chain transfer, and the like.
Hydrogen donor-
When the photosensitive resin composition layer in the present invention is a negative photosensitive resin composition layer, the photosensitive resin composition layer may further contain a hydrogen donor.
The hydrogen donor is not particularly limited as long as it can impart hydrogen to the photopolymerization initiator upon reaction in the exposed portion, and examples thereof include bis [4- (dimethylamino) phenyl ] methane, bis [4- (diethylamino) phenyl ] methane, and leuco crystal violet. These can be used alone in 1 or a combination of 2 or more.
When the negative photosensitive resin composition layer contains a hydrogen donor, the content thereof is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 2% by mass, based on the total mass of the photosensitive resin composition layer.
Heterocyclic compounds
The negative photosensitive resin composition layer in the present invention may contain a heterocyclic compound. The kind and content of the heterocyclic compound are the same as those of the positive photosensitive resin composition layer, and the description thereof will be omitted.
Other ingredients-
In the negative photosensitive resin composition layer of the present invention, as in the case of the positive photosensitive resin composition layer, known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors may be further added.
Preferable embodiments of the other components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present specification.
Method for forming photosensitive resin composition layer
The composition for forming a photosensitive resin composition layer can be prepared by mixing the respective components and the solvent at an arbitrary ratio and by an arbitrary method, and stirring and dissolving the mixture. For example, a composition can be prepared by dissolving each component in a solvent in advance, and then mixing the obtained solutions at a predetermined ratio. The composition prepared as described above can be used after filtration using a filter having a pore size of 0.2 to 30 μm, for example.
The photosensitive resin composition layer in the present invention can be formed by applying the composition for forming a photosensitive resin composition layer on the temporary support or the cover film and drying the composition.
The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
Further, the photosensitive resin composition layer may be formed on the temporary support or the cover film in addition to other layers described later.
< covering film >
The photosensitive transfer material according to the present invention preferably has a cover film.
The cover film may be a resin film, paper, or the like, and is preferably a resin film in view of strength, flexibility, or the like. 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, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.
The thickness of the coating film is not particularly limited, and is preferably 1 μm to 2mm, for example.
< intermediate layer >
The photosensitive transfer material according to the present invention preferably further includes an intermediate layer between the temporary support and the photosensitive resin composition layer. After the temporary support is peeled off and exposed, as shown in fig. 1(C), the protective film 42 is bonded to the intermediate layer 38 and wound up, whereby not only the protective film 42 but also absorption of the decomposed substance in the photosensitive resin composition layer in the intermediate layer 38 can be promoted, and further plasticization of the photosensitive resin composition layer can be suppressed.
< other layer >
The photosensitive transfer material according to the present invention may have a temporary support, a photosensitive resin composition layer, and a layer other than a cover film (hereinafter, may be referred to as "other layer"). Examples of the other layers include an intermediate layer, a contrast enhancement layer, a layer containing a known ultraviolet absorber, and an adhesive layer.
The intermediate layer is not particularly limited, and a known intermediate layer can be used in the field of transfer films and the like.
As the intermediate layer, for example, a layer containing a thermoplastic resin is cited, and as the intermediate layer, a thermoplastic resin layer described in paragraph 0026 of japanese patent No. 4502784 or the like is preferably used.
Examples of the thermoplastic resin include polyvinyl ether/maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, water-soluble salts of various starches and the like, styrene/maleic acid copolymers, and maleate resins described in the respective specifications of Japanese Kokai publication Sho-46-002121 and Japanese Kokoku publication Sho-56-040824.
Among these, from the viewpoint of peelability of the temporary support, a modified cellulose resin is preferable, and hydroxypropyl cellulose is more preferable.
The intermediate layer may contain inorganic particles such as silica particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin composition layer.
The method for forming the intermediate layer is not particularly limited, and the intermediate layer may be formed by a method such as applying a composition containing the thermoplastic resin described in paragraphs 0189 to 0193 of jp 2014-085643 a to a temporary support. In addition, a temporary support having an intermediate layer formed thereon can be obtained and used.
Contrast enhancement layer
The photosensitive transfer material of the present invention can have a contrast enhancement layer in addition to the photosensitive resin composition layer.
The Contrast Enhancement Layer (CEL) is a Layer containing a material (referred to as a photoaromatable dye component) which has a large absorption at an exposure wavelength before exposure but gradually decreases in absorption with exposure, that is, has a high transmittance of light. As the photobleaching pigment component, a diazonium salt, a styrylpyridinium (stilbazolium) salt, an arylnitroso salt, and the like are known. As the coating film-forming component, a phenol resin or the like can be used.
Further, as the contrast enhancement layer, materials described in paragraphs 0004 to 0051 of japanese patent application laid-open No. 6-097065, paragraphs 0012 to 0055 of japanese patent application laid-open No. 6-332167, a photopolymeric handbook, a photopolymeric symposium code, Kogyo chosai Publishing co., Ltd. (1989), photopolymeric technology, shanggang, guansong code, THE NIKKAN Kogyo SHIMBUN, Ltd. (1988) can be used.
A layer containing an ultraviolet absorber
The photosensitive transfer material according to the present invention may have a layer containing an ultraviolet absorber (ultraviolet absorbing layer).
The photosensitive resin composition layer preferably includes an ultraviolet absorbing layer on the side opposite to the temporary support. For example, a method in which an ultraviolet absorbing layer is provided between the cover film and the photosensitive resin composition layer can be cited.
When the photosensitive transfer material having such an ultraviolet absorbing layer is transferred onto a substrate, the ultraviolet absorbing layer is present between the substrate and the photosensitive resin composition layer.
It is considered that, according to this method, reflection of the exposure light by the substrate is reduced, and, for example, influence of a standing wave generated by interference between a reflected wave of the exposure light and an incident wave on the exposure is reduced.
The ultraviolet absorber is not particularly limited, and known ultraviolet absorbers can be used, and examples thereof include compounds such as salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, and hindered amine-based compounds, and inorganic ultraviolet absorbers such as polymers and metal oxides having these structures.
Adhesive layer-
The photosensitive transfer material according to the present invention may further include an adhesive layer as another layer between the cover film and the photosensitive resin composition layer.
By having the adhesive layer, adhesion property when transferring to a substrate or the like becomes good.
Examples
The embodiments of the present invention will be described in more detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the process order, and the like shown in the following examples can be appropriately changed 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, "part" and "%" are based on mass.
(Synthesis of Polymer for photosensitive resin composition)
Polymers A-1 to A-6 for positive photosensitive resin compositions and polymer A-9 for negative photosensitive resin compositions used for the preparation of photosensitive resin compositions of examples and comparative examples were synthesized. Abbreviations for the following materials used in the synthesis of the respective polymers are as follows.
ATHF: 2-tetrahydrofuryl acrylate (synthetic product)
AA: acrylic acid (Tokyo Chemical Industry Co., Ltd.)
EA: ethyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)
MMA: methyl methacrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)
CHA: cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)
PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)
MEK: methyl Ethyl ketone (manufactured by FUJIFILM Wako Pure Chemical Corporation)
V-601: dimethyl 2, 2' -azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)
MATHF: 2-tetrahydrofuryl methacrylate (synthetic)
tBuMA: t-butyl methacrylate (Tokyo Chemical Industry Co., Ltd., manufactured by Ltd.)
MAA: methacrylic acid (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)
St: styrene (Tokyo Chemical Industry Co., Ltd.)
BzMA: benzyl methacrylate (Tokyo Chemical Industry Co., Ltd.)
BPE-500: dimethacrylate of polyethylene glycol (Shin-NaKamura Chemical Co., Ltd.) in which ethylene oxide was added in an average amount of 5 moles per one end of bisphenol A
A-TMPT: trimethylolpropane triacrylate (Shin-NaKamura Chemical Co., Ltd., manufactured by Ltd.)
TD: 4, 4' -bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)
BCTB: 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (Tokyo Chemical Industry Co., Ltd.)
< example of Synthesis of Polymer A-1 >
PGMEA (75.0g) was added to a 3-neck flask and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution to which ATHF (40.0g), AA (10.0g), cyclohexyl acrylate (CHA, 50.0g), V-601(4.0g) and PGMEA (75.0g) were added was added dropwise over 2 hours to a solution in a 3-neck flask 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 concentration 40.0%, weight-average molecular weight 15,000) was obtained.
< example of Synthesis of Polymer A-2 >
Polymer A-2 (weight-average molecular weight: 15,000) was synthesized in the same manner as polymer A-1, except that CHA (50.0g) was changed to CHA (30g) and EA (20 g).
< example of Synthesis of Polymer A-3 >
Polymer A-3 (weight-average molecular weight: 18,000) was synthesized in the same manner as polymer A-1, except that ATHF was changed to MATHF, and CHA (50.0g) was changed to CHA (30g) and MMA (10 g).
< example of Synthesis of Polymer A-4 >
Polymer A-4 (PHS-EVE having the following structure, weight-average molecular weight: 20,000) was synthesized according to the method described in section 0232 of Japanese patent application laid-open No. 2014-085643. In the following structures, the numerical value of each structural unit represents the content (mass%) of the corresponding structural unit.
[ chemical formula 19]
Figure BDA0002969578740000591
< example of Synthesis of Polymer A-5 >
A polymer novolak-EVE (weight average molecular weight: 24,000) having the following structure was obtained according to the method described in paragraph 0234 of Japanese patent laid-open No. 2014-085643. In the following structures, the numerical value of each structural unit represents the content (mass%) of the corresponding structural unit.
[ chemical formula 20]
Polymer Novolac-EVE
Figure BDA0002969578740000592
< example of Synthesis of Polymer A-6 >
Polymer A-6 (weight-average molecular weight: 14,000) was obtained in the same manner as polymer A-1 except that ATHF (40.0g) was changed to tBuMA (40.0 g).
The following table 1 shows the mass ratios of the constitutional units constituting the polymers a-1 to a-6 for positive photosensitive resin compositions synthesized as described above. In Table 1, "-" indicates "none".
[ Table 1]
Figure BDA0002969578740000601
< example of Synthesis of Polymer A-9 >
MEK (75.0g) was charged into a 3-neck flask and warmed to 80 ℃ under nitrogen atmosphere. A solution to which MAA (40.0g), St (20.0g), BzMA (40.0g), V-601(1.5g) and MEK (75.0g) were added was added dropwise over 2 hours to a 3-neck flask solution heated under reflux at 80 ℃. After completion of the dropwise addition, stirring was carried out at 80 ℃ for 2 hours, whereby a polymer A-9 (solid content concentration 40.0%, weight average molecular weight: 55,000) was obtained.
< preparation of Positive photosensitive resin composition P-1 >
The following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 1.0 μm, thereby preparing a positive photosensitive resin composition P-1.
Polymer A-1 (weight average molecular weight 15,000): 9.41 parts
Photoacid generator (PAG 1 described below): 0.50 portion
Surfactant (MEGAFACE F552, manufactured by DIC CORPORATION): 0.01 part
An additive (basic compound of the following structure (manufacturer: TOYOKASEI CO., LTD.) system, material No.: CMTU)): 0.08 portion of
Propyl acetate (solvent): 90.00 parts
[ chemical formula 21]
Figure BDA0002969578740000611
< preparation of Positive photosensitive resin compositions P-2 to P-6 >
Positive photosensitive resin compositions P-2 to P-6 were prepared in the same manner as in the preparation of the positive photosensitive resin composition P-1, except that the polymer A-1 or the photoacid generator was changed to the species shown in Table 3.
The structure of a Photo Acid Generator (PAG) used for producing the positive photosensitive resin composition in each of examples and comparative examples will be shown below.
[ chemical formula 22]
Figure BDA0002969578740000612
< preparation of composition M-1 for intermediate layer formation >
The following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 1.0. mu.m, thereby preparing an intermediate layer-forming composition M-1.
Distilled water: 79.0 parts of
Methanol: 95.0 parts of
Hydroxypropyl cellulose (trade name: HPC-SSL, Nippon Soda co., ltd.): 6.0 parts of
SNOWTEX O (silica particles, manufactured by Nissan Chemical Corporation, average particle diameter 12 nm): 20.0 portion
Surfactant (MEGAFACE F444, manufactured by DIC CORPORATION): 0.025 parts
< preparation of photosensitive transfer Material without intermediate layer (examples 1 to 3 and 5 to 14) >
The positive photosensitive resin composition shown in table 3 was applied onto a polyethylene terephthalate film (26cm wide × 1,000m roll) having a thickness of 25 μm as a temporary support using a slit nozzle in an amount such that the dry film thickness became 5.0 μm, and was continuously passed through a dryer having a temperature adjusted to 100 ℃, thereby drying for 1 minute, and a positive photosensitive resin composition layer was formed.
A polyethylene film (OSM-N, manufactured by Tredegar Corporation) was pressure-bonded as a cover film to the positive photosensitive resin composition layer, thereby producing a photosensitive transfer material (26cm wide. times.1,000 m roll).
< preparation of photosensitive transfer Material in the Presence of intermediate layer (example 4) >
The intermediate layer was formed by applying the intermediate layer forming composition M-1 onto a 25 μ M thick polyethylene terephthalate film (26cm wide. times.1,000M roll) as a temporary support using a slit nozzle in such an amount that the dry film thickness became 2.0 μ M, and continuously passing the intermediate layer forming composition through a dryer adjusted to a temperature of 100 ℃ for 1 minute.
Next, the positive photosensitive resin compositions shown in table 3 were applied onto the intermediate layer using a slit nozzle in such an amount that the dry film thickness became 5.0 μm, and were continuously passed through a dryer adjusted to a temperature of 100 ℃, thereby drying for 1 minute, and thus a photosensitive resin composition layer was formed.
A polyethylene film (OSM-N, manufactured by Tredegar Corporation) was pressure-bonded as a cover film to the photosensitive resin composition layer, thereby producing a photosensitive transfer material (26cm wide. times.1,000 m roll).
(examples 1 to 14)
< fabrication of copper film substrate with resin Pattern >
A conductive substrate (a base material having a conductive layer, 26cm wide. times.500 m long) was prepared, on the surface of which a copper layer was formed by sputtering at a thickness of 500nm on a surface of a 188 μm thick PET film whose back surface was matte-treated.
The cover film of the photosensitive transfer material was peeled off, and the copper layer of the conductive substrate and the photosensitive resin composition layer of the photosensitive transfer material were laminated under lamination conditions of a lamination roll temperature of 90 ℃, a linear pressure of 0.6MPa, and a linear speed (lamination speed) of 3.6m/min, and then wound, thereby producing a roll-shaped laminate (26cm wide × 500m long) in which the conductive substrate and the photosensitive transfer material were integrated.
Subsequently, the wound roll-shaped laminate was unwound from the unwinding device at a conveyance speed of 3.6m/min, and the temporary support was peeled off, and the conveyance was stopped at the time of exposure, thereby forming a light-shielding film having a width passing through a line and a space (L) of 1 μm&S) to 50. mu.mL&An exposure machine of a high-pressure mercury lamp irradiating ghi rays to the mask having various resolution patterns up to S at 150mJ/cm2The exposure amount (i-ray conversion) was used for contact pattern exposure.
After exposure, the protective film shown in table 2 was wound while laminating it on the photosensitive resin composition layer side (on the photosensitive resin composition layer when no intermediate layer was present, and on the intermediate layer when an intermediate layer was present), thereby producing a roll laminate (26cm wide × 500m long) in which the protective film, the pattern-exposed photosensitive transfer material, and the conductive substrate were integrated.
Then, while unwinding the obtained roll laminate from an unwinding device at a feed speed of 3.6m/min, the protective film was peeled off, passed through a spray developing tank (2.5m) for spraying a 1.0% sodium carbonate aqueous solution at a pressure of 0.15MPa and a spray rinsing tank (2.5m) for spraying pure water at a pressure of 0.05MPa, dried with an air knife, and wound, thereby obtaining a resin-patterned copper film substrate.
[ Table 2]
Figure BDA0002969578740000631
Comparative example 1
< fabrication of copper film substrate with resin Pattern >
A roll-shaped laminate (26cm wide × 500m long) in which the conductive substrate and the photosensitive transfer material were integrated was produced using the photosensitive transfer material in the same manner as in example 1.
Subsequently, the obtained roll-shaped laminate was unwound from the unwinding device and the temporary support was peeled off in the same manner as in example 1, thereby performing contact pattern exposure.
After the exposure, the photosensitive resin composition layer was wound without laminating a protective film thereon, thereby producing a roll-shaped laminate (26cm wide × 500m long) in which the pattern-exposed photosensitive transfer material and the conductive substrate were integrated.
Next, the obtained roll-shaped laminate was unwound from the unwinding device at a conveyance speed of 3.6m/min, developed in the same manner as in example 1, and then dried and wound, thereby obtaining a resin-patterned copper film substrate.
[ evaluation ]
< Pattern formability >
The resolution pattern of the obtained resin-patterned copper film substrate was observed using an optical microscope and evaluated. Regarding the image quality, the resolution patterns of 4. mu.mL & S, 6. mu.mL & S, 8. mu.mL & S, 10. mu.mL & S, and 20. mu.mL & S (40 sets of L & S for each resolution) were observed, and the presence or absence of pattern peeling was evaluated. The resolution pattern was observed, and the number of line patterns with broken lines, partial disappearance, and the like was evaluated as "line patterns with peeling".
A: less than 5% of the pattern had peeling off
B: the pattern with peeling is more than 5%
< PED characteristics >
The stability with time after Exposure (Post Exposure Delay stability: PED) was evaluated as follows.
In the production of the copper film substrate with a resin pattern, pattern exposure is performed, and a roll-shaped laminate obtained by winding a protective film while laminating is left to stand at a temperature of 26 ℃ and a humidity of 55% for 3 hours or 24 hours. Hereinafter, the time described later in "PED" represents the elapsed time from the exposure to the start of development.
After that, the roll-shaped laminate was unwound and developed in accordance with the production of the resin-patterned copper film base material, thereby forming a resin pattern. The obtained resin-patterned copper film substrate was observed and evaluated for its resolution pattern by an optical microscope. The line width of the resolution pattern of 6 μmL & S was measured.
The amount of change in the line width of the resin pattern formed at PED24 hours from the line width of the resin pattern formed at PED3 hours was evaluated.
A: the line width variation is less than 1.0 μm
B: the line width variation value is more than 1.0 μm and less than 2.0 μm
C: the line width variation value is more than 2.0 μm and less than 3.0
D: the line width variation value is more than 3.0 μm
The evaluation results are shown in table 3 below.
Figure BDA0002969578740000661
< preparation of negative photosensitive resin composition N-1 >
The following components were mixed and filtered using a polytetrafluoroethylene filter having a pore size of 1.0 μm, thereby preparing a negative photosensitive resin composition N-1.
Polymer A-9 (weight-average molecular weight: 55,000): 8.3 parts of
Photopolymerization initiator TD: 0.02 portion
Photopolymerization initiator BCTB: 0.5 portion
Polymerizable monomer BPE-500: 4.8 parts of
Polymerizable monomer a-TMPT: 2.0 part by weight
Diamond green: 0.02 portion
Colorless crystal violet: 0.5 portion
Surfactants: 0.01 part
Propyl acetate (solvent): 83.85 parts
< production of photosensitive transfer Material >
The negative photosensitive resin composition shown in table 4 was applied onto a 25 μm thick polyethylene terephthalate film (26cm wide × 1,000m roll) as a temporary support by using a slit nozzle in an amount such that the dry film thickness became 5.0 μm, and was continuously passed through a dryer adjusted to a temperature of 100 ℃, thereby drying for 1 minute, and a negative photosensitive resin composition layer was formed.
A polyethylene film (OSM-N, manufactured by Tredegar Corporation) was pressure-bonded as a cover film on the negative photosensitive resin composition layer, thereby producing a photosensitive transfer material (roll of 26cm width × 1,000 m).
(example 101)
< fabrication of copper film substrate with resin Pattern >
A conductive substrate (a base material having a conductive layer, 26cm wide. times.500 m long) was prepared, on the surface of which a copper layer was formed by sputtering at a thickness of 500nm on a surface of a 188 μm thick PET film whose back surface was matte-treated.
The cover film of the photosensitive transfer material was peeled off, and the copper layer of the conductive substrate and the surface of the photosensitive resin composition layer having the photosensitive transfer material were laminated under lamination conditions of a lamination roll temperature of 90 ℃, a linear pressure of 0.6MPa, and a linear speed (lamination speed) of 3.6m/min, and then wound, thereby producing a roll-shaped laminate (26cm wide × 500m long) in which the conductive substrate and the photosensitive transfer material were integrated.
Subsequently, the wound roll-shaped laminate was unwound from the unwinding device at a conveyance speed of 3.6m/min, and the temporary support was peeled off, and the conveyance was stopped at the time of exposure, thereby forming a light-shielding film having a width passing through a line and a space (L) of 1 μm&S) to 50. mu.mL&An exposure machine of a high-pressure mercury lamp for irradiating ghi rays to the mask having various resolution patterns up to S at a rate of 75mJ/cm2The exposure amount (i-ray conversion) was used for contact pattern exposure.
After the exposure, the protective film shown in table 4 was laminated on the photosensitive resin composition layer side and wound up, thereby producing a roll-shaped laminate (26cm wide × 500m long) in which the protective film, the pattern-exposed photosensitive transfer material, and the conductive substrate were integrated.
Then, while unwinding the obtained roll laminate from an unwinding device at a feed speed of 3.6m/min, the protective film was peeled off, passed through a spray developing tank (2.5m) for spraying a 1.0% sodium carbonate aqueous solution at a pressure of 0.15MPa and a spray rinsing tank (2.5m) for spraying pure water at a pressure of 0.05MPa, dried with an air knife, and wound, thereby obtaining a resin-patterned copper film substrate.
Comparative example 201
< fabrication of copper film substrate with resin Pattern >
A roll-shaped laminate (26cm wide × 500m long) in which a conductive substrate and a photosensitive transfer material were integrated was produced using a photosensitive transfer material in the same manner as in example 101.
Subsequently, the obtained roll-shaped laminate was unwound from the unwinding device and the temporary support was peeled off in the same manner as in example 101, thereby performing contact pattern exposure.
After the exposure, the photosensitive resin composition layer was wound without laminating a protective film thereon, thereby producing a roll-shaped laminate (26cm wide × 500m long) in which the pattern-exposed photosensitive transfer material and the conductive substrate were integrated.
Next, the obtained roll-shaped laminate was unwound from the unwinding device at a conveyance speed of 3.6m/min, developed in the same manner as in example 101, and then dried and wound, thereby obtaining a resin-patterned copper film substrate.
[ evaluation ]
< Pattern formability >
The resolution pattern of the obtained resin-patterned copper film substrate was observed using an optical microscope and evaluated. Regarding the image quality, patterns of 4. mu.mL & S, 6. mu.mL & S, 8. mu.mL & S, 10. mu.mL & S, and 20. mu.mL & S were observed for resolution, and the presence or absence of pattern peeling was evaluated (40 sets of L & S for each resolution). The resolution pattern was observed, and the number of line patterns with broken lines, partial disappearance, and the like was evaluated as line patterns with peeling.
A: less than 5% of the pattern had peeling off
B: the pattern with peeling is more than 5%
< PED characteristics >
In the production of the copper film substrate with a resin pattern, pattern exposure is performed, and a roll-shaped laminate obtained by winding a protective film while laminating is left to stand at a temperature of 26 ℃ and a humidity of 55% for 3 hours or 24 hours.
After that, the roll-shaped laminate was unwound and developed in accordance with the production of the resin-patterned copper film base material, thereby forming a resin pattern. The obtained resin-patterned copper film substrate was observed and evaluated for its resolution pattern by an optical microscope. The line width of the resolution pattern of 6 μmL & S was measured.
The amount of change in the line width of the resin pattern formed at PED24 hours from the line width of the resin pattern formed at PED3 hours was evaluated.
A: the line width variation is less than 1.5 μm
B: the line width variation value is more than 1.5 μm
The evaluation results are shown in table 4 below.
[ Table 4]
Figure BDA0002969578740000691
In the examples, the positive photosensitive resin composition layer and the negative photosensitive resin composition layer were each less likely to peel off after exposure than in the comparative examples, and the pattern shape was more likely to change during the period from exposure to development.
Description of the symbols
12-unwind roll, 14-laminate, 15-roll, 16-feed roll, 17-roll, 18-temporary support, 18A, 18B-temporary support, 20A, 20B-peel roll, 22-laminate (before pattern exposure), 24-exposure device, 26A, 26B-exposure light source, 32-resin film, 33-photosensitive transfer material, 34A, 34B-copper layer, 35-substrate, 36-photosensitive resin composition layer, 36A, 36B-photosensitive resin composition layer, 38-intermediate layer, 39-laminate (after pattern exposure), 40-protective film roll, 42-protective film, 60-cover film, 70-mask.
The invention of japanese patent application 2018-185596, filed on 28/9/2018, is incorporated in its entirety by reference into the present specification.
All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims (8)

1. A method for manufacturing a patterned substrate, which comprises the following steps in sequence:
a step of bonding a substrate to a photosensitive resin composition layer side of a photosensitive transfer material having a temporary support and a photosensitive resin composition layer supported by the temporary support;
a step of peeling off the temporary support;
a step of pattern-exposing the photosensitive resin composition layer;
a step of bonding a protective film to the outermost layer on the photosensitive resin composition layer side exposed through the pattern when viewed from the base material side;
winding a laminate in which the base material, the photosensitive resin composition layer exposed to the pattern, and the protective film are sequentially laminated;
unwinding the wound laminate and peeling the protective film; and
and a step of developing the photosensitive resin composition layer exposed by the pattern to form a pattern of the photosensitive resin composition layer.
2. The method of manufacturing a patterned substrate of claim 1, wherein,
the photosensitive resin composition layer contains an acid-decomposable resin.
3. The method of manufacturing a patterned substrate of claim 2, wherein,
the acid-decomposable resin has a structural unit represented by the following formula A1, formula A2 or formula A3,
Figure FDA0002969578730000011
in the formula A1, R11And R12Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R11And R12Any of which is alkyl or aryl, R13Represents alkyl or aryl, optionally R11Or R12And R13Linked to form a cyclic ether, R14Represents a hydrogen atom or a methyl group, X1Represents a single bond or a divalent linking group, R15Represents a substituent, n represents an integer of 0 to 4,
in the formula A2, R21And R22Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R21And R22Any of which is alkyl or aryl, R23Represents alkyl or aryl, optionally R21Or R22And R23Linked to form a cyclic ether, R24Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, m represents an integer of 0 to 3,
in the formula A3, R31And R32Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R31And R32Any of which is alkyl or aryl, R33Represents alkyl or aryl, optionally R31Or R32And R33Linked to form a cyclic ether, R34Represents a hydrogen atom or a methyl group, X0Represents a single bond or a divalent linking group.
4. The method of manufacturing a patterned substrate according to any of claims 1 to 3, wherein,
the protective film is a protective film comprising a resin having a structural unit containing a phenolic hydroxyl group or a structural unit containing an alcoholic hydroxyl group not directly bonded to the main chain, or an acrylic resin.
5. The method of manufacturing a patterned substrate according to claim 4,
the resin having a structural unit containing the phenolic hydroxyl group or a structural unit containing an alcoholic hydroxyl group not directly bonded to the main chain is at least 1 resin selected from the group consisting of modified cellulose resins and novolac resins.
6. The method of manufacturing a patterned substrate according to any of claims 1 to 5, wherein,
the photosensitive transfer material is a photosensitive transfer material having an intermediate layer between the temporary support and the photosensitive resin composition layer.
7. A method for manufacturing a circuit board, which sequentially performs the following steps:
the method for producing a patterned substrate according to any one of claims 1 to 6, wherein a substrate having a conductive layer on a surface of the photosensitive transfer material on the photosensitive resin composition layer side is used as the substrate, thereby producing the patterned substrate;
etching the conductive layer exposed in a region of the patterned substrate where the pattern of the photosensitive resin composition layer is not formed; and
and removing the pattern of the photosensitive resin composition layer.
8. A method of manufacturing a touch panel, comprising the method of manufacturing a circuit substrate according to claim 7.
CN201980059678.8A 2018-09-28 2019-08-15 Method for manufacturing patterned base material, method for manufacturing circuit board, and method for manufacturing touch panel Pending CN112740107A (en)

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
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JP7389071B2 (en) * 2020-06-17 2023-11-29 富士フイルム株式会社 Method for forming conductive pattern, method for manufacturing metal mesh sensor, and method for manufacturing structure
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CN116235111A (en) * 2020-09-17 2023-06-06 富士胶片株式会社 Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel
KR20240021138A (en) * 2021-06-15 2024-02-16 가부시끼가이샤 레조낙 Photosensitive element and method of manufacturing the photosensitive element

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003177526A (en) * 2001-12-10 2003-06-27 Hitachi Chem Co Ltd Photosensitive element, method for producing photosensitive element, and method for producing resist pattern and method for producing printed wiring board by using the element
JP2004341447A (en) * 2003-05-19 2004-12-02 Hitachi Chem Co Ltd Photosensitive film
US20050053868A1 (en) * 2003-09-08 2005-03-10 Nitto Denko Corporation Process for producing wiring circuit board
JP2006317500A (en) * 2005-05-10 2006-11-24 Showa Denko Kk Photosensitive dry film roll for protective film for printed wiring board, and method for manufacturing the same
JP2009083943A (en) * 2007-09-27 2009-04-23 Fujifilm Corp Device and method for manufacturing photosensitive layered product
CN102405437A (en) * 2009-12-09 2012-04-04 住友化学株式会社 System for manufacturing optical display device and method for manufacturing the optical display device
WO2017213056A1 (en) * 2016-06-10 2017-12-14 富士フイルム株式会社 Method for manufacturing patterned substrate, and method for manufacturing circuit board

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06260421A (en) * 1993-03-08 1994-09-16 Canon Inc Continuous formation of functional deposited film and continuous forming device
JP5109606B2 (en) * 2007-11-15 2012-12-26 コニカミノルタホールディングス株式会社 Organic electroluminescence device manufacturing method and protective film
JP5609427B2 (en) * 2010-08-25 2014-10-22 コニカミノルタ株式会社 Polarizer protective film, roll-shaped polarizing plate, and liquid crystal display device
JP2012052170A (en) * 2010-08-31 2012-03-15 Fujifilm Corp Method of producing functional film
JP6711364B2 (en) * 2015-12-24 2020-06-17 コニカミノルタ株式会社 Optical film, optical film roll, and method for producing optical film

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003177526A (en) * 2001-12-10 2003-06-27 Hitachi Chem Co Ltd Photosensitive element, method for producing photosensitive element, and method for producing resist pattern and method for producing printed wiring board by using the element
JP2004341447A (en) * 2003-05-19 2004-12-02 Hitachi Chem Co Ltd Photosensitive film
US20050053868A1 (en) * 2003-09-08 2005-03-10 Nitto Denko Corporation Process for producing wiring circuit board
JP2006317500A (en) * 2005-05-10 2006-11-24 Showa Denko Kk Photosensitive dry film roll for protective film for printed wiring board, and method for manufacturing the same
JP2009083943A (en) * 2007-09-27 2009-04-23 Fujifilm Corp Device and method for manufacturing photosensitive layered product
CN102405437A (en) * 2009-12-09 2012-04-04 住友化学株式会社 System for manufacturing optical display device and method for manufacturing the optical display device
WO2017213056A1 (en) * 2016-06-10 2017-12-14 富士フイルム株式会社 Method for manufacturing patterned substrate, and method for manufacturing circuit board

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