WO2017130427A1 - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing touch panel - Google Patents
Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing touch panel Download PDFInfo
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- WO2017130427A1 WO2017130427A1 PCT/JP2016/059953 JP2016059953W WO2017130427A1 WO 2017130427 A1 WO2017130427 A1 WO 2017130427A1 JP 2016059953 W JP2016059953 W JP 2016059953W WO 2017130427 A1 WO2017130427 A1 WO 2017130427A1
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a photosensitive resin composition, a photosensitive element, a resist pattern forming method, and a touch panel manufacturing method.
- the touch sensor unit of the touch panel includes a sensor part for detecting position information due to contact with a human finger or the like in a range (view area) for displaying visual information, and a lead wiring part for transmitting the position information to an external element. It is configured to be equipped.
- the sensor part is formed with a conductive electrode pattern with little absorption and scattering of visible light. Further, a metal having a small resistance value is used for each wiring in the lead-out wiring region.
- FIG. 2 is a schematic cross-sectional view showing a conventional manufacturing method of the touch sensor portion of the touch panel.
- a photosensitive layer 16 is formed on a supporting substrate 12 (film substrate or glass substrate such as polyethylene terephthalate) having a transparent conductive layer 14 by applying a photosensitive resin composition (photosensitive layer forming step) (FIG. 2).
- A) photosensitive resin composition
- the exposed portion is cured by irradiating a predetermined portion of the photosensitive layer 16 with an actinic ray (exposure step).
- a resist pattern containing a photocured product of the photosensitive resin composition is formed on the transparent conductive layer 14 by removing the uncured portion from the transparent conductive layer 14 (development process) (FIG. 2B). .
- Etching is performed on the resist pattern, and a part of the transparent conductive layer 14 is removed from the support base 12 to form a pattern of the transparent conductive layer at the sensor site (etching step) (FIG. 2C). ).
- the resist pattern is peeled off from the transparent conductive layer 14 and removed (peeling step) (FIG. 2D).
- the lead wiring 18 from the pattern of the transparent conductive layer of the formed sensor part is formed by screen printing using a silver paste or the like, thereby manufacturing the touch sensor unit.
- a method of forming the touch sensor unit using a photolithography technique has been proposed (for example, see Patent Document 1). .
- a first photosensitive layer is formed using a photosensitive resin composition on a supporting substrate having a transparent conductive layer and a metal layer (first photosensitive layer forming step).
- first photosensitive layer forming step a predetermined portion of the photosensitive layer is irradiated with actinic rays to cure the exposed portion (first exposure step), and then the uncured portion is removed from the metal layer, thereby exposing the photosensitive layer to the photosensitive layer.
- a resist pattern containing a photocured product of the resin composition is formed (first development step).
- the metal layer and the transparent conductive layer are removed by an etching process (first etching step).
- the resist pattern is peeled off from the metal layer and removed (first peeling step).
- a second photosensitive layer is newly formed on the metal layer using the photosensitive resin composition (second photosensitive layer forming step).
- a predetermined portion of the photosensitive layer is irradiated with actinic rays to cure the exposed portion (second exposure step), and then the uncured portion is removed from the metal layer to form a resist pattern on the metal layer.
- second exposure step etching
- the resist pattern is peeled and removed to remove the touch sensor unit. Manufacturing.
- the transparent conductive layer of the touch sensor unit is formed, for example, by forming a film of indium tin oxide (ITO) using a sputtering technique.
- the metal layer formed on a transparent conductive layer is formed using the technique of sputtering similarly to a transparent conductive layer, for example. The surfaces of the transparent conductive layer and metal layer formed by using the sputtering technique have very high smoothness.
- the photosensitive resin composition to be used is required to have high adhesion to a metal layer in which a body, an alloy of silver, palladium, and copper is used.
- amorphous ITO is used from the viewpoint of easy etching.
- amorphous ITO has a high resistance value, the resistance value is lowered by, for example, crystallization of ITO by a heating (annealing) process.
- a film base material As a support base material for the touch panel portion.
- the dimensional stability deteriorates due to the shrinkage of the film substrate and the like when the annealing treatment is performed. Therefore, when using a film base material as a supporting base material, it is necessary to use crystalline ITO as the transparent conductive layer before forming the pattern of the transparent conductive layer.
- Amorphous ITO can be sufficiently dissolved with a weak acid such as oxalic acid, but crystalline ITO uses a strong acid such as concentrated hydrochloric acid (> 20% by mass) and heating conditions (about 40 to 50 ° C.). ) Need to be etched. Therefore, the photosensitive resin composition to be used is required to have high acid resistance, that is, adhesion with the metal layer can be ensured even by etching using a strong acid, and corrosion of the metal layer due to the strong acid can be suppressed.
- a technique for forming a wiring pattern (also referred to as a conductor pattern) having a high resolution by reducing the L / S of the resist pattern to 30/30 (unit: ⁇ m) or less
- the metal layer and the transparent conductive layer are etched together.
- ITO-4400Z manufactured by ADEKA Corporation
- ITO-4400Z is commercially available as a chemical solution for etching the metal layer and the transparent conductive layer at once.
- photosensitive resin compositions have been studied as photosensitive resin compositions used for forming resist patterns.
- a photosensitive resin composition it has been proposed to add a specific cross-linking agent, a specific silane coupling agent, etc., and to have a binder polymer having a specific structural unit as an essential component (for example, a patent Reference 3-7).
- Japanese Patent No. 4855536 Japanese Patent No. 4219641 Japanese Patent Laid-Open No. 2002-040645 JP 2002-268215 A JP 2008-112146 A JP 2009-042720 A JP 2003-107695 A
- the resist pattern When forming a resist pattern having a high resolution with the L / S of the resist pattern being 30/30 (unit: ⁇ m) or less, defects such as chipping, cracks, meandering, and peeling of the resist pattern are likely to occur. .
- the resist pattern is required more than before to be free from chipping, cracking, meandering, peeling and the like.
- the photosensitive resin composition described in Patent Document 2 it is difficult to form a resist pattern with excellent resolution, and a resist pattern may be defective.
- the photosensitive resin compositions described in Patent Documents 3 to 7 sometimes cause defects such as resist peeling and chipping during ITO etching.
- defects such as peeling and chipping occur in the resist pattern, and defects such as peeling and chipping do not occur in the resist pattern.
- the line shape of the wiring pattern to be formed tends to be loose.
- the present invention has been made to solve such problems, and there are few chips and cracks that can occur in a resist pattern, and the resist meanders and peels even when a strong etching solution is used. It aims at providing the photosensitive resin composition which can form the resist pattern which can suppress that generation
- production occurs. Another object of the present invention is to provide a photosensitive element, a resist pattern forming method and a touch panel manufacturing method using the photosensitive resin composition.
- a resist pattern having excellent characteristics can be formed by using a photosensitive resin composition containing a predetermined component.
- the first aspect of the present invention comprises (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator.
- the invention relates to a photosensitive resin composition comprising (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton.
- the component (B) may further contain a bisphenol A type di (meth) acrylate having a (poly) oxyethylene group. According to such a photosensitive resin composition, the acid resistance of the resist pattern is further improved, and meandering and peeling due to swelling of the resist pattern during ITO etching can be more significantly suppressed.
- a second aspect of the present invention includes a support and a photosensitive layer provided on one surface of the support and formed using the photosensitive resin composition according to the first aspect.
- a photosensitive element since it includes the photosensitive layer formed using the photosensitive resin composition according to the first aspect, even when a strong etching solution is used, the meandering and chipping of the resist are performed. It is possible to form a resist pattern that can suppress the occurrence of. Therefore, by using such a photosensitive element, a high-resolution fine circuit pattern can be efficiently formed.
- a part of the photosensitive layer is cured by irradiation with actinic rays to form a photocured product region, and a region other than the photocured product region of the photosensitive layer is removed from the substrate.
- a developing step for obtaining a resist pattern composed of the photocured product region According to such a resist pattern forming method, the resist pattern can be prevented from causing occurrence of meandering and peeling of the resist even when a strong etching solution is used, since there are few chips and cracks that can occur in the resist pattern. Can be formed.
- a fourth aspect of the present invention is a laminated base material comprising a support base material, a transparent conductive layer containing indium tin oxide provided on one surface of the support base material, and a metal layer provided on the transparent conductive layer
- a second step of forming a laminated pattern comprising the remainder of the transparent conductive layer and the remainder of the metal layer; and a transparent electrode comprising the remainder of the transparent conductive layer by removing the metal layer from a part of the laminated pattern
- a third step of forming a metal wiring composed of the remainder of the metal layer is a laminated base material comprising a support base material, a transparent conductive layer containing indium tin oxide provided on one surface of the support base material, and a metal layer provided on the transparent conductive layer
- the resist pattern is formed from the photocured product of the photosensitive resin composition according to the first aspect, the resist pattern is sufficiently peeled off during the etching process. It is possible to manufacture a narrow-pitch touch panel (for example, a touch panel having a lead-out line with an L / S of 30/30 or less) that is suppressed and easily and efficiently.
- the transparent conductive layer may contain crystalline indium tin oxide, and the etching in the second step may be etching with a strong acid.
- the said manufacturing method can be applied suitably for manufacture of the touch panel using the laminated base material provided with the transparent conductive layer containing crystalline indium tin oxide.
- a functional resin composition is provided. Moreover, according to this invention, the formation method of the photosensitive element using the said photosensitive resin composition, the resist pattern, and the manufacturing method of a touch panel are provided.
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acrylate means acrylate or a corresponding methacrylate
- (meth) acryloxy group means acryloxy group. Or the methacryloxy group corresponding to it.
- the (poly) oxyalkylene group means at least one polyoxyalkylene group in which an oxyalkylene group or two or more alkylene groups are linked by an ether bond. That is, (poly) oxyethylene group means at least one polyoxyethylene group in which an oxyethylene group or two or more ethylene groups are linked by an ether bond, and other similar expressions such as (poly) oxypropylene group The same applies to.
- the (poly) oxyethylene group may be referred to as “EO group” and the (poly) oxypropylene group may be referred to as “PO group”.
- the term “layer” includes a structure formed in a part in addition to a structure formed over the entire surface when observed as a plan view.
- the term “process” is included in this term as long as the intended purpose of the process is achieved, even when the process is not clearly distinguished from other processes.
- the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
- the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- the photosensitive resin composition according to the present embodiment includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component.
- the photosensitive resin composition According to such a photosensitive resin composition, it is possible to form a high-resolution resist pattern in which the occurrence of peeling and chipping is suppressed. In addition, since the resist pattern formed using the photosensitive resin composition suppresses the occurrence of meandering and peeling even when ITO is etched using a strong acid, the resulting circuit pattern has a line shape. It becomes good. Therefore, the photosensitive resin composition according to the present embodiment is suitable for etching ITO, particularly for etching a transparent conductive layer containing crystalline ITO.
- the flexibility of a resist pattern can also be improved.
- Binder polymer The photosensitive resin composition contains at least one binder polymer as the component (A).
- binder polymer include a polymer obtained by radical polymerization of a polymerizable monomer (monomer).
- (meth) acrylic acid As the polymerizable monomer (monomer), (meth) acrylic acid; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl, (meth) acrylic acid benzyl derivative, ( (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dimethylaminoethyl, (meta) ) Diethylaminoethyl acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, ⁇ -bromoacrylic acid, ⁇ -Chloracrylic acid,
- the component may have a structural unit derived from (meth) acrylic acid.
- the content rate is based on the total amount of the component (A) in terms of excellent resolution and peelability (resist peelability after etching). (100 mass%, the same shall apply hereinafter) may be 10 to 60 mass%, 15 to 50 mass%, or 20 to 35 mass%.
- total amount of component (A) means the total amount of solid content. The same applies to “total amount of component (A) and component (B)” described later.
- the “solid content” refers to the non-volatile content of the photosensitive resin composition excluding volatile substances such as water and solvent. That is, it refers to components other than the solvent that remains without being volatilized in the drying step, and includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C.
- the component (A) may have a structural unit derived from an alkyl (meth) acrylate from the viewpoint of further improving alkali developability and peelability.
- the (meth) acrylic acid alkyl ester may be an ester of (meth) acrylic acid and an alkyl alcohol having 1 to 12 carbon atoms.
- examples of such (meth) acrylic acid alkyl esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, Examples thereof include hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. These may be used alone or in any combination of two or more.
- the content is 40 to 90% by mass based on the total amount of the component (A) in terms of excellent resolution and adhesion. , 50 to 85% by mass, or 65% to 80% by mass.
- the acid value of the component (A) may be 90 to 250 mgKOH / g, 100 to 240 mgKOH / g, 120 to 235 mgKOH / g, or 130 mgKOH / g to 230 mgKOH / g in terms of excellent developability and adhesion. Good.
- the acid value may be 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g or more.
- this acid value is 250 mgKOH / g or less, 240 mgKOH / g or less, 235 mgKOH / g or less, or 230 mgKOH / g or less in that the adhesiveness of the photocured product of the photosensitive resin composition is further improved. Also good.
- the weight average molecular weight (Mw) of the component (A) is 10,000 to 200,000 in terms of excellent developability and adhesion when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). 20,000 to 100,000, 25,000 to 80,000, or 30,000 to 60,000. In the point which is excellent in developability, it may be 200000 or less, 100000 or less, 80000 or less, or 60000 or less. In the point which is excellent in adhesiveness, it may be 10,000 or more, 20000 or more, 25000 or more, or 30000 or more.
- the dispersity (weight average molecular weight / number average molecular weight) of the component (A) may be 3.0 or less, 2.8 or less, or 2.5 or less in terms of excellent resolution and adhesion.
- one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination.
- the content of the component (A) in the photosensitive resin composition is 30 to 70 parts by weight, 35 parts in 100 parts by weight of the total amount of the components (A) and (B) in terms of excellent film formability, sensitivity and resolution. It may be ⁇ 65 parts by mass or 40-60 parts by mass. In view of formability of the film (photosensitive layer), the content may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. Further, from the viewpoint of improving the sensitivity and resolution in a balanced manner, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.
- Component (B) Photopolymerizable compound
- the photosensitive resin composition contains (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton as the component (B). .
- Examples of (meth) acrylate having six ethylenically unsaturated bonds in the molecule include dipentaerythritol hexa (meth) acrylate. These may have an EO group or a PO group.
- the number of EO groups in the molecule is 6 to 30, 6 to 24, or from the viewpoint of improving adhesion. It may be 6-12.
- the number of PO groups in the molecule is 6 to 30, 6 to 24, or 6 to 6 from the viewpoint of improving adhesion. 12 may be sufficient.
- KAYARAD DPHA Nippon Kayaku Co., Ltd., trade name, number of EO groups: 6
- KAYARAD DPEA-12 Nippon Kayaku Co., Ltd., trade name, number of EO groups: 12
- A-DPH-6E Shin Nakamura Chemical Co., Ltd., trade name, number of EO groups: 6
- A-DPH-6P Shin-Nakamura Chemical Co., Ltd., trade name, number of PO groups: 6
- One (meth) acrylate having six ethylenically unsaturated bonds in the molecule may be used alone, or two or more may be used in combination.
- dipentaerythritol hexa (meth) acrylate having an EO group or a PO group include compounds represented by the following general formula (1).
- each R independently represents a hydrogen atom or a methyl group.
- a plurality of R may be the same as or different from each other.
- A represents an alkylene group having 2 to 6 carbon atoms, an alkylene group having 2 to 5 carbon atoms, or an alkylene group having 2 to 4 carbon atoms.
- alkylene group having 2 to 6 carbon atoms include ethylene group, propylene group, isopropylene group, butylene group, pentylene group and hexylene group.
- an ethylene group or an isopropylene group or an ethylene group may be used from the viewpoint of improving the resolution, adhesion, and resist bottom generation suppression.
- a plurality of A's may be the same or different.
- each n is independently an integer of 0 to 20. From the viewpoint of further improving the resolution, n may be 1 to 20, 1 to 7, 1 to 5, 1 to 4, or 1 to 2.
- the sum of the six ns in the general formula (1) may be 6-30, 6-24, or 6-12.
- the content of the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule is from the viewpoint of improving the adhesion and releasability after etching in a balanced manner.
- the total amount of the component (B) may be 3 to 20 parts by mass, 3 to 15 parts by mass, or 3 to 10 parts by mass.
- the (meth) acrylate having an isocyanuric ring skeleton may contain a compound represented by the following general formula (2) from the viewpoint of improving the acid resistance and flexibility of the resist pattern.
- the (meth) acrylate having an isocyanuric ring skeleton may be used alone or in combination of two or more.
- R 21 , R 22 and R 23 each independently represents an alkylene group having 1 to 20 carbon atoms
- R 24 , R 25 and R 26 each independently represents a hydrogen atom or a methyl group
- X 21 , X 22 and X 23 each independently represent a (poly) oxyalkylene group (oxyalkylene group or polyoxyalkylene group) containing at least one selected from the group consisting of an EO group and a PO group.
- X 21 , X 22 and X 23 have a total number of EO groups and PO groups (total number in the molecule) of 0 to 120. When both the EO group and the PO group are present, the EO group and the PO group may be present at random and may form a block.
- the total number of EO groups and PO groups contained in X 21 , X 22 and X 23 is 3 to 60, 3 to 30, 3 to 20, or 3 to 15 from the viewpoint of flexibility and acid resistance. Also good.
- the content of the (meth) acrylate having an isocyanuric ring skeleton is 1 to 100 parts by mass in the total amount of the component (A) and the component (B) from the viewpoint of improving the acid resistance and flexibility of the resist pattern in a balanced manner. It may be 50 parts by mass. Further, from the viewpoint of further improving acid resistance and flexibility, the lower limit may be 3 parts by mass or more, or 5 parts by mass or more. Further, from the same viewpoint, the lower limit may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 16 parts by mass or less.
- the component (B) may further contain a photopolymerizable compound other than (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton.
- Other photopolymerizable compounds are not particularly limited as long as they are compounds capable of photopolymerization.
- the other photopolymerizable compound may be a radical polymerizable compound or a compound having an ethylenically unsaturated bond.
- the compound having an ethylenically unsaturated bond a compound having one ethylenically unsaturated bond in the molecule ((meth) acrylate), a compound having two ethylenically unsaturated bonds in the molecule ((meth) acrylate) And compounds having three or more ethylenically unsaturated bonds ((meth) acrylate) in the molecule.
- Another photopolymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- the component may further contain a compound having two ethylenically unsaturated bonds in the molecule.
- Examples of the compound having two ethylenically unsaturated bonds in the molecule include bisphenol A type di (meth) acrylate, hydrogenated bisphenol A type di (meth) acrylate, and di (meth) acrylate having a urethane bond in the molecule. And polyalkylene glycol di (meth) acrylate having both (poly) oxyethylene group and (poly) oxypropylene group in the molecule, and trimethylolpropane di (meth) acrylate.
- the component (B) may contain bisphenol A type di (meth) acrylate from the viewpoint of further improving acid resistance.
- Examples of the bisphenol A type di (meth) acrylate include compounds represented by the following general formula (3).
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
- XO and YO each independently represent an oxyethylene group or an oxypropylene group.
- m 1 , m 2 , n 1 and n 2 each independently represents 0 to 40.
- m 1 + n 1 and m 2 + n 2 are both 1 or more.
- XO is an oxyethylene group and YO is an oxypropylene group
- m 1 + m 2 is 1 to 40
- n 1 + n 2 is 0 to 20.
- m 1 + m 2 is 0 to 20
- n 1 + n 2 is 1 to 40.
- m 1 , m 2 , n 1 and n 2 represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units.
- n 1 + n 2 may be 8 to 40, 8 to 20, or 8 to 10.
- the photosensitive resin composition contains bisphenol A type di (meth) acrylate as the component (B), the content thereof is that of the components (A) and (B) from the viewpoint of improving the adhesion after etching.
- the total amount may be 1 to 50 parts by mass, or 5 to 50 parts by mass in 100 parts by mass.
- the total content of component (B) in the photosensitive resin composition is 30 to 70 parts by weight, 35 to 65 parts by weight, 40 to 60 parts by weight with respect to 100 parts by weight as the total of component (A) and component (B). Or 35 to 55 parts by mass.
- this content is 30 parts by mass or more, the sensitivity and resolution tend to be improved in a balanced manner.
- the amount is 70 parts by mass or less, a film (photosensitive layer) tends to be easily formed, and a good resist pattern shape tends to be easily obtained.
- Component (C) Photopolymerization initiator
- the photosensitive resin composition contains at least one photopolymerization initiator as the component (C).
- the photopolymerization initiator is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators.
- component (C) examples include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as propanone-1; quinones such as alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl)- 2,4,5-triarylimidazole dimers such as 4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, 1, Induction of acridine such as 7- (9,9'-acridinyl) heptane And the like.
- Component (C) may contain at least one 2,4,5-triarylimidazole dimer from the viewpoint of further improving sensitivity and adhesion, and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer may be included.
- the 2,4,5-triarylimidazole dimer may be symmetric or asymmetric in structure.
- the content of the component (C) in the photosensitive resin composition is 0.1 to 10 parts by weight, 1 to 7 parts by weight, and 2 to 6 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). Or 3 to 5 parts by mass.
- this content is 0.1 parts by mass or more, good sensitivity, resolution or adhesion tends to be obtained, and when it is 10 parts by mass or less, a good resist pattern shape tends to be obtained. .
- the photosensitive resin composition may further contain a silane coupling agent as the component (D).
- a silane coupling agent As the silane coupling agent, (D1) component: a silane compound having a mercaptoalkyl group, (D2) component: a silane compound having an amino group (preferably a silane compound having a ureido group), (D3) component: (meta And silane compounds having an acryloxy group.
- the photosensitive resin composition contains the component (D1) as the component (D), the photosensitive resin composition has excellent adhesion to a substrate having high smoothness, and has excellent acid resistance that hardly peels off even by ITO etching with hydrochloric acid. The outstanding effect that the resist pattern which it has can be formed can be show
- the photosensitive resin composition may contain a silane coupling agent other than the component (D1) as the component (D).
- the component (D1) and the component (D3) can be used in combination as the component (D).
- the photosensitive resin composition contains only the component (D1) as the component (D)
- a resist pattern exhibiting excellent adhesion can be obtained, while development residue on a copper substrate or the like is likely to occur (that is, on the copper substrate).
- the formed resist pattern tends to be difficult to peel off after etching, and the etching time tends to increase.
- the photosensitive resin composition contains the component (D1) and the component (D3) as the component (D), it suppresses the generation of development residue on the copper substrate while maintaining excellent adhesion.
- the etching time can be shortened.
- the photosensitive resin composition may contain all the (D1) component, (D2) component, and (D3) component as (D) component. According to such a photosensitive resin composition, higher adhesion can be realized while suppressing the occurrence of development residue on a copper substrate or the like.
- the component (D1) may be a silane compound having a mercaptoalkyl group and an alkoxy group (mercaptoalkylalkoxysilane).
- Examples of the component (D1) include mercaptopropylmethyldimethoxysilane and mercaptopropyltrimethoxysilane. And mercaptopropyltriethoxysilane.
- mercaptopropyltrimethoxysilane which is easily hydrolyzed and can be crosslinked at three points is most preferable for the expression of adhesion. These can be used alone or in combination of two or more.
- the component (D2) may be a silane compound having a primary amino group at the terminal.
- Examples of the component (D2) include 3-aminopropylmethoxysilane, aminopropylethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, Examples include 2-ureidoethyltriethoxysilane, 4-ureidobutyltrimethoxysilane, and 4-ureidobutyltriethoxysilane.
- the binder polymer may be a silane compound having a functional group having a low reactivity with a carboxylic acid group such as a ureido group, and developed when used in combination with the component (D1).
- a silane compound having a functional group having a low reactivity with a carboxylic acid group such as a ureido group
- Most preferred is 3-ureidopropyltriethoxysilane, in which the remaining inhibitory effect is particularly noticeable.
- Examples of the component (D3) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
- 3-methacryloxypropyltrimethoxysilane which is easily hydrolyzed and can be crosslinked at three points is most preferable for the expression of adhesion. These can be used alone or in combination of two or more.
- the content of the component (D) in the photosensitive resin composition is 0.01 to 10 parts by mass, 0. 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent adhesion. It may be 05 to 5 parts by mass, or 0.1 to 3 parts by mass. If the content of the component (D) is more than the above range, there is a tendency that development residue on a copper substrate or the like is likely to occur, and there is insufficient curing of the resist bottom due to a decrease in resolution and a significant increase in sensitivity. May occur.
- the content of the component (D) is within the above range, the curability at the bottom of the resist tends to be improved while sufficiently suppressing the development residue on the copper substrate or the like.
- a good resist pattern shape can be obtained and the resistance to the etching solution can be further improved.
- the photosensitive resin composition may contain components other than the components (A) to (D) as necessary.
- the photosensitive resin composition comprises at least one selected from the group consisting of a sensitizing dye, bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. Can be contained.
- sensitizing dye The photosensitive resin composition concerning this embodiment may further contain a sensitizing dye as (E) component.
- sensitizing dyes include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds.
- a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound These can be used alone or in combination of two or more.
- a pyrazoline compound may be contained from the viewpoint of further improving the degree of curing of the resist bottom and excellent adhesion.
- the content improves the degree of cure at the bottom of the resist, and further improves the adhesion, so that the total amount of the component (A) and the component (B) is 100. It may be 0.01 to 5 parts by mass, 0.01 to 1 part by mass, or 0.01 to 0.2 parts by mass with respect to parts by mass.
- the photosensitive resin composition includes a polymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule (such as an oxetane compound); a cationic polymerization initiator; malachite green, Victoria pure blue, brilliant green, methyl violet.
- a polymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule such as an oxetane compound
- a cationic polymerization initiator malachite green, Victoria pure blue, brilliant green, methyl violet.
- Dyes such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, etc .; thermochromic inhibitors; plasticizers such as p-toluenesulfonamide; pigments; fillers An antifoaming agent, a flame retardant, a stabilizer, an adhesion-imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, and the like. These can be used alone or in combination of two or more.
- the photosensitive resin composition contains other components (components other than the components (A) to (D)), these contents are based on 100 parts by mass of the total amount of the components (A) and (B). Each may be about 0.01 to 20 parts by mass.
- the photosensitive resin composition may be a liquid composition further containing at least one organic solvent.
- Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. These may be used alone or in admixture of two or more.
- the content of the organic solvent contained in the photosensitive resin composition can be appropriately selected depending on the purpose and the like.
- the photosensitive resin composition is used as a liquid composition having a solid content of about 30% by mass to 60% by mass (hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”). it can.
- the photosensitive layer which is a coating film of the photosensitive resin composition can be formed by applying the coating liquid on the surface of a support, a metal plate, etc., which will be described later, and drying it. It does not restrict
- a metal plate the metal plate which consists of metals, such as copper, copper-type alloy, iron-type alloys, such as nickel, chromium, iron, stainless steel, can be mentioned.
- a metal plate made of a metal such as copper, a copper-based alloy, or an iron-based alloy can be given.
- the thickness of the photosensitive layer to be formed is not particularly limited and can be appropriately selected depending on the application.
- the thickness of the photosensitive layer (thickness after drying) may be about 1 to 100 ⁇ m.
- the surface of the photosensitive layer opposite to the metal plate may be covered with a protective layer.
- the protective layer include polymer films such as polyethylene and polypropylene.
- a photosensitive element according to the present embodiment is a photosensitive body formed using a support and the photosensitive resin composition provided on one surface of the support. A layer. According to such a photosensitive element, since it includes a photosensitive layer formed using the photosensitive resin composition, there are few chips and cracks that can occur in the resist pattern, and a strong etching solution is used. However, it is possible to suppress the occurrence of resist peeling and chipping, and to obtain a wiring pattern having a good line shape without backlash, and to form a resist pattern having a sufficiently short peeling time. In addition, it is possible to efficiently form a resist pattern having sufficient adhesion to a highly smooth substrate and having excellent acid resistance.
- the photosensitive element may have other layers, such as a protective layer, as needed.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present invention.
- the support 2 the photosensitive layer 4 formed using the photosensitive resin composition, and the protective layer 6 are laminated in this order.
- the photosensitive layer 4 can also be referred to as a coating film of a photosensitive resin composition.
- the coating film is one in which the photosensitive resin composition is in an uncured state.
- the photosensitive element 10 can be obtained as follows, for example. First, on the support 2, a coating solution that is a photosensitive resin composition containing an organic solvent is applied to form a coating layer, which is dried (at least a part of the organic solvent is removed from the coating layer). A photosensitive layer 4 is formed. Next, the surface of the photosensitive layer 4 opposite to the support 2 is covered with a protective layer 6, so that the support 2, the photosensitive layer 4 laminated on the support 2, and the photosensitive layer 4 are covered. The photosensitive element 10 provided with the protective layer 6 laminated
- a film made of a polymer having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate; polyolefin such as polypropylene and polyethylene can be used.
- the thickness of the support 2 may be 1 to 100 ⁇ m, 5 to 50 ⁇ m, or 5 to 30 ⁇ m.
- the support body 2 can be prevented from being broken when the support body 2 is peeled off.
- the fall of the resolution at the time of exposing through the support body 2 is suppressed because it is 100 micrometers or less.
- the adhesive force to the photosensitive layer 4 may be smaller than the adhesive force of the support 2 to the photosensitive layer 4.
- a film made of a polymer having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate; polyolefin such as polypropylene and polyethylene can be used.
- Commercially available products include polypropylene films such as Alfan MA-410 and E-200 manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., PS-25 such as PS-25 manufactured by Teijin Limited, and Tamapoly.
- An example is NF-15A manufactured by KK.
- the protective layer 6 may be the same as the support 2.
- the thickness of the protective layer 6 may be 1 to 100 ⁇ m, 5 to 50 ⁇ m, 5 to 30 ⁇ m, or 15 to 30 ⁇ m.
- the protective layer 6 can be prevented from being broken when the photosensitive layer 4 and the support 2 are laminated on the substrate while peeling off the protective layer 6.
- it is 100 ⁇ m or less, it is excellent in handleability and inexpensiveness.
- the photosensitive element 10 can be manufactured as follows, for example. That is, the photosensitive element 10 includes a step of preparing a coating solution containing a photosensitive resin composition, a step of coating the coating solution on the support 2 to form a coating layer, and drying the coating layer. And a step of forming the photosensitive layer 4.
- Application of the coating liquid onto the support 2 can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.
- the drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it may be performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive layer 4 may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
- the thickness of the photosensitive layer 4 in the photosensitive element 10 can be appropriately selected depending on the application.
- the thickness after drying may be 1 to 100 ⁇ m, 1 to 50 ⁇ m, or 5 to 40 ⁇ m. Industrial coating becomes easy because the thickness of the photosensitive layer 4 is 1 ⁇ m or more. When it is 100 ⁇ m or less, adhesion and resolution tend to be sufficiently obtained.
- the photosensitive element 10 can be suitably used, for example, in a resist pattern forming method described later.
- the resist pattern forming method includes (i) a photosensitive layer forming step of forming a photosensitive layer on a substrate using a photosensitive resin composition or a photosensitive element, and (ii) a part of the photosensitive layer. (Iii) removing the region other than the photocured product region of the photosensitive layer from the substrate, and curing the region of the above by irradiation with actinic rays to form a photocured product region, And a developing step of forming a resist pattern made of a photocured product (photocured product region) of the photosensitive resin composition.
- the method for forming a resist pattern may further include other steps as necessary.
- a resist pattern is a resin pattern or a relief pattern.
- Photosensitive layer forming step In the photosensitive layer forming step, a photosensitive layer is formed using a photosensitive resin composition on a substrate.
- Examples of the method for forming the photosensitive layer on the substrate include a method in which a coating liquid containing a photosensitive resin composition is applied on the substrate and then dried.
- a method for forming a photosensitive layer on a substrate for example, a method of laminating the photosensitive layer of the photosensitive element on the substrate after removing the protective layer from the photosensitive element as necessary. Lamination can be performed by pressure-bonding the photosensitive layer of the photosensitive element to the substrate while heating. By this lamination, a laminate in which the substrate, the photosensitive layer, and the support are laminated in this order is obtained.
- Lamination may be performed at a temperature of 70 to 130 ° C., for example, or may be performed by pressure bonding at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm 2 ). These conditions can be adjusted as needed.
- the substrate may be preheated, and the photosensitive layer may be heated to 70 to 130 ° C.
- (Ii) Exposure Step a part of the photosensitive layer is irradiated with actinic rays, whereby the exposed portion irradiated with the actinic rays is photocured to form a latent image.
- a photosensitive element is used in the photosensitive layer forming step, a support is present on the photosensitive layer, but when the support is transparent to actinic light, active light is transmitted through the support. Can be irradiated.
- the support is light-shielding against actinic rays, the photosensitive layer is irradiated with actinic rays after the support is removed.
- Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method).
- a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method and a DLP (Digital Light Processing) exposure method may be employed.
- LDI Laser Direct Imaging
- DLP Digital Light Processing
- the wavelength of the actinic ray may be 340 to 430 nm or 350 to 420 nm from the viewpoint of obtaining the effect of the present invention more reliably.
- (Iii) Development process In the development process, a region other than the photocured product region of the photosensitive layer (that is, an uncured portion of the photosensitive layer) is removed from the substrate by a development treatment, and a resist made of the photocured product of the photosensitive layer is formed. A pattern is formed on the substrate.
- a developing process is performed after removing a support body.
- the development processing includes wet development and dry development, and wet development is preferably used.
- development is performed by a known development method using a developer corresponding to the photosensitive resin composition.
- the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.
- the developer can be appropriately selected according to the configuration of the photosensitive resin composition.
- the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like.
- Examples of the alkaline aqueous solution used for development include 0.1 to 5% by weight sodium carbonate aqueous solution, 0.1 to 5% by weight potassium carbonate aqueous solution, 0.1 to 5% by weight sodium hydroxide aqueous solution, and 0.1 to 5% by weight four. It may be a sodium borate aqueous solution or the like.
- the pH of the alkaline aqueous solution may be 9-11. The temperature is adjusted according to the alkali developability of the photosensitive layer.
- a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
- the resist pattern is formed by removing the unexposed portion and further curing the resist pattern by heating at about 60 to 250 ° C. and / or exposing at about 0.2 to 10 J / cm 2 as necessary. You may have further the process to do.
- the manufacturing method of the touch panel according to the present embodiment includes a step of etching the base material on which the resist pattern is formed by the resist pattern forming method.
- the etching process is performed on the conductor layer of the base material using the formed resist pattern as a mask (also referred to as “resist”).
- the touch panel is manufactured by forming the lead wiring and the pattern of the transparent electrode by the etching process.
- FIG. 3 is a schematic cross-sectional view showing one embodiment of the touch panel manufacturing method of the present invention.
- the manufacturing method of this aspect is a laminated base material comprising a support base material 22, a transparent conductive layer 24 provided on one surface of the support base material 22, and a metal layer 26 provided on the transparent conductive layer 24.
- the support base 22, the transparent conductive layer 24 provided on one surface of the support base 22, and the transparent conductive layer 24 were provided.
- a photosensitive layer 28 is formed using a photosensitive resin composition on the metal layer 26 of the laminated base material including the metal layer 26.
- the photosensitive layer 28 may include a support on the surface opposite to the metal layer 26.
- a metal layer containing copper may be used.
- the metal layer containing copper include a metal layer containing copper, a copper-nickel alloy, a copper-nickel-titanium alloy, a molybdenum-aluminum-molybdenum laminate, a silver-palladium-copper alloy, and the like.
- a metal layer containing copper, an alloy of copper and nickel, or an alloy of copper, nickel and titanium can be suitably used from the viewpoint that the effects of the present invention can be obtained more remarkably.
- the transparent conductive layer 24 contains indium tin oxide (ITO).
- ITO indium tin oxide
- the transparent conductive layer 24 may contain crystalline ITO from the viewpoint that the annealing process is unnecessary.
- the photosensitive layer 28 is cured by irradiation with actinic rays to form a photocured product region, and regions other than the photocured product region of the photosensitive layer are removed from the laminated substrate.
- the resist pattern 29 is formed on a laminated base material.
- the metal layer 26 and the transparent conductive layer 24 in a region not masked by the resist pattern 29 are removed from the support substrate 22 by etching.
- the etching method is appropriately selected according to the layer to be removed.
- the etching solution for removing the metal layer include a cupric chloride solution, a ferric chloride solution, and a phosphoric acid solution.
- oxalic acid, hydrochloric acid, aqua regia, etc. are used as etching liquid for removing a transparent conductive layer.
- the transparent conductive layer 24 contains crystalline ITO
- a strong acid such as concentrated hydrochloric acid or aqua regia or a chemical solution for etching the metal layer and the transparent conductive layer in a lump (for example, it is necessary to use ITO series such as ITO-4400Z).
- the resist pattern is made of a photocured product of the photosensitive resin composition. However, resist pattern peeling and the like are sufficiently suppressed.
- the photosensitive resin composition according to the present embodiment is suitably used as an etching photosensitive resin composition using the above-described strong acid such as concentrated hydrochloric acid or aqua regia or a chemical solution that etches the metal layer and the transparent conductive layer at once. Can be used.
- FIG. 3C is a diagram showing the state after the etching process.
- the stack composed of the remainder of the metal layer 26, the remainder of the transparent conductive layer 24, and the remainder of the resist pattern 29 on the support substrate 22.
- the body is formed.
- the resist pattern 29 is removed from the laminate.
- the removal of the resist pattern 29 can be performed using, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step described above.
- an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step described above.
- a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used.
- a 1 to 10% by mass sodium hydroxide aqueous solution or a 1 to 10% by mass potassium hydroxide aqueous solution may be used, and a 1 to 5% by mass sodium hydroxide aqueous solution or a 1 to 5% by mass potassium hydroxide aqueous solution may be used.
- Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination.
- FIG. 3D is a view showing the resist pattern after peeling.
- a laminated pattern composed of the remainder of the metal layer 26 and the remainder of the transparent conductive layer 24 is formed on the support base material 22. ing.
- a part of the metal layer 26 other than a part for forming the metal wiring is removed from the laminated pattern, and the metal wiring composed of the remaining part of the metal layer 26 and the transparent electrode composed of the remaining part of the transparent conductive layer 24 are formed.
- an etching method is employed as a method of removing the metal layer 26 in the third step, but the method of removing the metal layer 26 in the third step is not necessarily limited to etching.
- the photosensitive layer 30 is formed on the laminated substrate subjected to the second step (FIG. 3E).
- a resist 31 made of a photocured product of the photosensitive layer 30 is formed through exposure and development of the photosensitive layer 30 (FIG. 3F).
- the photosensitive layer may be a layer formed using the above-described photosensitive resin composition according to the present embodiment, or a layer formed using a conventionally known photosensitive resin composition for etching. May be.
- the metal layer 26 is removed from the portion of the laminated pattern where the resist 31 is not formed by an etching process.
- the etching treatment liquid the same one as the etching liquid for removing the metal layer can be used.
- FIG. 3G is a diagram showing the state after the etching process.
- a transparent electrode composed of the remaining portion of the transparent conductive layer 24 is formed on the support base material 22, and a part of the transparent electrode is formed.
- a laminate composed of the metal layer 26 and the resist 31 is formed on the electrode.
- the transparent electrode composed of the remaining portion of the transparent conductive layer 24 and the metal wiring composed of the remaining portion of the metal layer 26 are formed on the support substrate 22. And are formed.
- FIG. 4 is a top view showing an aspect of a touch panel obtained by using the present invention.
- X electrodes 52 and Y electrodes 54 which are transparent electrodes, are alternately arranged in parallel, and the X electrodes 52 provided in the same row in the longitudinal direction are connected to each other by a single lead wiring 56, The Y electrodes 54 provided in the same row in the width direction are connected to each other by one lead-out wiring 57.
- a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 100 g of a mixture of 80 g of acetone and 20 g of propylene glycol monomethyl ether (mass ratio 4: 1), and nitrogen was introduced into the flask.
- the mixture was heated with stirring while blowing gas, and the temperature was raised to 80 ° C.
- the solution a was dropped into the mixed solution in the flask at a constant dropping rate over 4 hours, and then the solution in the flask was stirred at 80 ° C. for 2 hours.
- the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 hours.
- the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of binder polymer (A-1).
- the nonvolatile content (solid content) of the solution of the binder polymer (A-1) was 42.8% by mass.
- the weight average molecular weight of the binder polymer (A-1) was 50,000, the acid value was 195 mgKOH / g, and the degree of dispersion was 2.58.
- the weight average molecular weight and degree of dispersion were determined by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
- GPC conditions are shown below.
- Eluent Tetrahydrofuran (THF)
- the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. And after precisely weighing 1 g of the polymer of the solid content, 30 g of acetone was added to the polymer, and this was uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
- Acid value 0.1 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I / 100)
- Vf represents the titration amount (mL) of the KOH aqueous solution
- Wp represents the mass (g) of the measured polymer solution
- I represents the ratio (mass%) of the non-volatile content in the measured polymer solution.
- ((A) component) A-1 Binder polymer (A-1) obtained in Production Example 1.
- ((C) component) B-CIM 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Changzhou Power Electronics New Materials Co., Ltd.)
- LCV Leuco Crystal Violet (Yamada Chemical Co., Ltd.)
- TBC 4-t-butylcatechol (DIC Corporation, “DIC-TBC-5P”)
- SF-808H Mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (Sanwa Kasei Co., Ltd., “SF-808H”)
- AZCV-PW [4- ⁇ bis (4-dimethylaminophenyl) methylene ⁇ -2,5-cyclohexadiene-1-ylidene] (Hodogaya Chemical Co., Ltd.)
- ⁇ Production of photosensitive element> The coating solution of the photosensitive resin composition obtained above was applied on a polyethylene terephthalate film (product name “FB-40”, manufactured by Toray Industries, Inc.) having a thickness of 16 ⁇ m so as to have a uniform thickness, and 70 ° C. Then, a drying process was sequentially performed with a hot air convection dryer at 110 ° C. to form a photosensitive layer having a thickness of 15 ⁇ m after drying.
- a protective layer product name “NF-15A”, manufactured by Tamapoly Co., Ltd.
- a transparent conductive layer made of crystalline ITO was formed on the upper layer of the polyethylene terephthalate material, and a metal layer made of copper was formed on the upper layer of the polyethylene terephthalate material.
- the photosensitive element produced above was laminated (laminated
- Lamination is performed under conditions of a temperature of 110 ° C. and a lamination pressure of 4 kgf / cm 2 (0.4 MPa) so that the photosensitive layer of the photosensitive element is in close contact with the surface of the metal layer of the substrate while removing the protective layer. It was. In this way, a laminated substrate in which the photosensitive layer and the support were laminated on the surface of the metal layer of the substrate was obtained.
- the obtained laminated substrate was allowed to cool to 23 ° C.
- the laminated substrate is divided into three regions, and on one of the regions, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm ⁇ 187 mm, each step.
- a phototool having a 41-step tablet having a size of 3 mm ⁇ 12 mm was adhered.
- a parallel light exposure machine product name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.
- a short arc UV lamp product name “AHD-5000R” manufactured by Oak Manufacturing Co., Ltd.
- the photosensitive layer was exposed through a photo tool and a support with an energy amount (exposure amount) of 100 mJ / cm 2 . At this time, other areas not used were covered with a black sheet. Moreover, it exposed with the energy amount of 200mJ / cm ⁇ 2 > and 400mJ / cm ⁇ 2 > separately with respect to each different area
- the illuminance was measured using an ultraviolet illuminance meter (product name “UIT-150” manufactured by USHIO INC.) To which a 405 nm probe was applied.
- the support was peeled off from the laminated base material, the photosensitive layer was exposed, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed for 16 seconds to remove unexposed portions.
- the resist pattern which consists of a photocured material of the photosensitive resin composition was formed on the metal layer surface of a base material.
- a calibration curve between the exposure amount and the step step number is created from the remaining step number (step step number) of the step tablet obtained as a resist pattern (cured film) at each exposure amount, and the exposure amount at which the step step number is 17 steps is obtained.
- the sensitivity of the photosensitive resin composition was evaluated. The sensitivity is indicated by the exposure amount at which the number of step steps obtained from the calibration curve is 17, and the smaller the exposure amount, the better the sensitivity.
- the adhesion after etching of the resist pattern was evaluated as follows. Using a mask pattern having an L / S of 4/400 to 47/400 (unit: ⁇ m), the photosensitive layer of the laminated base material is exposed with an energy amount that makes the remaining number of steps of the 41-step tablet tablet 23. did. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a patterned substrate.
- the obtained base material was etched at 40 ° C. for 30 seconds using ITO-4400Z (trade name, manufactured by ADEKA Corporation), and then washed and dried.
- the line shape after the etching of the wiring pattern is the digital microscope for the wiring pattern formed under the resist pattern having L / S of 47/400 (unit: ⁇ m) in the evaluation of the adhesion after the etching. Observation was performed using VHX-2000 (manufactured by Keyence Corporation). Further, the side etching width was calculated from the difference between the line width of the resist pattern and the line width of the circuit pattern after etching. The line shape after etching the wiring pattern was evaluated according to the following criteria based on the value of the side etching width and the presence or absence of rattling. The results are shown in Tables 3 and 4.
- A There is no backlash in the line shape after etching the wiring pattern, and the value of the side etching width is less than 5 ⁇ m.
- B Although there is no backlash in the line shape after etching the wiring pattern, the value of the side etching width is 5 ⁇ m or more and less than 8 ⁇ m.
- C The line shape after the etching of the wiring pattern is not rattled, but the value of the side etching width is 8 ⁇ m or more.
- D Roughness is observed in the line shape after etching the wiring pattern.
- the flexibility of the resist pattern was evaluated by a mandrel test (JIS K5600-5-1). Using a polyethylene terephthalate negative (a negative that can expose the entire surface), the photosensitive layer of the laminated base material was exposed with an energy amount such that the number of remaining stages of the 41-step tablet was 17. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a laminated base material on which a cured film was formed. The laminated base material on which this cured film was formed was cut out to 10 mm ⁇ 100 mm to obtain a test piece for a mandrel test.
- test piece was bent at 180 ° along the side of a cylindrical rod (mandrel jig) having diameters of 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 25 mm, and then tested.
- a cylindrical rod manufacturedrel jig
- the two-thirds of the test piece was slid 5 times at a constant speed along the side surface of the mandrel jig.
- the minimum diameter which does not peel and crack between a base material and a resist pattern was calculated
- the results are shown in Tables 3 and 4.
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Abstract
A photosensitive resin composition which contains a binder polymer (component (A)), a photopolymerizable compound (component (B)) and a photopolymerization initiator (component (C)), and wherein the component (B) contains a (meth)acrylate having 6 ethylenically unsaturated bonds in each molecule and a (meth)acrylate having an isocyanuric ring skeleton.
Description
本発明は、感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びタッチパネルの製造方法に関する。
The present invention relates to a photosensitive resin composition, a photosensitive element, a resist pattern forming method, and a touch panel manufacturing method.
タッチパネルのタッチセンサー部は、視覚的情報を表示する範囲(ビューエリア)において、人の指等の接触による位置情報を検出するセンサー部位と、位置情報を外部素子に伝えるための引き出し配線部位とを備える構成となっている。
The touch sensor unit of the touch panel includes a sensor part for detecting position information due to contact with a human finger or the like in a range (view area) for displaying visual information, and a lead wiring part for transmitting the position information to an external element. It is configured to be equipped.
上記センサー部位には、可視光の吸収及び散乱が少なく、且つ導電性を有する電極のパターンが形成されている。また、引き出し配線部位の各々の配線には抵抗値の小さい金属が用いられている。
The sensor part is formed with a conductive electrode pattern with little absorption and scattering of visible light. Further, a metal having a small resistance value is used for each wiring in the lead-out wiring region.
このようなセンサー部位及び引き出し配線部位は、例えば、ネガ型感光性樹脂組成物を用いて、図2のようにして製造される。なお、図2は、タッチパネルのタッチセンサー部の従来の製造方法を示す模式断面図である。まず、透明導電層14を有する支持基材12(ポリエチレンテレフタレート等のフィルム基板又はガラス基板)上に感光性樹脂組成物の塗布等によって、感光層16を形成する(感光層形成工程)(図2(a))。次に、感光層16の所定部分に活性光線を照射して露光部分を硬化させる(露光工程)。その後、未硬化部分を透明導電層14上から除去することにより、透明導電層14上に感光性樹脂組成物の光硬化物を含むレジストパターンを形成する(現像工程)(図2(b))。レジストパターンに対してエッチング処理を施して、支持基材12上から透明導電層14の一部を除去して、センサー部位の透明導電層のパターンを形成する(エッチング工程)(図2(c))。次いで、透明導電層14からレジストパターンを剥離し、除去する(剥離工程)(図2(d))。続いて、形成したセンサー部位の透明導電層のパターンからの引き出し配線18を、銀ペースト等を用いたスクリーン印刷で形成することで、タッチセンサー部を製造する。
Such sensor parts and lead-out wiring parts are manufactured as shown in FIG. 2 using, for example, a negative photosensitive resin composition. FIG. 2 is a schematic cross-sectional view showing a conventional manufacturing method of the touch sensor portion of the touch panel. First, a photosensitive layer 16 is formed on a supporting substrate 12 (film substrate or glass substrate such as polyethylene terephthalate) having a transparent conductive layer 14 by applying a photosensitive resin composition (photosensitive layer forming step) (FIG. 2). (A)). Next, the exposed portion is cured by irradiating a predetermined portion of the photosensitive layer 16 with an actinic ray (exposure step). Then, a resist pattern containing a photocured product of the photosensitive resin composition is formed on the transparent conductive layer 14 by removing the uncured portion from the transparent conductive layer 14 (development process) (FIG. 2B). . Etching is performed on the resist pattern, and a part of the transparent conductive layer 14 is removed from the support base 12 to form a pattern of the transparent conductive layer at the sensor site (etching step) (FIG. 2C). ). Next, the resist pattern is peeled off from the transparent conductive layer 14 and removed (peeling step) (FIG. 2D). Subsequently, the lead wiring 18 from the pattern of the transparent conductive layer of the formed sensor part is formed by screen printing using a silver paste or the like, thereby manufacturing the touch sensor unit.
また、タッチパネルの額縁(ベゼル)の狭小化によって、引き出し配線部位における配線幅及びピッチの狭小化が求められている。銀ペーストを用いたスクリーン印刷ではL/S(ライン幅/スペース幅)が50/50(単位:μm)程度のパターン形成が限度とされるが、額縁の狭小化に対応するためにL/Sが30/30(単位:μm)以下のパターン形成が要求されている。
Also, due to the narrowing of the frame (bezel) of the touch panel, it is required to narrow the wiring width and pitch at the lead-out wiring site. In screen printing using silver paste, pattern formation with L / S (line width / space width) of about 50/50 (unit: μm) is the limit, but L / S is required to cope with the narrowing of the frame. Is required to form a pattern of 30/30 (unit: μm) or less.
L/Sが小さく、ピッチが狭小な引き出し配線のパターンを有するタッチセンサー部を製造するため、フォトリソグラフィの技法を用いたタッチセンサー部の形成方法が提案されている(例えば、特許文献1参照)。このタッチセンサー部の製造方法では、まず、透明導電層及び金属層を有する支持基材上に、感光性樹脂組成物を用いて、第一の感光層を形成する(第1の感光層形成工程)。次に、感光層の所定部分に活性光線を照射して露光部分を硬化させ(第1の露光工程)、その後、未硬化部分を金属層上から除去することにより、金属層上に、感光性樹脂組成物の光硬化物を含むレジストパターンを形成する(第1の現像工程)。次に、エッチング処理によって、金属層及び透明導電層を除去する(第1のエッチング工程)。次いで、レジストパターンを金属層上から剥離し、除去する(第1の剥離工程)。続いて、新たに、感光性樹脂組成物を用いて、金属層上に第二の感光層を形成する(第2の感光層形成工程)。次に、感光層の所定部分に活性光線を照射して露光部分を硬化させ(第2の露光工程)、その後、未硬化部分を金属層上から除去することにより、金属層上に、レジストパターンを形成する(第2の現像工程)。次に、センサー部位で不要な、レジストパターンが形成されていない金属層のみをエッチング処理によって除去し(第2のエッチング工程)、最終的に、レジストパターンを剥離し、除去することでタッチセンサー部を製造する。
In order to manufacture a touch sensor unit having a pattern of a lead wiring with a small L / S and a narrow pitch, a method of forming the touch sensor unit using a photolithography technique has been proposed (for example, see Patent Document 1). . In this method for manufacturing a touch sensor unit, first, a first photosensitive layer is formed using a photosensitive resin composition on a supporting substrate having a transparent conductive layer and a metal layer (first photosensitive layer forming step). ). Next, a predetermined portion of the photosensitive layer is irradiated with actinic rays to cure the exposed portion (first exposure step), and then the uncured portion is removed from the metal layer, thereby exposing the photosensitive layer to the photosensitive layer. A resist pattern containing a photocured product of the resin composition is formed (first development step). Next, the metal layer and the transparent conductive layer are removed by an etching process (first etching step). Next, the resist pattern is peeled off from the metal layer and removed (first peeling step). Subsequently, a second photosensitive layer is newly formed on the metal layer using the photosensitive resin composition (second photosensitive layer forming step). Next, a predetermined portion of the photosensitive layer is irradiated with actinic rays to cure the exposed portion (second exposure step), and then the uncured portion is removed from the metal layer to form a resist pattern on the metal layer. (Second development step). Next, only the metal layer on which the resist pattern is not formed at the sensor part is removed by etching (second etching process), and finally the resist pattern is peeled and removed to remove the touch sensor unit. Manufacturing.
このようなタッチセンサー部の製造方法では、フォトリソグラフィの技法を用いることで、原理的にL/Sを30/30(単位:μm)以下にすることが可能であり、タッチパネルの薄型軽量化に大いに貢献できる。一方で、タッチセンサー部の透明導電層は、例えば、酸化インジウムスズ(ITO)をスパッタリングの技法を用いて製膜することで形成される。また、透明導電層の上に形成される金属層は、例えば、透明導電層と同様に、スパッタリングの技法を用いて形成される。スパッタリングの技法を用いて形成した透明導電層及び金属層の表面は非常に高い平滑性を有している。非常に高い平滑性を有する金属層と感光性樹脂組成物との密着性は低下する場合があるため、銅、銅とニッケルとの合金、銅とニッケルとチタンの合金、モリブデン-アルミニウム-モリブデン積層体、銀とパラジウムと銅との合金等が用いられる金属層に対して、使用する感光性樹脂組成物には、高い密着性が求められる。
In such a touch sensor manufacturing method, by using a photolithography technique, in principle, L / S can be reduced to 30/30 (unit: μm) or less, and the touch panel can be made thin and light. You can contribute a lot. On the other hand, the transparent conductive layer of the touch sensor unit is formed, for example, by forming a film of indium tin oxide (ITO) using a sputtering technique. Moreover, the metal layer formed on a transparent conductive layer is formed using the technique of sputtering similarly to a transparent conductive layer, for example. The surfaces of the transparent conductive layer and metal layer formed by using the sputtering technique have very high smoothness. Since the adhesion between the metal layer having very high smoothness and the photosensitive resin composition may be lowered, copper, an alloy of copper and nickel, an alloy of copper, nickel and titanium, and a molybdenum-aluminum-molybdenum laminate The photosensitive resin composition to be used is required to have high adhesion to a metal layer in which a body, an alloy of silver, palladium, and copper is used.
また、透明導電層には、エッチング処理のし易さの観点から、例えば、非晶性のITOが用いられる。しかし、非晶性のITOは抵抗値が高いため、例えば、加熱(アニール)処理によってITOの結晶化を行うことで、抵抗値を下げている。しかし、近年、タッチパネルの薄型軽量化に伴い、タッチパネル部の支持基材として、フィルム基材を用いることが求められている。支持基材としてフィルム基材を用いる場合、アニール処理を行うとフィルム基材の収縮が起こる等して寸法安定性が悪化する。そのため、支持基材としてフィルム基材を用いる場合は、透明導電層のパターンを形成する前に、透明導電層として結晶性のITOを用いることが必要となる。
For the transparent conductive layer, for example, amorphous ITO is used from the viewpoint of easy etching. However, since amorphous ITO has a high resistance value, the resistance value is lowered by, for example, crystallization of ITO by a heating (annealing) process. However, in recent years, with the reduction in thickness and weight of touch panels, it is required to use a film base material as a support base material for the touch panel portion. When a film substrate is used as the support substrate, the dimensional stability deteriorates due to the shrinkage of the film substrate and the like when the annealing treatment is performed. Therefore, when using a film base material as a supporting base material, it is necessary to use crystalline ITO as the transparent conductive layer before forming the pattern of the transparent conductive layer.
非晶性のITOは、シュウ酸等の弱酸で充分に溶解することができるが、結晶性のITOは濃塩酸(>20質量%)等の強酸を用い、且つ加熱条件(40~50℃程度)でエッチングする必要がある。そのため、用いる感光性樹脂組成物には、高い耐酸性、すなわち、強酸を用いたエッチングによっても、金属層との密着性が確保でき、強酸による金属層の腐食を抑制できることが求められる。
Amorphous ITO can be sufficiently dissolved with a weak acid such as oxalic acid, but crystalline ITO uses a strong acid such as concentrated hydrochloric acid (> 20% by mass) and heating conditions (about 40 to 50 ° C.). ) Need to be etched. Therefore, the photosensitive resin composition to be used is required to have high acid resistance, that is, adhesion with the metal layer can be ensured even by etching using a strong acid, and corrosion of the metal layer due to the strong acid can be suppressed.
また、レジストパターンのL/Sを30/30(単位:μm)以下にして高解像性を有する配線パターン(導体パターンともいえる)を形成する手法として、金属層と透明導電層を一括でエッチングする手法がある。従来までの金属層をエッチングした後、透明導電層をエッチングする手法では、エッチング時の面内バラつきが大きくなるため、高解像性を有する配線パターンを得ることが困難であった。金属層と透明導電層を一括でエッチングする薬液としては、ITO-4400Z(株式会社ADEKA製)が商業的に入手可能である。
In addition, as a technique for forming a wiring pattern (also referred to as a conductor pattern) having a high resolution by reducing the L / S of the resist pattern to 30/30 (unit: μm) or less, the metal layer and the transparent conductive layer are etched together. There is a technique to do. In the conventional method of etching a transparent conductive layer after etching a metal layer, it has been difficult to obtain a wiring pattern having high resolution because in-plane variation during etching becomes large. ITO-4400Z (manufactured by ADEKA Corporation) is commercially available as a chemical solution for etching the metal layer and the transparent conductive layer at once.
また、耐酸性(強酸中に浸漬した後の密着性)を向上させる技術として、特定のエポキシ化合物、光重合性化合物及び光重合開始剤を必須成分とする感光性樹脂組成物が提案されている(例えば、特許文献2参照)。
Further, as a technique for improving acid resistance (adhesion after being immersed in a strong acid), a photosensitive resin composition containing a specific epoxy compound, a photopolymerizable compound and a photopolymerization initiator as essential components has been proposed. (For example, refer to Patent Document 2).
更に、レジストパターンの形成に用いる感光性樹脂組成物として、種々の感光性樹脂組成物が検討されている。例えば、感光性樹脂組成物において、特定の架橋剤、特定のシランカップリング剤等を添加すること、特定の構造単位を有するバインダーポリマーを必須成分とすることなどが提案されている(例えば、特許文献3~7参照)。
Furthermore, various photosensitive resin compositions have been studied as photosensitive resin compositions used for forming resist patterns. For example, in a photosensitive resin composition, it has been proposed to add a specific cross-linking agent, a specific silane coupling agent, etc., and to have a binder polymer having a specific structural unit as an essential component (for example, a patent Reference 3-7).
レジストパターンのL/Sを30/30(単位:μm)以下にして、高い解像性を有するレジストパターンを形成する場合、レジストパターンの欠け、クラック、蛇行、剥がれ等の不良が発生しやすくなる。特に、この分野においては、不良の発生により、センサー部位の電極及び引き出し配線に、短絡及び断線が生じる可能性がある。したがって、レジストパターンには、欠け、クラック、蛇行、剥がれ等が発生しないことが、従来以上に求められる。
When forming a resist pattern having a high resolution with the L / S of the resist pattern being 30/30 (unit: μm) or less, defects such as chipping, cracks, meandering, and peeling of the resist pattern are likely to occur. . In particular, in this field, due to the occurrence of a defect, there is a possibility that a short circuit and a disconnection may occur in the electrode of the sensor part and the lead-out wiring. Therefore, the resist pattern is required more than before to be free from chipping, cracking, meandering, peeling and the like.
しかしながら、特許文献2に記載の感光性樹脂組成物は、解像性に優れたレジストパターンを形成することが困難であり、レジストパターンの不良が発生する場合があった。また、特許文献3~7に記載の感光性樹脂組成物は、ITOエッチングの際にレジストの剥がれ、欠け等の不良が生じる場合があった。とりわけ、ITOを除去するために用いられる、強いエッチング液を用いた場合に、レジストパターンに剥がれ及び欠け等の不良が発生したり、また、レジストパターンに剥がれ及び欠け等の不良が発生していなくても、形成される配線パターンのライン形状にガタツキが発生したりしやすくなる傾向があることが分かった。また、レジストパターンに発生し得る不良が少なく、配線パターンのライン形状が良好であることと、をバランスよく高水準で両立させることが困難であることが分かった。
However, in the photosensitive resin composition described in Patent Document 2, it is difficult to form a resist pattern with excellent resolution, and a resist pattern may be defective. In addition, the photosensitive resin compositions described in Patent Documents 3 to 7 sometimes cause defects such as resist peeling and chipping during ITO etching. In particular, when a strong etching solution used for removing ITO is used, defects such as peeling and chipping occur in the resist pattern, and defects such as peeling and chipping do not occur in the resist pattern. However, it has been found that there is a tendency that the line shape of the wiring pattern to be formed tends to be loose. Further, it has been found that there are few defects that can occur in the resist pattern, and that the line shape of the wiring pattern is good and that it is difficult to achieve both a balanced and high level.
本発明は、このような課題を解決するためになされたものであり、レジストパターンに発生し得る欠け及びクラックが少なく、且つ、強いエッチング液を用いた場合であっても、レジストの蛇行及び剥がれが発生することを抑制できるレジストパターンが形成可能となる感光性樹脂組成物を提供することを目的とする。本発明はまた、上記感光性樹脂組成物を用いた感光性エレメント、レジストパターンの形成方法及びタッチパネルの製造方法を提供することを目的とする。
The present invention has been made to solve such problems, and there are few chips and cracks that can occur in a resist pattern, and the resist meanders and peels even when a strong etching solution is used. It aims at providing the photosensitive resin composition which can form the resist pattern which can suppress that generation | occurrence | production occurs. Another object of the present invention is to provide a photosensitive element, a resist pattern forming method and a touch panel manufacturing method using the photosensitive resin composition.
本発明者らは、上記課題を解決するべく鋭意検討を重ねた結果、所定の成分を含有する感光性樹脂組成物を用いることで優れた特性を有するレジストパターンを形成できることを見出した。
As a result of intensive studies to solve the above problems, the present inventors have found that a resist pattern having excellent characteristics can be formed by using a photosensitive resin composition containing a predetermined component.
すなわち、本発明の第一の態様は、(A)成分:バインダーポリマー、(B)成分:光重合性化合物、及び、(C)成分:光重合開始剤を含有し、上記(B)成分が、分子内に6つのエチレン性不飽和結合を有する(メタ)アクリレートと、イソシアヌル環骨格を有する(メタ)アクリレートとを含む、感光性樹脂組成物に関する。
That is, the first aspect of the present invention comprises (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator. The invention relates to a photosensitive resin composition comprising (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton.
このような感光性樹脂組成物によれば、レジストパターンに発生し得る欠け及びクラックが少なく、且つ、強いエッチング液を用いた場合であっても、レジストの蛇行及び剥がれが発生することを抑制できる。そのため、このような感光性樹脂組成物を用いることで、高解像な微細回路パターンを形成することができる。
According to such a photosensitive resin composition, there are few cracks and cracks that can occur in the resist pattern, and even when a strong etching solution is used, the occurrence of resist meandering and peeling can be suppressed. . Therefore, by using such a photosensitive resin composition, a high-resolution fine circuit pattern can be formed.
上記(B)成分は、(ポリ)オキシエチレン基を有するビスフェノールA型ジ(メタ)アクリレートを更に含んでいてもよい。このような感光性樹脂組成物によれば、レジストパターンの耐酸性が一層向上し、ITOエッチングの際にレジストパターンの膨潤による蛇行及び剥がれを一層顕著に抑制することができる。
The component (B) may further contain a bisphenol A type di (meth) acrylate having a (poly) oxyethylene group. According to such a photosensitive resin composition, the acid resistance of the resist pattern is further improved, and meandering and peeling due to swelling of the resist pattern during ITO etching can be more significantly suppressed.
本発明の第二の態様は、支持体と、該支持体の一面上に設けられた、上記第一の態様に係る感光性樹脂組成物を用いて形成された感光層と、を備える、感光性エレメントに関する。このような感光性エレメントによれば、第一の態様に係る感光性樹脂組成物を用いて形成された感光層を備えるため、強いエッチング液を用いた場合であっても、レジストの蛇行及び欠けが発生することを抑制できるレジストパターンを形成できる。そのため、このような感光性エレメントを用いることで、効率的に高解像な微細回路パターンを形成することができる。
A second aspect of the present invention includes a support and a photosensitive layer provided on one surface of the support and formed using the photosensitive resin composition according to the first aspect. Related to sex elements. According to such a photosensitive element, since it includes the photosensitive layer formed using the photosensitive resin composition according to the first aspect, even when a strong etching solution is used, the meandering and chipping of the resist are performed. It is possible to form a resist pattern that can suppress the occurrence of. Therefore, by using such a photosensitive element, a high-resolution fine circuit pattern can be efficiently formed.
本発明の第三の態様は、基材上に、上記第一の態様に係る感光性樹脂組成物又は上記第二の態様に係る感光性エレメントを用いて感光層を形成する感光層形成工程と、上記感光層の一部の領域を活性光線の照射により硬化して、光硬化物領域を形成する露光工程と、上記感光層の上記光硬化物領域以外の領域を上記基材上から除去して、上記光硬化物領域からなるレジストパターンを得る現像工程と、を有する、レジストパターンの形成方法に関する。このようなレジストパターンの形成方法によれば、レジストパターンに発生し得る欠け及びクラックが少なく、強いエッチング液を用いた場合であっても、レジストの蛇行及び剥がれが発生することを抑制できるレジストパターンを形成することができる。また、このようなレジストパターンの形成方法によれば、平滑性の高い基板に対しても優れた密着性を有し、解像性に優れたレジストパターンを形成することが可能である。
According to a third aspect of the present invention, there is provided a photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to the first aspect or the photosensitive element according to the second aspect. A part of the photosensitive layer is cured by irradiation with actinic rays to form a photocured product region, and a region other than the photocured product region of the photosensitive layer is removed from the substrate. And a developing step for obtaining a resist pattern composed of the photocured product region. According to such a resist pattern forming method, the resist pattern can be prevented from causing occurrence of meandering and peeling of the resist even when a strong etching solution is used, since there are few chips and cracks that can occur in the resist pattern. Can be formed. In addition, according to such a resist pattern forming method, it is possible to form a resist pattern having excellent adhesion to a substrate having high smoothness and excellent resolution.
本発明の第四の態様は、支持基材と該支持基材の一面上に設けられた酸化インジウムスズを含む透明導電層と該透明導電層上に設けられた金属層とを備える積層基材の、上記金属層上に、上記第一の態様に係る感光性樹脂組成物の光硬化物からなるレジストパターンを形成する第1の工程と、上記金属層及び上記透明導電層をエッチングして、上記透明導電層の残部及び上記金属層の残部からなる積層パターンを形成する第2の工程と、上記積層パターンの一部から上記金属層を除去して、上記透明導電層の残部からなる透明電極と上記金属層の残部からなる金属配線とを形成する第3の工程と、を有する、タッチパネルの製造方法に関する。
A fourth aspect of the present invention is a laminated base material comprising a support base material, a transparent conductive layer containing indium tin oxide provided on one surface of the support base material, and a metal layer provided on the transparent conductive layer A first step of forming a resist pattern made of a photocured product of the photosensitive resin composition according to the first aspect on the metal layer, and etching the metal layer and the transparent conductive layer, A second step of forming a laminated pattern comprising the remainder of the transparent conductive layer and the remainder of the metal layer; and a transparent electrode comprising the remainder of the transparent conductive layer by removing the metal layer from a part of the laminated pattern And a third step of forming a metal wiring composed of the remainder of the metal layer.
このようなタッチパネルの製造方法によれば、レジストパターンが上記第一の態様に係る感光性樹脂組成物の光硬化物から形成されたものであるため、エッチング処理におけるレジストパターンの剥離等が充分に抑制され、容易に且つ効率良く狭ピッチのタッチパネル(例えば、L/Sが30/30以下の引出配線を有するタッチパネル)を製造することができる。
According to such a touch panel manufacturing method, since the resist pattern is formed from the photocured product of the photosensitive resin composition according to the first aspect, the resist pattern is sufficiently peeled off during the etching process. It is possible to manufacture a narrow-pitch touch panel (for example, a touch panel having a lead-out line with an L / S of 30/30 or less) that is suppressed and easily and efficiently.
上記透明導電層は、結晶性の酸化インジウムスズを含んでいてもよく、上記第2の工程におけるエッチングは、強酸によるエッチングであってもよい。上記製造方法においては、レジストパターンが上記第一の態様に係る感光性樹脂組成物の光硬化物から形成されたものであるため、強酸によるエッチングによってもレジストパターンの剥離等が充分に抑制される。そのため、上記製造方法は、結晶性の酸化インジウムスズを含む透明導電層を備える積層基材を用いたタッチパネルの製造に好適に適用することができる。
The transparent conductive layer may contain crystalline indium tin oxide, and the etching in the second step may be etching with a strong acid. In the manufacturing method, since the resist pattern is formed from the photocured product of the photosensitive resin composition according to the first aspect, peeling of the resist pattern is sufficiently suppressed even by etching with a strong acid. . Therefore, the said manufacturing method can be applied suitably for manufacture of the touch panel using the laminated base material provided with the transparent conductive layer containing crystalline indium tin oxide.
本発明によれば、レジストパターンに発生し得る欠け及びクラックが少なく、強いエッチング液を用いた場合であっても、レジストの蛇行及び剥がれが発生することを抑制できるレジストパターンが形成可能となる感光性樹脂組成物が提供される。また、本発明によれば、当該感光性樹脂組成物を用いた感光性エレメント、レジストパターンの形成方法及びタッチパネルの製造方法が提供される。
According to the present invention, there are few chips and cracks that can occur in a resist pattern, and even when a strong etching solution is used, a resist pattern that can suppress the occurrence of resist meandering and peeling can be formed. A functional resin composition is provided. Moreover, according to this invention, the formation method of the photosensitive element using the said photosensitive resin composition, the resist pattern, and the manufacturing method of a touch panel are provided.
以下、本発明を実施するための形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。なお、本明細書において、(メタ)アクリル酸とは、アクリル酸又はメタクリル酸を意味し、(メタ)アクリレートとは、アクリレート又はそれに対応するメタクリレートを意味し、(メタ)アクリロキシ基とはアクリロキシ基又はそれに対応するメタクリロキシ基を意味する。
Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or a corresponding methacrylate, and (meth) acryloxy group means acryloxy group. Or the methacryloxy group corresponding to it.
また、本明細書において、(ポリ)オキシアルキレン基とは、オキシアルキレン基又は2以上のアルキレン基がエーテル結合で連結したポリオキシアルキレン基の少なくとも1種を意味する。すなわち、(ポリ)オキシエチレン基とは、オキシエチレン基又は2以上のエチレン基がエーテル結合で連結したポリオキシエチレン基の少なくとも1種を意味し、(ポリ)オキシプロピレン基等の他の類似表現についても同様である。なお、(ポリ)オキシエチレン基を、「EO基」と、(ポリ)オキシプロピレン基を、「PO基」と称する場合がある。また、「層」との語は、平面図として観察したときに、全面に形成されている形状の構造に加え、一部に形成されている形状の構造も包含される。また、「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば、本用語に含まれる。また、「~」を用いて示された数値範囲は、「~」の前後に記載される数値を、それぞれ最小値及び最大値として含む範囲を示す。また、本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
In the present specification, the (poly) oxyalkylene group means at least one polyoxyalkylene group in which an oxyalkylene group or two or more alkylene groups are linked by an ether bond. That is, (poly) oxyethylene group means at least one polyoxyethylene group in which an oxyethylene group or two or more ethylene groups are linked by an ether bond, and other similar expressions such as (poly) oxypropylene group The same applies to. The (poly) oxyethylene group may be referred to as “EO group” and the (poly) oxypropylene group may be referred to as “PO group”. Further, the term “layer” includes a structure formed in a part in addition to a structure formed over the entire surface when observed as a plan view. Further, the term “process” is included in this term as long as the intended purpose of the process is achieved, even when the process is not clearly distinguished from other processes. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
<感光性樹脂組成物>
本実施形態に係る感光性樹脂組成物(以下、単に「感光性樹脂組成物」という。)は、(A)成分:バインダーポリマー、(B)成分:光重合性化合物、及び、(C)成分:光重合開始剤を含有し、上記(B)成分が、分子内に6つのエチレン性不飽和結合を有する(メタ)アクリレートと、イソシアヌル環骨格を有する(メタ)アクリレートとを含む、感光性樹脂組成物である。 <Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment (hereinafter simply referred to as “photosensitive resin composition”) includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component. : A photosensitive resin containing a photopolymerization initiator, wherein the component (B) includes (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton. It is a composition.
本実施形態に係る感光性樹脂組成物(以下、単に「感光性樹脂組成物」という。)は、(A)成分:バインダーポリマー、(B)成分:光重合性化合物、及び、(C)成分:光重合開始剤を含有し、上記(B)成分が、分子内に6つのエチレン性不飽和結合を有する(メタ)アクリレートと、イソシアヌル環骨格を有する(メタ)アクリレートとを含む、感光性樹脂組成物である。 <Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment (hereinafter simply referred to as “photosensitive resin composition”) includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component. : A photosensitive resin containing a photopolymerization initiator, wherein the component (B) includes (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton. It is a composition.
このような感光性樹脂組成物によれば、剥がれ及び欠けの発生が抑制された高解像なレジストパターンが形成可能となる。また、上記感光性樹脂組成物を用いて形成されたレジストパターンは、強酸を用いてITOをエッチングした場合であっても蛇行及び剥がれの発生が抑制されるため、得られる回路パターンはライン形状が良好となる。そのため、本実施形態に係る感光性樹脂組成物は、ITOエッチング用として、特に結晶性ITOを含む透明導電層のエッチング用として、好適である。
According to such a photosensitive resin composition, it is possible to form a high-resolution resist pattern in which the occurrence of peeling and chipping is suppressed. In addition, since the resist pattern formed using the photosensitive resin composition suppresses the occurrence of meandering and peeling even when ITO is etched using a strong acid, the resulting circuit pattern has a line shape. It becomes good. Therefore, the photosensitive resin composition according to the present embodiment is suitable for etching ITO, particularly for etching a transparent conductive layer containing crystalline ITO.
また、レジストパターンに発生し得る欠け及びクラックを更に抑制する観点から、感光性樹脂組成物から形成されるレジストパターンの可とう性を向上させることを要求される場合もある。本実施形態にかかる感光性樹脂組成物によれば、レジストパターンの可とう性も向上させることができる。
Further, from the viewpoint of further suppressing chipping and cracks that may occur in the resist pattern, it may be required to improve the flexibility of the resist pattern formed from the photosensitive resin composition. According to the photosensitive resin composition concerning this embodiment, the flexibility of a resist pattern can also be improved.
(A)成分:バインダーポリマー
感光性樹脂組成物は、(A)成分としてバインダーポリマーを少なくとも1種含有する。バインダーポリマーとしては、例えば、重合性単量体(モノマー)をラジカル重合させて得られる重合体が挙げられる。 (A) component: Binder polymer The photosensitive resin composition contains at least one binder polymer as the component (A). Examples of the binder polymer include a polymer obtained by radical polymerization of a polymerizable monomer (monomer).
感光性樹脂組成物は、(A)成分としてバインダーポリマーを少なくとも1種含有する。バインダーポリマーとしては、例えば、重合性単量体(モノマー)をラジカル重合させて得られる重合体が挙げられる。 (A) component: Binder polymer The photosensitive resin composition contains at least one binder polymer as the component (A). Examples of the binder polymer include a polymer obtained by radical polymerization of a polymerizable monomer (monomer).
重合性単量体(モノマー)としては、(メタ)アクリル酸;(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸シクロアルキルエステル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸ベンジル誘導体、(メタ)アクリル酸フルフリル、(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸アダマンチル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ジエチルアミノエチル、(メタ)アクリル酸グリシジル、2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,3,3-テトラフルオロプロピル(メタ)アクリレート、α-ブロモアクリル酸、α-クロルアクリル酸、(メタ)アクリル酸ジシクロペンテニルオキシエチル、(メタ)アクリル酸ジシクロペンタニルオキシエチル、(メタ)アクリル酸イソボルニルオキシエチル、(メタ)アクリル酸シクロヘキシルオキシエチル、(メタ)アクリル酸アダマンチルオキシエチル、(メタ)アクリル酸ジシクロペンテニルオキシプロピルオキシエチル、(メタ)アクリル酸ジシクロペンタニルオキシプロピルオキシエチル、(メタ)アクリル酸ジシクロペンテニルオキシプロピルオキシエチル、(メタ)アクリル酸アダマンチルオキシプロピルオキシエチル、β-フリル(メタ)アクリル酸、β-スチリル(メタ)アクリル酸等の(メタ)アクリル酸エステル;スチレン;ビニルトルエン、α-メチルスチレン等のα-位又は芳香族環において置換されている重合可能なスチレン誘導体;ジアセトンアクリルアミド等のアクリルアミド;アクリロニトリル;ビニル-n-ブチルエーテル等のビニルアルコールのエーテル化合物;マレイン酸;マレイン酸無水物;マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル等のマレイン酸モノエステル;フマール酸、ケイ皮酸、α-シアノケイ皮酸、イタコン酸、クロトン酸、プロピオール酸等の不飽和カルボン酸誘導体;などが挙げられる。これらは単独で又は2種類以上を任意に組み合わせて用いることができる。
As the polymerizable monomer (monomer), (meth) acrylic acid; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl, (meth) acrylic acid benzyl derivative, ( (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dimethylaminoethyl, (meta) ) Diethylaminoethyl acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromoacrylic acid, α -Chloracrylic acid, (meth) acrylic acid dicyclopente Nyloxyethyl, (meth) acrylic acid dicyclopentanyloxyethyl, (meth) acrylic acid isobornyloxyethyl, (meth) acrylic acid cyclohexyloxyethyl, (meth) acrylic acid adamantyloxyethyl, (meth) acrylic acid Dicyclopentenyloxypropyloxyethyl, dicyclopentanyloxypropyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, adamantyloxypropyloxyethyl (meth) acrylate, β-furyl ( (Meth) acrylic acid esters such as (meth) acrylic acid and β-styryl (meth) acrylic acid; styrene; vinyl-toluene, α-methylstyrene and other polymerizable styrene derivatives substituted at the α-position or aromatic ring Diacetone Acrylamide such as chloramide; Acrylonitrile; Ether compound of vinyl alcohol such as vinyl-n-butyl ether; Maleic acid; Maleic anhydride; Maleic monoester such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; And an unsaturated carboxylic acid derivative such as cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These may be used alone or in any combination of two or more.
(A)成分は、(メタ)アクリル酸に由来する構造単位を有してもよい。(A)成分が、(メタ)アクリル酸に由来する構造単位を有するとき、その含有率は、解像度及び剥離性(エッチング後のレジスト剥離性)に優れる点では、(A)成分の全量を基準(100質量%、以下同様)として、10~60質量%、15~50質量%、又は、20~35質量%であってもよい。なお、本明細書において、「(A)成分の全量」は、そのうちの固形分の全量を意味する。また、後述する「(A)成分及び(B)成分の総量」も、同様である。なお、「固形分」とは、感光性樹脂組成物の水、溶媒等の揮発する物質を除いた不揮発分を指す。すなわち、乾燥工程で揮発せずに残る溶媒以外の成分を指し、25℃付近の室温で液状、水飴状及びワックス状のものも含む。
(A) The component may have a structural unit derived from (meth) acrylic acid. When the component (A) has a structural unit derived from (meth) acrylic acid, the content rate is based on the total amount of the component (A) in terms of excellent resolution and peelability (resist peelability after etching). (100 mass%, the same shall apply hereinafter) may be 10 to 60 mass%, 15 to 50 mass%, or 20 to 35 mass%. In the present specification, “total amount of component (A)” means the total amount of solid content. The same applies to “total amount of component (A) and component (B)” described later. The “solid content” refers to the non-volatile content of the photosensitive resin composition excluding volatile substances such as water and solvent. That is, it refers to components other than the solvent that remains without being volatilized in the drying step, and includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C.
また、(A)成分は、アルカリ現像性及び剥離性が一層向上する観点から、(メタ)アクリル酸アルキルエステルに由来する構造単位を有してもよい。
In addition, the component (A) may have a structural unit derived from an alkyl (meth) acrylate from the viewpoint of further improving alkali developability and peelability.
(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸と炭素数1~12のアルキルアルコールとのエステルであってもよい。このような(メタ)アクリル酸アルキルエステルとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル及び(メタ)アクリル酸2-エチルヘキシルが挙げられる。これらは単独で又は2種以上を任意に組み合わせて用いることができる。
The (meth) acrylic acid alkyl ester may be an ester of (meth) acrylic acid and an alkyl alcohol having 1 to 12 carbon atoms. Examples of such (meth) acrylic acid alkyl esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, Examples thereof include hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. These may be used alone or in any combination of two or more.
(A)成分が(メタ)アクリル酸アルキルエステルに由来する構造単位を有するとき、その含有率は、解像度及び密着性に優れる点では、(A)成分の全量を基準として、40~90質量%、50~85質量%、又は、65質量%~80質量%であってもよい。
When the component (A) has a structural unit derived from a (meth) acrylic acid alkyl ester, the content is 40 to 90% by mass based on the total amount of the component (A) in terms of excellent resolution and adhesion. , 50 to 85% by mass, or 65% to 80% by mass.
(A)成分の酸価は、現像性及び密着性に優れる点では、90~250mgKOH/g、100~240mgKOH/g、120~235mgKOH/g、又は、130mgKOH/g~230mgKOH/gであってもよい。
The acid value of the component (A) may be 90 to 250 mgKOH / g, 100 to 240 mgKOH / g, 120 to 235 mgKOH / g, or 130 mgKOH / g to 230 mgKOH / g in terms of excellent developability and adhesion. Good.
現像時間を短縮する点から、この酸価は、90mgKOH/g以上、100mgKOH/g以上、120mgKOH/g以上、又は、130mgKOH/g以上であってもよい。
From the viewpoint of shortening the developing time, the acid value may be 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g or more.
また、感光性樹脂組成物の光硬化物の密着性が一層向上する点で、この酸価は、250mgKOH/g以下、240mgKOH/g以下、235mgKOH/g以下、又は、230mgKOH/g以下であってもよい。なお、溶剤現像を行う場合は、(メタ)アクリル酸等のカルボキシ基を有する重合性単量体(モノマー)を少量に調整してもよい。
In addition, this acid value is 250 mgKOH / g or less, 240 mgKOH / g or less, 235 mgKOH / g or less, or 230 mgKOH / g or less in that the adhesiveness of the photocured product of the photosensitive resin composition is further improved. Also good. In addition, when performing solvent image development, you may adjust the polymerizable monomer (monomer) which has carboxy groups, such as (meth) acrylic acid, to a small quantity.
(A)成分の重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー(GPC)により測定(標準ポリスチレンを用いた検量線により換算)した場合、現像性及び密着性に優れる点では、10000~200000、20000~100000、25000~80000、又は、30000~60000であってもよい。現像性に優れる点では、200000以下、100000以下、80000以下、又は、60000以下であってもよい。密着性に優れる点では、10000以上、20000以上、25000以上、又は、30000以上であってもよい。
The weight average molecular weight (Mw) of the component (A) is 10,000 to 200,000 in terms of excellent developability and adhesion when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). 20,000 to 100,000, 25,000 to 80,000, or 30,000 to 60,000. In the point which is excellent in developability, it may be 200000 or less, 100000 or less, 80000 or less, or 60000 or less. In the point which is excellent in adhesiveness, it may be 10,000 or more, 20000 or more, 25000 or more, or 30000 or more.
(A)成分の分散度(重量平均分子量/数平均分子量)は、解像度、密着性に優れる点では、3.0以下、2.8以下、又は、2.5以下であってもよい。
The dispersity (weight average molecular weight / number average molecular weight) of the component (A) may be 3.0 or less, 2.8 or less, or 2.5 or less in terms of excellent resolution and adhesion.
(A)成分としては、1種類のバインダーポリマーを単独で使用してもよく、2種類以上のバインダーポリマーを任意に組み合わせて使用してもよい。
As the component (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination.
感光性樹脂組成物における(A)成分の含有量は、フィルム形成性、感度及び解像度に優れる点では、(A)成分及び(B)成分の総量100質量部中に30~70質量部、35~65質量部、又は、40~60質量部であってもよい。フィルム(感光層)の形成性の点から、この含有量は30質量部以上、35質量部以上、又は、40質量部以上であってもよい。また、感度及び解像度がバランスよく向上する点からは、この含有量は70質量部以下、65質量部以下、又は、60質量部以下であってもよい。
The content of the component (A) in the photosensitive resin composition is 30 to 70 parts by weight, 35 parts in 100 parts by weight of the total amount of the components (A) and (B) in terms of excellent film formability, sensitivity and resolution. It may be ~ 65 parts by mass or 40-60 parts by mass. In view of formability of the film (photosensitive layer), the content may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. Further, from the viewpoint of improving the sensitivity and resolution in a balanced manner, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.
(B)成分:光重合性化合物
感光性樹脂組成物は、(B)成分として分子内に6つのエチレン性不飽和結合を有する(メタ)アクリレート及びイソシアヌル環骨格を有する(メタ)アクリレートを含有する。 Component (B): Photopolymerizable compound The photosensitive resin composition contains (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton as the component (B). .
感光性樹脂組成物は、(B)成分として分子内に6つのエチレン性不飽和結合を有する(メタ)アクリレート及びイソシアヌル環骨格を有する(メタ)アクリレートを含有する。 Component (B): Photopolymerizable compound The photosensitive resin composition contains (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton as the component (B). .
分子内にエチレン性不飽和結合を6つ有する(メタ)アクリレートとしては、例えば、ジペンタエリスリトールヘキサ(メタ)アクリレートが挙げられる。これらは、EO基又はPO基を有してもよい。なお、分子内にエチレン性不飽和結合を6つ有する(メタ)アクリレートがEO基を有する場合、分子内のEO基の数は、密着性を向上させる観点から、6~30、6~24又は6~12であってもよい。分子内にエチレン性不飽和結合を6つ有する(メタ)アクリレートがPO基を有する場合、分子内のPO基の数は、密着性を向上させる観点から、6~30、6~24又は6~12であってもよい。
Examples of (meth) acrylate having six ethylenically unsaturated bonds in the molecule include dipentaerythritol hexa (meth) acrylate. These may have an EO group or a PO group. When the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule has an EO group, the number of EO groups in the molecule is 6 to 30, 6 to 24, or from the viewpoint of improving adhesion. It may be 6-12. When the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule has a PO group, the number of PO groups in the molecule is 6 to 30, 6 to 24, or 6 to 6 from the viewpoint of improving adhesion. 12 may be sufficient.
EO基を有するものとしては、KAYARAD DPHA(日本化薬株式会社、商品名、EO基の数:6)、KAYARAD DPEA-12(日本化薬株式会社、商品名、EO基の数:12)、A-DPH-6E(新中村化学工業株式会社、商品名、EO基の数:6)が商業的に入手可能である。また、PO基を有するものとしては、A-DPH-6P(新中村化学工業株式会社、商品名、PO基の数:6)が商業的に入手可能である。分子内にエチレン性不飽和結合を6つ有する(メタ)アクリレートは、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
As those having an EO group, KAYARAD DPHA (Nippon Kayaku Co., Ltd., trade name, number of EO groups: 6), KAYARAD DPEA-12 (Nippon Kayaku Co., Ltd., trade name, number of EO groups: 12), A-DPH-6E (Shin Nakamura Chemical Co., Ltd., trade name, number of EO groups: 6) is commercially available. In addition, A-DPH-6P (Shin-Nakamura Chemical Co., Ltd., trade name, number of PO groups: 6) is commercially available as having PO groups. One (meth) acrylate having six ethylenically unsaturated bonds in the molecule may be used alone, or two or more may be used in combination.
EO基又はPO基を有するジペンタエリスリトールヘキサ(メタ)アクリレートとして、より具体的には、例えば、下記一般式(1)で表される化合物が挙げられる。
More specifically, examples of the dipentaerythritol hexa (meth) acrylate having an EO group or a PO group include compounds represented by the following general formula (1).
一般式(1)中、Rは各々独立に、水素原子又はメチル基を示す。なお、複数存在するRは、互いに同一であっても異なっていてもよい。
In the general formula (1), each R independently represents a hydrogen atom or a methyl group. A plurality of R may be the same as or different from each other.
一般式(1)中、Aは炭素数2~6のアルキレン基、炭素数2~5のアルキレン基、又は、炭素数2~4のアルキレン基を示す。炭素数2~6のアルキレン基としては、例えば、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、ペンチレン基及びへキシレン基等が挙げられる。これらの中では、解像度、密着性、及びレジストすそ発生の抑制性を向上させる見地から、エチレン基又はイソプロピレン基であってもよく、エチレン基であってもよい。なお、複数存在するAは、互いに同一であっても異なっていてもよい。
In general formula (1), A represents an alkylene group having 2 to 6 carbon atoms, an alkylene group having 2 to 5 carbon atoms, or an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 6 carbon atoms include ethylene group, propylene group, isopropylene group, butylene group, pentylene group and hexylene group. Among these, an ethylene group or an isopropylene group or an ethylene group may be used from the viewpoint of improving the resolution, adhesion, and resist bottom generation suppression. A plurality of A's may be the same or different.
一般式(1)中、nは各々独立に、0~20の整数である。解像度を更に向上させる見地から、nは、1~20、1~7、1~5、1~4又は1~2であってもよい。一般式(1)中の6つのnの合計は、6~30、6~24又は6~12であってもよい。
In the general formula (1), each n is independently an integer of 0 to 20. From the viewpoint of further improving the resolution, n may be 1 to 20, 1 to 7, 1 to 5, 1 to 4, or 1 to 2. The sum of the six ns in the general formula (1) may be 6-30, 6-24, or 6-12.
感光性樹脂組成物における、分子内にエチレン性不飽和結合を6つ有する(メタ)アクリレートの含有量は、エッチング後の密着性と剥離性とをバランスよく向上させる観点から、(A)成分及び(B)成分の総量100質量部中に、3~20質量部、3~15質量部又は3~10質量部であってもよい。
In the photosensitive resin composition, the content of the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule is from the viewpoint of improving the adhesion and releasability after etching in a balanced manner. The total amount of the component (B) may be 3 to 20 parts by mass, 3 to 15 parts by mass, or 3 to 10 parts by mass.
イソシアヌル環骨格を有する(メタ)アクリレートとしては、レジストパターンの耐酸性及び可とう性を向上させる観点で、下記一般式(2)で表される化合物を含んでもよい。イソシアヌル環骨格を有する(メタ)アクリレートは、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
The (meth) acrylate having an isocyanuric ring skeleton may contain a compound represented by the following general formula (2) from the viewpoint of improving the acid resistance and flexibility of the resist pattern. The (meth) acrylate having an isocyanuric ring skeleton may be used alone or in combination of two or more.
一般式(2)中、R21、R22及びR23は、各々独立に炭素数1~20のアルキレン基を示し、R24、R25及びR26は、各々独立に水素原子又はメチル基を示し、X21、X22及びX23は、各々独立に、EO基及びPO基からなる群より選ばれる少なくとも1種を含む(ポリ)オキシアルキレン基(オキシアルキレン基又はポリオキシアルキレン基)を示し、X21、X22及びX23に含まれるEO基及びPO基の総数(分子内の総数)が0~120である。EO基及びPO基の双方が存在する場合、EO基及びPO基は、ランダムに存在してもよく、ブロックを形成してもよい。
In the general formula (2), R 21 , R 22 and R 23 each independently represents an alkylene group having 1 to 20 carbon atoms, and R 24 , R 25 and R 26 each independently represents a hydrogen atom or a methyl group. X 21 , X 22 and X 23 each independently represent a (poly) oxyalkylene group (oxyalkylene group or polyoxyalkylene group) containing at least one selected from the group consisting of an EO group and a PO group. , X 21 , X 22 and X 23 have a total number of EO groups and PO groups (total number in the molecule) of 0 to 120. When both the EO group and the PO group are present, the EO group and the PO group may be present at random and may form a block.
X21、X22及びX23に含まれるEO基及びPO基の総数は、可とう性及び耐酸性の観点から、3~60、3~30、3~20、又は、3~15であってもよい。
The total number of EO groups and PO groups contained in X 21 , X 22 and X 23 is 3 to 60, 3 to 30, 3 to 20, or 3 to 15 from the viewpoint of flexibility and acid resistance. Also good.
また、上記一般式(2)で表される化合物の中で、商業的に入手可能なものとして、UA-21(新中村化学工業社製、商品名)、UA-7100(新中村化学工業社製、商品名)等が挙げられる。
Among the compounds represented by the general formula (2), commercially available compounds include UA-21 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name), UA-7100 (Shin-Nakamura Chemical Co., Ltd.). Product name).
イソシアヌル環骨格を有する(メタ)アクリレートの含有量は、レジストパターンの耐酸性及び可とう性をバランスよく向上させる観点で、(A)成分及び(B)成分の総量100質量部中に、1~50質量部であってもよい。また、更に耐酸性及び可とう性を向上させる観点で、その下限値は、3質量部以上、又は、5質量部以上であってもよい。また、同様の観点で、その下限値は、40質量部以下、30質量部以下、20質量部以下、又は、16質量部以下であってもよい。
The content of the (meth) acrylate having an isocyanuric ring skeleton is 1 to 100 parts by mass in the total amount of the component (A) and the component (B) from the viewpoint of improving the acid resistance and flexibility of the resist pattern in a balanced manner. It may be 50 parts by mass. Further, from the viewpoint of further improving acid resistance and flexibility, the lower limit may be 3 parts by mass or more, or 5 parts by mass or more. Further, from the same viewpoint, the lower limit may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 16 parts by mass or less.
(B)成分は、分子内に6つのエチレン性不飽和結合を有する(メタ)アクリレート及びイソシアヌル環骨格を有する(メタ)アクリレート以外のその他の光重合性化合物を更に含有してもよい。その他の光重合性化合物は、光重合が可能な化合物であれば特に制限はない。その他の光重合性化合物は、ラジカル重合性化合物、又は、エチレン性不飽和結合を有する化合物であってもよい。エチレン性不飽和結合を有する化合物としては、分子内にエチレン性不飽和結合を1つ有する化合物((メタ)アクリレート)、分子内にエチレン性不飽和結合を2つ有する化合物((メタ)アクリレート)、分子内にエチレン性不飽和結合を3つ以上有する化合物((メタ)アクリレート)等が挙げられる。その他の光重合性化合物は、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
The component (B) may further contain a photopolymerizable compound other than (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton. Other photopolymerizable compounds are not particularly limited as long as they are compounds capable of photopolymerization. The other photopolymerizable compound may be a radical polymerizable compound or a compound having an ethylenically unsaturated bond. As the compound having an ethylenically unsaturated bond, a compound having one ethylenically unsaturated bond in the molecule ((meth) acrylate), a compound having two ethylenically unsaturated bonds in the molecule ((meth) acrylate) And compounds having three or more ethylenically unsaturated bonds ((meth) acrylate) in the molecule. Another photopolymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more type.
(B)成分は、分子内にエチレン性不飽和結合を2つ有する化合物を更に含有してもよい。
(B) The component may further contain a compound having two ethylenically unsaturated bonds in the molecule.
分子内にエチレン性不飽和結合を2つ有する化合物としては、例えば、ビスフェノールA型ジ(メタ)アクリレート、水添ビスフェノールA型ジ(メタ)アクリレート、分子内にウレタン結合を有するジ(メタ)アクリレート、分子内に(ポリ)オキシエチレン基及び(ポリ)オキシプロピレン基の双方を有するポリアルキレングリコールジ(メタ)アクリレート、及びトリメチロールプロパンジ(メタ)アクリレートが挙げられる。
Examples of the compound having two ethylenically unsaturated bonds in the molecule include bisphenol A type di (meth) acrylate, hydrogenated bisphenol A type di (meth) acrylate, and di (meth) acrylate having a urethane bond in the molecule. And polyalkylene glycol di (meth) acrylate having both (poly) oxyethylene group and (poly) oxypropylene group in the molecule, and trimethylolpropane di (meth) acrylate.
(B)成分は、耐酸性を一層向上させる観点から、ビスフェノールA型ジ(メタ)アクリレートを含んでもよい。
The component (B) may contain bisphenol A type di (meth) acrylate from the viewpoint of further improving acid resistance.
ビスフェノールA型ジ(メタ)アクリレートとしては、下記一般式(3)で表される化合物が挙げられる。
Examples of the bisphenol A type di (meth) acrylate include compounds represented by the following general formula (3).
一般式(3)中、R1及びR2はそれぞれ独立に、水素原子又はメチル基を示す。XO及びYOはそれぞれ独立に、オキシエチレン基又はオキシプロピレン基を示す。m1、m2、n1及びn2はそれぞれ独立に0~40を示す。ただし、m1+n1及びm2+n2はいずれも1以上である。XOがオキシエチレン基、YOがオキシプロピレン基である場合、m1+m2は1~40であり、n1+n2は0~20である。XOがオキシプロピレン基、YOがオキシエチレン基の場合、m1+m2は0~20であり、n1+n2は1~40である。m1、m2、n1及びn2は構造単位の構造単位数を示す。したがって単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。以下、構造単位の構造単位数については同様である。
In General Formula (3), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an oxyethylene group or an oxypropylene group. m 1 , m 2 , n 1 and n 2 each independently represents 0 to 40. However, m 1 + n 1 and m 2 + n 2 are both 1 or more. When XO is an oxyethylene group and YO is an oxypropylene group, m 1 + m 2 is 1 to 40, and n 1 + n 2 is 0 to 20. When XO is an oxypropylene group and YO is an oxyethylene group, m 1 + m 2 is 0 to 20, and n 1 + n 2 is 1 to 40. m 1 , m 2 , n 1 and n 2 represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units.
耐酸性に優れる点では、一般式(3)中、XOがオキシエチレン基、YOがオキシプロピレン基である場合、m1+m2は8~40、8~20、又は、8~10であってもよく、XOがオキシプロピレン基、YOがオキシエチレン基である場合、n1+n2は8~40、8~20、又は、8~10であってもよい。
In terms of excellent acid resistance, in the general formula (3), when XO is an oxyethylene group and YO is an oxypropylene group, m 1 + m 2 is 8 to 40, 8 to 20, or 8 to 10; In addition, when XO is an oxypropylene group and YO is an oxyethylene group, n 1 + n 2 may be 8 to 40, 8 to 20, or 8 to 10.
感光性樹脂組成物が(B)成分としてビスフェノールA型ジ(メタ)アクリレートを含む場合、その含有量としては、エッチング後の密着性を向上する観点から、(A)成分及び(B)成分の総量100質量部中に、1~50質量部、又は、5~50質量部であってもよい。
When the photosensitive resin composition contains bisphenol A type di (meth) acrylate as the component (B), the content thereof is that of the components (A) and (B) from the viewpoint of improving the adhesion after etching. The total amount may be 1 to 50 parts by mass, or 5 to 50 parts by mass in 100 parts by mass.
感光性樹脂組成物における(B)成分全体の含有量は、(A)成分及び(B)成分の総量100質量部に対して30~70質量部、35~65質量部、40~60質量部、又は、35~55質量部であってもよい。この含有量が30質量部以上であると、感度及び解像度がバランスよく向上する傾向がある。70質量部以下であると、フィルム(感光層)を形成し易くなる傾向があり、また良好なレジストパターン形状が得られ易くなる傾向がある。
The total content of component (B) in the photosensitive resin composition is 30 to 70 parts by weight, 35 to 65 parts by weight, 40 to 60 parts by weight with respect to 100 parts by weight as the total of component (A) and component (B). Or 35 to 55 parts by mass. When this content is 30 parts by mass or more, the sensitivity and resolution tend to be improved in a balanced manner. When the amount is 70 parts by mass or less, a film (photosensitive layer) tends to be easily formed, and a good resist pattern shape tends to be easily obtained.
(C)成分:光重合開始剤
感光性樹脂組成物は、(C)成分として光重合開始剤を少なくとも1種含有する。光重合開始剤は、(B)成分を重合させることができるものであれば特に制限はなく、通常用いられる光重合開始剤から適宜選択することができる。 Component (C): Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). The photopolymerization initiator is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators.
感光性樹脂組成物は、(C)成分として光重合開始剤を少なくとも1種含有する。光重合開始剤は、(B)成分を重合させることができるものであれば特に制限はなく、通常用いられる光重合開始剤から適宜選択することができる。 Component (C): Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). The photopolymerization initiator is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators.
(C)成分としては、ベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-プロパノン-1等の芳香族ケトン;アルキルアントラキノン等のキノン類;ベンゾインアルキルエーテル等のベンゾインエーテル化合物;ベンゾイン、アルキルベンゾイン等のベンゾイン化合物;ベンジルジメチルケタール等のベンジル誘導体;2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体等の2,4,5-トリアリールイミダゾール二量体;9-フェニルアクリジン、1,7-(9,9’-アクリジニル)ヘプタン等のアクリジン誘導体などが挙げられる。これらは単独で又は2種類以上を組み合わせて用いることができる。
Examples of the component (C) include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as propanone-1; quinones such as alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl)- 2,4,5-triarylimidazole dimers such as 4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, 1, Induction of acridine such as 7- (9,9'-acridinyl) heptane And the like. These can be used alone or in combination of two or more.
(C)成分は、感度及び密着性を一層向上させる観点から、2,4,5-トリアリールイミダゾール二量体の少なくとも1種を含んでいてもよく、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体を含んでもよい。2,4,5-トリアリールイミダゾール二量体は、その構造が対称であっても非対称であってもよい。
Component (C) may contain at least one 2,4,5-triarylimidazole dimer from the viewpoint of further improving sensitivity and adhesion, and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer may be included. The 2,4,5-triarylimidazole dimer may be symmetric or asymmetric in structure.
感光性樹脂組成物における(C)成分の含有量は、(A)成分及び(B)成分の総量100質量部に対して0.1~10質量部、1~7質量部、2~6質量部、又は、3~5質量部であってもよい。この含有量が0.1質量部以上であると良好な感度、解像度又は密着性が得られ易くなる傾向があり、10質量部以下であると良好なレジストパターン形状を得られ易くなる傾向がある。
The content of the component (C) in the photosensitive resin composition is 0.1 to 10 parts by weight, 1 to 7 parts by weight, and 2 to 6 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). Or 3 to 5 parts by mass. When this content is 0.1 parts by mass or more, good sensitivity, resolution or adhesion tends to be obtained, and when it is 10 parts by mass or less, a good resist pattern shape tends to be obtained. .
(D):シランカップリング剤
感光性樹脂組成物は、(D)成分としてシランカップリング剤を更に含有していてもよい。シランカップリング剤としては、(D1)成分:メルカプトアルキル基を有するシラン化合物、(D2)成分:アミノ基を有するシラン化合物(好ましくは、ウレイド基を有するシラン化合物)、(D3)成分:(メタ)アクリロキシ基を有するシラン化合物が挙げられる。 (D): Silane coupling agent The photosensitive resin composition may further contain a silane coupling agent as the component (D). As the silane coupling agent, (D1) component: a silane compound having a mercaptoalkyl group, (D2) component: a silane compound having an amino group (preferably a silane compound having a ureido group), (D3) component: (meta And silane compounds having an acryloxy group.
感光性樹脂組成物は、(D)成分としてシランカップリング剤を更に含有していてもよい。シランカップリング剤としては、(D1)成分:メルカプトアルキル基を有するシラン化合物、(D2)成分:アミノ基を有するシラン化合物(好ましくは、ウレイド基を有するシラン化合物)、(D3)成分:(メタ)アクリロキシ基を有するシラン化合物が挙げられる。 (D): Silane coupling agent The photosensitive resin composition may further contain a silane coupling agent as the component (D). As the silane coupling agent, (D1) component: a silane compound having a mercaptoalkyl group, (D2) component: a silane compound having an amino group (preferably a silane compound having a ureido group), (D3) component: (meta And silane compounds having an acryloxy group.
感光性樹脂組成物は、(D)成分として(D1)成分を含有する場合、平滑性の高い基材に対する密着性に優れ、且つ塩酸によるITOエッチングによっても剥がれ等が生じ難い優れた耐酸性を有するレジストパターンを形成できるという、優れた効果を奏することができる。
When the photosensitive resin composition contains the component (D1) as the component (D), the photosensitive resin composition has excellent adhesion to a substrate having high smoothness, and has excellent acid resistance that hardly peels off even by ITO etching with hydrochloric acid. The outstanding effect that the resist pattern which it has can be formed can be show | played.
また、感光性樹脂組成物は、(D)成分として、(D1)成分以外のシランカップリング剤を含有していてもよい。
Moreover, the photosensitive resin composition may contain a silane coupling agent other than the component (D1) as the component (D).
例えば、感光性樹脂組成物は、(D)成分として、(D1)成分と(D3)成分とを併用することができる。感光性樹脂組成物が(D)成分として(D1)成分のみを含む場合、優れた密着性を示すレジストパターンが得られる一方、銅基板等に対する現像残りが発生しやすい(すなわち、銅基板上に形成したレジストパターンが、エッチング後に剥離しにくい)傾向にあり、エッチング時間が増加する傾向にある。これに対して、感光性樹脂組成物が(D)成分として(D1)成分及び(D3)成分を含有する場合、優れた密着性を維持しつつ、銅基板等に対する現像残りの発生を抑制して、エッチング時間の短縮を図ることができる。
For example, in the photosensitive resin composition, the component (D1) and the component (D3) can be used in combination as the component (D). When the photosensitive resin composition contains only the component (D1) as the component (D), a resist pattern exhibiting excellent adhesion can be obtained, while development residue on a copper substrate or the like is likely to occur (that is, on the copper substrate). The formed resist pattern tends to be difficult to peel off after etching, and the etching time tends to increase. On the other hand, when the photosensitive resin composition contains the component (D1) and the component (D3) as the component (D), it suppresses the generation of development residue on the copper substrate while maintaining excellent adhesion. Thus, the etching time can be shortened.
また、感光性樹脂組成物は、(D)成分として、(D1)成分、(D2)成分及び(D3)成分を全て含有していてもよい。このような感光性樹脂組成物によれば、銅基板等に対する現像残りの発生を抑制しつつ、より高い密着性を実現できる。
Moreover, the photosensitive resin composition may contain all the (D1) component, (D2) component, and (D3) component as (D) component. According to such a photosensitive resin composition, higher adhesion can be realized while suppressing the occurrence of development residue on a copper substrate or the like.
(D1)成分としては、メルカプトアルキル基及びアルコキシ基を有するシラン化合物(メルカプトアルキルアルコキシシラン)であってもよく、このような(D1)成分としては、メルカプトプロピルメチルジメトキシシラン、メルカプトプロピルトリメトキシシラン、メルカプトプロピルトリエトキシシラン等が挙げられる。これらの中でも、加水分解が起こりやすく、且つ3点での架橋が可能なメルカプトプロピルトリメトキシシランが最も密着性の発現に対して好ましい。これらは単独で又は2種類以上を組み合わせて用いることができる。
The component (D1) may be a silane compound having a mercaptoalkyl group and an alkoxy group (mercaptoalkylalkoxysilane). Examples of the component (D1) include mercaptopropylmethyldimethoxysilane and mercaptopropyltrimethoxysilane. And mercaptopropyltriethoxysilane. Among these, mercaptopropyltrimethoxysilane which is easily hydrolyzed and can be crosslinked at three points is most preferable for the expression of adhesion. These can be used alone or in combination of two or more.
(D2)成分としては、末端に1級アミノ基を有するシラン化合物であってもよく、このような(D2)成分としては、例えば、3-アミノプロピルメトキシシラン、アミノプロピルエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-ウレイドプロピルトリメトキシシラン、ウレイドメチルトリメトキシシラン、ウレイドメチルトリエトキシシラン、2-ウレイドエチルトリメトキシシラン、2-ウレイドエチルトリエトキシシラン、4-ウレイドブチルトリメトキシシラン、4-ウレイドブチルトリエトキシシラン等が挙げられる。これらの中でも、バインダーポリマーとの反応性を考慮して、ウレイド基等のカルボン酸基との反応性が低い官能基を有するシラン化合物であってもよく、(D1)成分と併用した際に現像残りの抑制効果が特に顕著に見られる3-ウレイドプロピルトリエトキシシランが最も好ましい。これらは単独で又は2種類以上を組み合わせて用いることができる。
The component (D2) may be a silane compound having a primary amino group at the terminal. Examples of the component (D2) include 3-aminopropylmethoxysilane, aminopropylethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, Examples include 2-ureidoethyltriethoxysilane, 4-ureidobutyltrimethoxysilane, and 4-ureidobutyltriethoxysilane. Among these, considering the reactivity with the binder polymer, it may be a silane compound having a functional group having a low reactivity with a carboxylic acid group such as a ureido group, and developed when used in combination with the component (D1). Most preferred is 3-ureidopropyltriethoxysilane, in which the remaining inhibitory effect is particularly noticeable. These can be used alone or in combination of two or more.
(D3)成分としては、例えば、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシランが挙げられる。これらの中でも、加水分解を起こしやすく、且つ3点での架橋が可能な3-メタクリロキシプロピルトリメトキシシランが最も密着性の発現に対して好ましい。これらは単独で又は2種類以上を組み合わせて用いることができる。
Examples of the component (D3) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Among these, 3-methacryloxypropyltrimethoxysilane which is easily hydrolyzed and can be crosslinked at three points is most preferable for the expression of adhesion. These can be used alone or in combination of two or more.
感光性樹脂組成物における(D)成分の含有量は、密着性に優れる点では、(A)成分及び(B)成分の総量100質量部に対して、0.01~10質量部、0.05~5質量部、又は、0.1~3質量部であってもよい。(D)成分の含有量が上記範囲より多いと、銅基板等に対する現像残りが発生し易くなる傾向があり、また、解像性の低下・感度の大幅な上昇によるレジスト底部の硬化不足等が生じるおそれがある。これに対して、(D)成分の含有量が上記範囲内であると、銅基板等に対する現像残りを充分に抑制しつつ、レジスト底部での硬化性を向上する傾向がある。レジスト底部まで充分に硬化することで、良好なレジストパターン形状が得られるとともに、エッチング液への耐性が一層良好になる。
The content of the component (D) in the photosensitive resin composition is 0.01 to 10 parts by mass, 0. 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent adhesion. It may be 05 to 5 parts by mass, or 0.1 to 3 parts by mass. If the content of the component (D) is more than the above range, there is a tendency that development residue on a copper substrate or the like is likely to occur, and there is insufficient curing of the resist bottom due to a decrease in resolution and a significant increase in sensitivity. May occur. On the other hand, when the content of the component (D) is within the above range, the curability at the bottom of the resist tends to be improved while sufficiently suppressing the development residue on the copper substrate or the like. By sufficiently curing to the bottom of the resist, a good resist pattern shape can be obtained and the resistance to the etching solution can be further improved.
(その他の成分)
感光性樹脂組成物は、必要に応じて上記(A)~(D)成分以外の成分を含有していてもよい。例えば、感光性樹脂組成物は、増感色素、ビス[4-(ジメチルアミノ)フェニル]メタン、ビス[4-(ジエチルアミノ)フェニル]メタン及びロイコクリスタルバイオレットからなる群より選択される少なくとも1種を含有することができる。 (Other ingredients)
The photosensitive resin composition may contain components other than the components (A) to (D) as necessary. For example, the photosensitive resin composition comprises at least one selected from the group consisting of a sensitizing dye, bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. Can be contained.
感光性樹脂組成物は、必要に応じて上記(A)~(D)成分以外の成分を含有していてもよい。例えば、感光性樹脂組成物は、増感色素、ビス[4-(ジメチルアミノ)フェニル]メタン、ビス[4-(ジエチルアミノ)フェニル]メタン及びロイコクリスタルバイオレットからなる群より選択される少なくとも1種を含有することができる。 (Other ingredients)
The photosensitive resin composition may contain components other than the components (A) to (D) as necessary. For example, the photosensitive resin composition comprises at least one selected from the group consisting of a sensitizing dye, bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. Can be contained.
(E)成分:増感色素
本実施形態にかかる感光性樹脂組成物は、(E)成分として、増感色素を更に含有してもよい。増感色素としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物、及びアミノアクリジン化合物が挙げられる。これらは単独で、又は2種以上を組み合わせて用いることができる。レジスト底部の硬化度を更に向上し、密着性に優れるという観点で、ピラゾリン化合物を含有してもよい。 (E) component: Sensitizing dye The photosensitive resin composition concerning this embodiment may further contain a sensitizing dye as (E) component. Examples of sensitizing dyes include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds. , A thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound. These can be used alone or in combination of two or more. A pyrazoline compound may be contained from the viewpoint of further improving the degree of curing of the resist bottom and excellent adhesion.
本実施形態にかかる感光性樹脂組成物は、(E)成分として、増感色素を更に含有してもよい。増感色素としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物、及びアミノアクリジン化合物が挙げられる。これらは単独で、又は2種以上を組み合わせて用いることができる。レジスト底部の硬化度を更に向上し、密着性に優れるという観点で、ピラゾリン化合物を含有してもよい。 (E) component: Sensitizing dye The photosensitive resin composition concerning this embodiment may further contain a sensitizing dye as (E) component. Examples of sensitizing dyes include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds. , A thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound. These can be used alone or in combination of two or more. A pyrazoline compound may be contained from the viewpoint of further improving the degree of curing of the resist bottom and excellent adhesion.
感光性樹脂組成物が(E)成分を含有する場合、その含有量は、レジスト底部の硬化度を向上させ、更に密着性を向上させる観点では、(A)成分及び(B)成分の総量100質量部に対して、0.01~5質量部、0.01~1質量部、又は、0.01~0.2質量部であってもよい。
When the photosensitive resin composition contains the component (E), the content improves the degree of cure at the bottom of the resist, and further improves the adhesion, so that the total amount of the component (A) and the component (B) is 100. It may be 0.01 to 5 parts by mass, 0.01 to 1 part by mass, or 0.01 to 0.2 parts by mass with respect to parts by mass.
また、感光性樹脂組成物は、分子内に少なくとも1つのカチオン重合可能な環状エーテル基を有する重合性化合物(オキセタン化合物等);カチオン重合開始剤;マラカイトグリーン、ビクトリアピュアブルー、ブリリアントグリーン、メチルバイオレット等の染料;トリブロモフェニルスルホン、ジフェニルアミン、ベンジルアミン、トリフェニルアミン、ジエチルアニリン、o-クロロアニリン等の光発色剤;熱発色防止剤;p-トルエンスルホンアミド等の可塑剤;顔料;充填剤;消泡剤;難燃剤;安定剤;密着性付与剤;レベリング剤;剥離促進剤;酸化防止剤;香料;イメージング剤;熱架橋剤;などを含有してもよい。これらは、単独で又は2種類以上を組み合わせて使用することができる。
The photosensitive resin composition includes a polymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule (such as an oxetane compound); a cationic polymerization initiator; malachite green, Victoria pure blue, brilliant green, methyl violet. Dyes such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, etc .; thermochromic inhibitors; plasticizers such as p-toluenesulfonamide; pigments; fillers An antifoaming agent, a flame retardant, a stabilizer, an adhesion-imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, and the like. These can be used alone or in combination of two or more.
感光性樹脂組成物がその他の成分((A)~(D)成分以外の成分)を含む場合、これらの含有量は、(A)成分及び(B)成分の総量100質量部に対して、それぞれ0.01質量部~20質量部程度であってもよい。
When the photosensitive resin composition contains other components (components other than the components (A) to (D)), these contents are based on 100 parts by mass of the total amount of the components (A) and (B). Each may be about 0.01 to 20 parts by mass.
[感光性樹脂組成物の溶液]
感光性樹脂組成物は、有機溶剤の少なくとも1種を更に含む液状組成物であってもよい。有機溶剤としては、メタノール、エタノール等のアルコール溶剤;アセトン、メチルエチルケトン等のケトン溶剤;メチルセロソルブ、エチルセロソルブ、プロピレングリコールモノメチルエーテル等のグリコールエーテル溶剤;トルエン等の芳香族炭化水素溶剤;N,N-ジメチルホルムアミド等の非プロトン性極性溶剤などが挙げられる。これらは単独でも、2種以上を混合して用いてもよい。 [Solution of photosensitive resin composition]
The photosensitive resin composition may be a liquid composition further containing at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. These may be used alone or in admixture of two or more.
感光性樹脂組成物は、有機溶剤の少なくとも1種を更に含む液状組成物であってもよい。有機溶剤としては、メタノール、エタノール等のアルコール溶剤;アセトン、メチルエチルケトン等のケトン溶剤;メチルセロソルブ、エチルセロソルブ、プロピレングリコールモノメチルエーテル等のグリコールエーテル溶剤;トルエン等の芳香族炭化水素溶剤;N,N-ジメチルホルムアミド等の非プロトン性極性溶剤などが挙げられる。これらは単独でも、2種以上を混合して用いてもよい。 [Solution of photosensitive resin composition]
The photosensitive resin composition may be a liquid composition further containing at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. These may be used alone or in admixture of two or more.
感光性樹脂組成物に含まれる有機溶剤の含有量は、目的等に応じて適宜選択することができる。例えば、感光性樹脂組成物は、固形分が30質量%~60質量%程度となる液状組成物(以下、有機溶剤を含む感光性樹脂組成物を「塗布液」ともいう。)として用いることができる。
The content of the organic solvent contained in the photosensitive resin composition can be appropriately selected depending on the purpose and the like. For example, the photosensitive resin composition is used as a liquid composition having a solid content of about 30% by mass to 60% by mass (hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”). it can.
塗布液を、後述する支持体、金属板等の表面上に塗布し、乾燥させることにより、感光性樹脂組成物の塗膜である感光層を形成することができる。金属板としては特に制限されず目的等に応じて適宜選択できる。金属板としては、銅、銅系合金、ニッケル、クロム、鉄、ステンレス等の鉄系合金などの金属からなる金属板を挙げることができる。好ましい金属板としては、銅、銅系合金、鉄系合金等の金属からなる金属板が挙げられる。
The photosensitive layer which is a coating film of the photosensitive resin composition can be formed by applying the coating liquid on the surface of a support, a metal plate, etc., which will be described later, and drying it. It does not restrict | limit especially as a metal plate, According to the objective etc., it can select suitably. As a metal plate, the metal plate which consists of metals, such as copper, copper-type alloy, iron-type alloys, such as nickel, chromium, iron, stainless steel, can be mentioned. As a preferable metal plate, a metal plate made of a metal such as copper, a copper-based alloy, or an iron-based alloy can be given.
形成される感光層の厚みは特に制限されず、その用途に応じて適宜選択できる。感光層の厚み(乾燥後の厚み)は、1~100μm程度であってもよい。
The thickness of the photosensitive layer to be formed is not particularly limited and can be appropriately selected depending on the application. The thickness of the photosensitive layer (thickness after drying) may be about 1 to 100 μm.
金属板上に感光層を形成した場合、感光層の金属板とは反対側の表面を、保護層で被覆してもよい。保護層としては、ポリエチレン、ポリプロピレン等の重合体フィルムなどが挙げられる。
When a photosensitive layer is formed on a metal plate, the surface of the photosensitive layer opposite to the metal plate may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.
<感光性エレメント>
本実施形態に係る感光性エレメント(以下、単に「感光性エレメント」という。)は、支持体と、該支持体の一面上に設けられた、上記感光性樹脂組成物を用いて形成された感光層と、を備える。このような感光性エレメントによれば、上記感光性樹脂組成物を用いて形成された感光層を備えるため、レジストパターンに発生し得る欠け及びクラックが少なく、強いエッチング液を用いた場合であっても、レジストの剥がれ及び欠けが発生することを抑制でき、且つ、ガタツキのない良好なライン形状を有する配線パターンを得ることができるとともに、剥離時間が充分に短いレジストパターンを形成することができる。また、平滑性の高い基板に対しても充分な密着性を有し、且つ優れた耐酸性を有するレジストパターンを効率的に形成することができる。感光性エレメントは、必要に応じて保護層等のその他の層を有していてもよい。 <Photosensitive element>
A photosensitive element according to the present embodiment (hereinafter simply referred to as “photosensitive element”) is a photosensitive body formed using a support and the photosensitive resin composition provided on one surface of the support. A layer. According to such a photosensitive element, since it includes a photosensitive layer formed using the photosensitive resin composition, there are few chips and cracks that can occur in the resist pattern, and a strong etching solution is used. However, it is possible to suppress the occurrence of resist peeling and chipping, and to obtain a wiring pattern having a good line shape without backlash, and to form a resist pattern having a sufficiently short peeling time. In addition, it is possible to efficiently form a resist pattern having sufficient adhesion to a highly smooth substrate and having excellent acid resistance. The photosensitive element may have other layers, such as a protective layer, as needed.
本実施形態に係る感光性エレメント(以下、単に「感光性エレメント」という。)は、支持体と、該支持体の一面上に設けられた、上記感光性樹脂組成物を用いて形成された感光層と、を備える。このような感光性エレメントによれば、上記感光性樹脂組成物を用いて形成された感光層を備えるため、レジストパターンに発生し得る欠け及びクラックが少なく、強いエッチング液を用いた場合であっても、レジストの剥がれ及び欠けが発生することを抑制でき、且つ、ガタツキのない良好なライン形状を有する配線パターンを得ることができるとともに、剥離時間が充分に短いレジストパターンを形成することができる。また、平滑性の高い基板に対しても充分な密着性を有し、且つ優れた耐酸性を有するレジストパターンを効率的に形成することができる。感光性エレメントは、必要に応じて保護層等のその他の層を有していてもよい。 <Photosensitive element>
A photosensitive element according to the present embodiment (hereinafter simply referred to as “photosensitive element”) is a photosensitive body formed using a support and the photosensitive resin composition provided on one surface of the support. A layer. According to such a photosensitive element, since it includes a photosensitive layer formed using the photosensitive resin composition, there are few chips and cracks that can occur in the resist pattern, and a strong etching solution is used. However, it is possible to suppress the occurrence of resist peeling and chipping, and to obtain a wiring pattern having a good line shape without backlash, and to form a resist pattern having a sufficiently short peeling time. In addition, it is possible to efficiently form a resist pattern having sufficient adhesion to a highly smooth substrate and having excellent acid resistance. The photosensitive element may have other layers, such as a protective layer, as needed.
図1は、本発明の感光性エレメントの一実施形態を示す模式断面図である。図1に示す感光性エレメント10では、支持体2、感光性樹脂組成物を用いて形成された感光層4及び保護層6がこの順に積層されている。感光層4は、感光性樹脂組成物の塗膜ということもできる。なお塗膜は、感光性樹脂組成物が未硬化状態のものである。
FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present invention. In the photosensitive element 10 shown in FIG. 1, the support 2, the photosensitive layer 4 formed using the photosensitive resin composition, and the protective layer 6 are laminated in this order. The photosensitive layer 4 can also be referred to as a coating film of a photosensitive resin composition. The coating film is one in which the photosensitive resin composition is in an uncured state.
感光性エレメント10は、例えば、以下のようにして得ることができる。まず、支持体2上に、有機溶剤を含む感光性樹脂組成物である塗布液を塗布して塗布層を形成し、これを乾燥(塗布層から有機溶剤の少なくとも一部を除去)することで感光層4を形成する。次いで、感光層4の支持体2とは反対側の面を保護層6で被覆することにより、支持体2と、該支持体2上に積層された感光層4と、該感光層4上に積層された保護層6とを備える、感光性エレメント10が得られる。なお、感光性エレメント10は、保護層6を必ずしも備えなくてもよい。
The photosensitive element 10 can be obtained as follows, for example. First, on the support 2, a coating solution that is a photosensitive resin composition containing an organic solvent is applied to form a coating layer, which is dried (at least a part of the organic solvent is removed from the coating layer). A photosensitive layer 4 is formed. Next, the surface of the photosensitive layer 4 opposite to the support 2 is covered with a protective layer 6, so that the support 2, the photosensitive layer 4 laminated on the support 2, and the photosensitive layer 4 are covered. The photosensitive element 10 provided with the protective layer 6 laminated | stacked is obtained. Note that the photosensitive element 10 does not necessarily include the protective layer 6.
支持体2としては、ポリエチレンテレフタレート等のポリエステル;ポリプロピレン、ポリエチレン等のポリオレフィンなどの、耐熱性及び耐溶剤性を有する重合体からなるフィルムを用いることができる。
As the support 2, a film made of a polymer having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate; polyolefin such as polypropylene and polyethylene can be used.
支持体2の厚みは、1~100μm、5~50μm、又は、5~30μmであってもよい。支持体2の厚みが1μm以上であることで、支持体2を剥離する際に支持体2が破れることを抑制できる。また、100μm以下であることで、支持体2を通して露光した場合の解像度の低下が抑制される。
The thickness of the support 2 may be 1 to 100 μm, 5 to 50 μm, or 5 to 30 μm. When the thickness of the support body 2 is 1 μm or more, the support body 2 can be prevented from being broken when the support body 2 is peeled off. Moreover, the fall of the resolution at the time of exposing through the support body 2 is suppressed because it is 100 micrometers or less.
保護層6としては、感光層4に対する接着力が、支持体2の感光層4に対する接着力よりも小さいものであってもよい。具体的に、保護層6としては、ポリエチレンテレフタレート等のポリエステル;ポリプロピレン、ポリエチレン等のポリオレフィンなどの、耐熱性及び耐溶剤性を有する重合体からなるフィルムを用いることができる。市販のものとしては、王子製紙株式会社製のアルファンMA-410、E-200、信越フィルム株式会社製等のポリプロピレンフィルム、帝人株式会社製のPS-25等のPSシリーズのポリエチレンテレフタレートフィルム、タマポリ株式会社製のNF-15Aが挙げられる。なお、保護層6は支持体2と同一のものでもよい。
As the protective layer 6, the adhesive force to the photosensitive layer 4 may be smaller than the adhesive force of the support 2 to the photosensitive layer 4. Specifically, as the protective layer 6, a film made of a polymer having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate; polyolefin such as polypropylene and polyethylene can be used. Commercially available products include polypropylene films such as Alfan MA-410 and E-200 manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., PS-25 such as PS-25 manufactured by Teijin Limited, and Tamapoly. An example is NF-15A manufactured by KK. The protective layer 6 may be the same as the support 2.
保護層6の厚みは、1~100μm、5~50μm、5~30μm、又は、15~30μmであってもよい。保護層6の厚みが1μm以上であると、保護層6を剥がしながら、感光層4及び支持体2を基材上にラミネートする際、保護層6が破れることを抑制できる。100μm以下であると、取扱い性と廉価性に優れる。
The thickness of the protective layer 6 may be 1 to 100 μm, 5 to 50 μm, 5 to 30 μm, or 15 to 30 μm. When the thickness of the protective layer 6 is 1 μm or more, the protective layer 6 can be prevented from being broken when the photosensitive layer 4 and the support 2 are laminated on the substrate while peeling off the protective layer 6. When it is 100 μm or less, it is excellent in handleability and inexpensiveness.
感光性エレメント10は、具体的には例えば以下のようにして製造することができる。すなわち、感光性エレメント10は、感光性樹脂組成物を含む塗布液を準備する工程と、上記塗布液を支持体2上に塗布して塗布層を形成する工程と、上記塗布層を乾燥して感光層4を形成する工程と、を含む製造方法で製造することができる。
Specifically, the photosensitive element 10 can be manufactured as follows, for example. That is, the photosensitive element 10 includes a step of preparing a coating solution containing a photosensitive resin composition, a step of coating the coating solution on the support 2 to form a coating layer, and drying the coating layer. And a step of forming the photosensitive layer 4.
塗布液の支持体2上への塗布は、ロールコート、コンマコート、グラビアコート、エアーナイフコート、ダイコート、バーコート等の公知の方法により行うことができる。
Application of the coating liquid onto the support 2 can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.
塗布層の乾燥は、塗布層から有機溶剤の少なくとも一部を除去することができれば特に制限はない。例えば、70~150℃にて、5~30分間程度行ってもよい。乾燥後、感光層4中の残存有機溶剤量は、後の工程での有機溶剤の拡散を防止する観点から、2質量%以下であってもよい。
The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it may be performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive layer 4 may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
感光性エレメント10における感光層4の厚みは、用途により適宜選択することができる。乾燥後の厚みで1~100μm、1~50μm、又は、5~40μmであってもよい。感光層4の厚みが1μm以上であることで、工業的な塗工が容易になる。100μm以下であると、密着性及び解像度が充分に得られる傾向がある。
The thickness of the photosensitive layer 4 in the photosensitive element 10 can be appropriately selected depending on the application. The thickness after drying may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm. Industrial coating becomes easy because the thickness of the photosensitive layer 4 is 1 μm or more. When it is 100 μm or less, adhesion and resolution tend to be sufficiently obtained.
感光性エレメント10は、例えば、後述するレジストパターンの形成方法に好適に用いることができる。
The photosensitive element 10 can be suitably used, for example, in a resist pattern forming method described later.
<レジストパターンの形成方法>
本実施形態に係るレジストパターンの形成方法は、(i)基材上に感光性樹脂組成物又は感光性エレメントを用いて感光層を形成する感光層形成工程と、(ii)感光層の一部の領域を活性光線の照射により硬化して、光硬化物領域を形成する露光工程と、(iii)感光層の光硬化物領域以外の領域を基材上から除去して、基材上に、感光性樹脂組成物の光硬化物(光硬化物領域)からなるレジストパターンを形成する現像工程と、を有する。レジストパターンの形成方法は、必要に応じて更にその他の工程を有していてもよい。なお、レジストパターンとは、樹脂パターン、又は、レリーフパターンともいえる。以下、各工程について詳述する。 <Method for forming resist pattern>
The resist pattern forming method according to the present embodiment includes (i) a photosensitive layer forming step of forming a photosensitive layer on a substrate using a photosensitive resin composition or a photosensitive element, and (ii) a part of the photosensitive layer. (Iii) removing the region other than the photocured product region of the photosensitive layer from the substrate, and curing the region of the above by irradiation with actinic rays to form a photocured product region, And a developing step of forming a resist pattern made of a photocured product (photocured product region) of the photosensitive resin composition. The method for forming a resist pattern may further include other steps as necessary. In addition, it can be said that a resist pattern is a resin pattern or a relief pattern. Hereinafter, each process is explained in full detail.
本実施形態に係るレジストパターンの形成方法は、(i)基材上に感光性樹脂組成物又は感光性エレメントを用いて感光層を形成する感光層形成工程と、(ii)感光層の一部の領域を活性光線の照射により硬化して、光硬化物領域を形成する露光工程と、(iii)感光層の光硬化物領域以外の領域を基材上から除去して、基材上に、感光性樹脂組成物の光硬化物(光硬化物領域)からなるレジストパターンを形成する現像工程と、を有する。レジストパターンの形成方法は、必要に応じて更にその他の工程を有していてもよい。なお、レジストパターンとは、樹脂パターン、又は、レリーフパターンともいえる。以下、各工程について詳述する。 <Method for forming resist pattern>
The resist pattern forming method according to the present embodiment includes (i) a photosensitive layer forming step of forming a photosensitive layer on a substrate using a photosensitive resin composition or a photosensitive element, and (ii) a part of the photosensitive layer. (Iii) removing the region other than the photocured product region of the photosensitive layer from the substrate, and curing the region of the above by irradiation with actinic rays to form a photocured product region, And a developing step of forming a resist pattern made of a photocured product (photocured product region) of the photosensitive resin composition. The method for forming a resist pattern may further include other steps as necessary. In addition, it can be said that a resist pattern is a resin pattern or a relief pattern. Hereinafter, each process is explained in full detail.
(i)感光層形成工程
感光層形成工程では、基材上に感光性樹脂組成物を用いて感光層を形成する。 (I) Photosensitive layer forming step In the photosensitive layer forming step, a photosensitive layer is formed using a photosensitive resin composition on a substrate.
感光層形成工程では、基材上に感光性樹脂組成物を用いて感光層を形成する。 (I) Photosensitive layer forming step In the photosensitive layer forming step, a photosensitive layer is formed using a photosensitive resin composition on a substrate.
基材上に感光層を形成する方法としては、例えば、基材上に、感光性樹脂組成物を含む塗布液を塗布した後、乾燥させる方法が挙げられる。
Examples of the method for forming the photosensitive layer on the substrate include a method in which a coating liquid containing a photosensitive resin composition is applied on the substrate and then dried.
また、基材上に感光層を形成する方法としては、例えば、感光性エレメントから必要に応じて保護層を除去した後、感光性エレメントの感光層を基材上にラミネートする方法が挙げられる。ラミネートは、感光性エレメントの感光層を加熱しながら基材に圧着することにより、行うことができる。このラミネートにより、基材と感光層と支持体とがこの順に積層された積層体が得られる。
Further, as a method for forming a photosensitive layer on a substrate, for example, a method of laminating the photosensitive layer of the photosensitive element on the substrate after removing the protective layer from the photosensitive element as necessary. Lamination can be performed by pressure-bonding the photosensitive layer of the photosensitive element to the substrate while heating. By this lamination, a laminate in which the substrate, the photosensitive layer, and the support are laminated in this order is obtained.
ラミネートは、例えば70~130℃の温度で行ってもよく、0.1~1.0MPa程度(1~10kgf/cm2程度)の圧力で圧着して行ってもよい。これらの条件は必要に応じて適宜調整することができる。ラミネートに際しては、基材が予熱処理されていてもよく、感光層が70~130℃に加熱されていてもよい。
Lamination may be performed at a temperature of 70 to 130 ° C., for example, or may be performed by pressure bonding at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm 2 ). These conditions can be adjusted as needed. When laminating, the substrate may be preheated, and the photosensitive layer may be heated to 70 to 130 ° C.
(ii)露光工程
露光工程では、感光層の一部の領域に活性光線を照射することで、活性光線が照射された露光部が光硬化して、潜像が形成される。ここで、感光層形成工程で感光性エレメントを用いたとき、感光層上には支持体が存在するが、支持体が活性光線に対して透過性を有する場合には、支持体を通して活性光線を照射することができる。一方、支持体が活性光線に対して遮光性を示す場合には、支持体を除去した後に、感光層に活性光線を照射する。 (Ii) Exposure Step In the exposure step, a part of the photosensitive layer is irradiated with actinic rays, whereby the exposed portion irradiated with the actinic rays is photocured to form a latent image. Here, when a photosensitive element is used in the photosensitive layer forming step, a support is present on the photosensitive layer, but when the support is transparent to actinic light, active light is transmitted through the support. Can be irradiated. On the other hand, when the support is light-shielding against actinic rays, the photosensitive layer is irradiated with actinic rays after the support is removed.
露光工程では、感光層の一部の領域に活性光線を照射することで、活性光線が照射された露光部が光硬化して、潜像が形成される。ここで、感光層形成工程で感光性エレメントを用いたとき、感光層上には支持体が存在するが、支持体が活性光線に対して透過性を有する場合には、支持体を通して活性光線を照射することができる。一方、支持体が活性光線に対して遮光性を示す場合には、支持体を除去した後に、感光層に活性光線を照射する。 (Ii) Exposure Step In the exposure step, a part of the photosensitive layer is irradiated with actinic rays, whereby the exposed portion irradiated with the actinic rays is photocured to form a latent image. Here, when a photosensitive element is used in the photosensitive layer forming step, a support is present on the photosensitive layer, but when the support is transparent to actinic light, active light is transmitted through the support. Can be irradiated. On the other hand, when the support is light-shielding against actinic rays, the photosensitive layer is irradiated with actinic rays after the support is removed.
露光方法としては、アートワークと呼ばれるネガ又はポジマスクパターンを通して活性光線を画像状に照射する方法(マスク露光法)が挙げられる。また、LDI(Laser Direct Imaging)露光法及びDLP(Digital Light Processing)露光法等の直接描画露光法により活性光線を画像状に照射する方法を採用してもよい。
Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method and a DLP (Digital Light Processing) exposure method may be employed.
活性光線の波長(露光波長)としては、本発明の効果をより確実に得る観点から、340~430nm、又は、350~420nmであってもよい。
The wavelength of the actinic ray (exposure wavelength) may be 340 to 430 nm or 350 to 420 nm from the viewpoint of obtaining the effect of the present invention more reliably.
(iii)現像工程
現像工程では、感光層の光硬化物領域以外の領域(すなわち、感光層の未硬化部分)を基材上から現像処理により除去して、感光層の光硬化物からなるレジストパターンを基材上に形成する。なお、露光工程を経た感光層上に支持体が存在している場合には、支持体を除去してから現像工程を行う。現像処理には、ウェット現像とドライ現像とがあるが、ウェット現像が好適に用いられる。 (Iii) Development process In the development process, a region other than the photocured product region of the photosensitive layer (that is, an uncured portion of the photosensitive layer) is removed from the substrate by a development treatment, and a resist made of the photocured product of the photosensitive layer is formed. A pattern is formed on the substrate. In addition, when the support body exists on the photosensitive layer which passed through the exposure process, a developing process is performed after removing a support body. The development processing includes wet development and dry development, and wet development is preferably used.
現像工程では、感光層の光硬化物領域以外の領域(すなわち、感光層の未硬化部分)を基材上から現像処理により除去して、感光層の光硬化物からなるレジストパターンを基材上に形成する。なお、露光工程を経た感光層上に支持体が存在している場合には、支持体を除去してから現像工程を行う。現像処理には、ウェット現像とドライ現像とがあるが、ウェット現像が好適に用いられる。 (Iii) Development process In the development process, a region other than the photocured product region of the photosensitive layer (that is, an uncured portion of the photosensitive layer) is removed from the substrate by a development treatment, and a resist made of the photocured product of the photosensitive layer is formed. A pattern is formed on the substrate. In addition, when the support body exists on the photosensitive layer which passed through the exposure process, a developing process is performed after removing a support body. The development processing includes wet development and dry development, and wet development is preferably used.
ウェット現像では、感光性樹脂組成物に対応した現像液を用いて、公知の現像方法により現像を行う。現像方法としては、ディップ方式、パドル方式、スプレー方式、ブラッシング、スラッピング、スクラッビング、揺動浸漬等を用いた方法が挙げられ、解像度向上の観点からは、高圧スプレー方式が最も適している。これら2種以上の方法を組み合わせて現像を行ってもよい。
In wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.
現像液は、感光性樹脂組成物の構成に応じて適宜選択できる。現像液としては、アルカリ性水溶液、水系現像液、有機溶剤系現像液等が挙げられる。
The developer can be appropriately selected according to the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like.
現像に用いるアルカリ性水溶液としては、0.1~5質量%炭酸ナトリウム水溶液、0.1~5質量%炭酸カリウム水溶液、0.1~5質量%水酸化ナトリウム水溶液、0.1~5質量%四ホウ酸ナトリウム水溶液等であってもよい。アルカリ性水溶液のpHは9~11であってもよい。また、その温度は、感光層のアルカリ現像性に合わせて調節される。アルカリ性水溶液中には、表面活性剤、消泡剤、現像を促進させるための少量の有機溶剤等を混入させてもよい。
Examples of the alkaline aqueous solution used for development include 0.1 to 5% by weight sodium carbonate aqueous solution, 0.1 to 5% by weight potassium carbonate aqueous solution, 0.1 to 5% by weight sodium hydroxide aqueous solution, and 0.1 to 5% by weight four. It may be a sodium borate aqueous solution or the like. The pH of the alkaline aqueous solution may be 9-11. The temperature is adjusted according to the alkali developability of the photosensitive layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
レジストパターンの形成方法は、未露光部分を除去した後、必要に応じて60~250℃程度の加熱及び/又は0.2~10J/cm2程度の露光を行うことにより、レジストパターンを更に硬化する工程を更に有していてもよい。
The resist pattern is formed by removing the unexposed portion and further curing the resist pattern by heating at about 60 to 250 ° C. and / or exposing at about 0.2 to 10 J / cm 2 as necessary. You may have further the process to do.
<タッチパネルの製造方法>
本実施形態に係るタッチパネルの製造方法は、上記レジストパターンの形成方法によりレジストパターンが形成された基材を、エッチング処理する工程を有する。エッチング処理は、形成されたレジストパターンをマスク(「レジスト」ともいえる)として、基材の導体層等に対して行われる。エッチング処理により、引き出し配線と透明電極のパターンとを形成することで、タッチパネルが製造される。 <Manufacturing method of touch panel>
The manufacturing method of the touch panel according to the present embodiment includes a step of etching the base material on which the resist pattern is formed by the resist pattern forming method. The etching process is performed on the conductor layer of the base material using the formed resist pattern as a mask (also referred to as “resist”). The touch panel is manufactured by forming the lead wiring and the pattern of the transparent electrode by the etching process.
本実施形態に係るタッチパネルの製造方法は、上記レジストパターンの形成方法によりレジストパターンが形成された基材を、エッチング処理する工程を有する。エッチング処理は、形成されたレジストパターンをマスク(「レジスト」ともいえる)として、基材の導体層等に対して行われる。エッチング処理により、引き出し配線と透明電極のパターンとを形成することで、タッチパネルが製造される。 <Manufacturing method of touch panel>
The manufacturing method of the touch panel according to the present embodiment includes a step of etching the base material on which the resist pattern is formed by the resist pattern forming method. The etching process is performed on the conductor layer of the base material using the formed resist pattern as a mask (also referred to as “resist”). The touch panel is manufactured by forming the lead wiring and the pattern of the transparent electrode by the etching process.
図3は、本発明のタッチパネルの製造方法の一態様を示す模式断面図である。本態様の製造方法は、支持基材22と、支持基材22の一面上に設けられた透明導電層24と、透明導電層24上に設けられた金属層26とを備える積層基材の、金属層26上に、感光性樹脂組成物の光硬化物からなるレジストパターン29を形成する第1の工程と、金属層26及び透明導電層24をエッチングして、透明導電層24の残部及び金属層26の残部からなる積層パターン(図3(d)における24+26)を形成する第2の工程と、積層パターンの一部から金属層を除去して、透明導電層24の残部からなる透明電極と金属層の残部からなる金属配線とを形成する第3の工程と、を有する。
FIG. 3 is a schematic cross-sectional view showing one embodiment of the touch panel manufacturing method of the present invention. The manufacturing method of this aspect is a laminated base material comprising a support base material 22, a transparent conductive layer 24 provided on one surface of the support base material 22, and a metal layer 26 provided on the transparent conductive layer 24. A first step of forming a resist pattern 29 made of a photo-cured product of the photosensitive resin composition on the metal layer 26, and etching the metal layer 26 and the transparent conductive layer 24, the remainder of the transparent conductive layer 24 and the metal A second step of forming a laminated pattern (24 + 26 in FIG. 3D) consisting of the remainder of the layer 26, a transparent electrode consisting of the remainder of the transparent conductive layer 24 by removing the metal layer from a part of the laminated pattern, and And a third step of forming a metal wiring composed of the remainder of the metal layer.
第1の工程では、まず、図3(a)に示すように、支持基材22と、支持基材22の一面上に設けられた透明導電層24と、透明導電層24上に設けられた金属層26とを備える積層基材の、金属層26上に、感光性樹脂組成物を用いて感光層28を形成する。感光層28は、金属層26と反対側の面上に支持体を備えていてもよい。
In the first step, first, as shown in FIG. 3A, the support base 22, the transparent conductive layer 24 provided on one surface of the support base 22, and the transparent conductive layer 24 were provided. A photosensitive layer 28 is formed using a photosensitive resin composition on the metal layer 26 of the laminated base material including the metal layer 26. The photosensitive layer 28 may include a support on the surface opposite to the metal layer 26.
金属層26としては、例えば、銅を含む金属層であってもよい。また、銅を含む金属層としては、銅、銅とニッケルの合金、銅とニッケルとチタンの合金、モリブデン-アルミ-モリブデン積層体、銀とパラジウムと銅の合金等を含む金属層が挙げられる。これらのうち、本発明の効果が一層顕著に得られる観点から、銅、銅とニッケルの合金又は銅とニッケルとチタンの合金を含む金属層を好適に用いることができる。
As the metal layer 26, for example, a metal layer containing copper may be used. Examples of the metal layer containing copper include a metal layer containing copper, a copper-nickel alloy, a copper-nickel-titanium alloy, a molybdenum-aluminum-molybdenum laminate, a silver-palladium-copper alloy, and the like. Of these, a metal layer containing copper, an alloy of copper and nickel, or an alloy of copper, nickel and titanium can be suitably used from the viewpoint that the effects of the present invention can be obtained more remarkably.
透明導電層24は、酸化インジウムスズ(ITO)を含有する。透明導電層24は、アニール処理が不要となる観点から、結晶性のITOを含むものであってもよい。
The transparent conductive layer 24 contains indium tin oxide (ITO). The transparent conductive layer 24 may contain crystalline ITO from the viewpoint that the annealing process is unnecessary.
次いで、感光層28の一部の領域を活性光線の照射により硬化して、光硬化物領域を形成し、感光層の光硬化物領域以外の領域を積層基材上から除去する。これにより、図3(b)に示すように、積層基材上にレジストパターン29が形成される。
Next, a part of the photosensitive layer 28 is cured by irradiation with actinic rays to form a photocured product region, and regions other than the photocured product region of the photosensitive layer are removed from the laminated substrate. Thereby, as shown in FIG.3 (b), the resist pattern 29 is formed on a laminated base material.
第2の工程では、エッチング処理により、レジストパターン29でマスクされていない領域の金属層26及び透明導電層24を、支持基材22上から除去する。
In the second step, the metal layer 26 and the transparent conductive layer 24 in a region not masked by the resist pattern 29 are removed from the support substrate 22 by etching.
エッチング処理の方法は、除去すべき層に応じて適宜選択される。例えば、金属層を除去するためのエッチング液としては、塩化第二銅溶液、塩化第二鉄溶液、リン酸溶液等が挙げられる。また、透明導電層を除去するためのエッチング液としては、シュウ酸、塩酸、王水等が用いられる。
The etching method is appropriately selected according to the layer to be removed. For example, examples of the etching solution for removing the metal layer include a cupric chloride solution, a ferric chloride solution, and a phosphoric acid solution. Moreover, oxalic acid, hydrochloric acid, aqua regia, etc. are used as etching liquid for removing a transparent conductive layer.
透明導電層24が結晶性のITOを含むものである場合、透明導電層24を除去するためのエッチング液としては、濃塩酸、王水等の強酸又は金属層と透明導電層を一括でエッチングする薬液(例えば、ITO-4400Z等のITOシリーズ)を用いる必要があるが、本態様の製造方法では、レジストパターンが上記感光性樹脂組成物の光硬化物からなるものであるため、強酸等によるエッチング処理下でもレジストパターンの剥離等が充分に抑制される。本実施形態に係る感光性樹脂組成物は、エッチング液として上述した濃塩酸、王水等の強酸又は金属層と透明導電層を一括でエッチングする薬液を用いるエッチング用感光性樹脂組成物として好適に使用することができる。
When the transparent conductive layer 24 contains crystalline ITO, as an etching solution for removing the transparent conductive layer 24, a strong acid such as concentrated hydrochloric acid or aqua regia or a chemical solution for etching the metal layer and the transparent conductive layer in a lump ( For example, it is necessary to use ITO series such as ITO-4400Z). However, in the manufacturing method of this embodiment, the resist pattern is made of a photocured product of the photosensitive resin composition. However, resist pattern peeling and the like are sufficiently suppressed. The photosensitive resin composition according to the present embodiment is suitably used as an etching photosensitive resin composition using the above-described strong acid such as concentrated hydrochloric acid or aqua regia or a chemical solution that etches the metal layer and the transparent conductive layer at once. Can be used.
図3(c)はエッチング処理後を示す図であり、図3(c)においては支持基材22上に、金属層26の残部、透明導電層24の残部及びレジストパターン29の残部からなる積層体が形成されている。本態様の製造方法においては、この積層体からレジストパターン29が除去される。
FIG. 3C is a diagram showing the state after the etching process. In FIG. 3C, the stack composed of the remainder of the metal layer 26, the remainder of the transparent conductive layer 24, and the remainder of the resist pattern 29 on the support substrate 22. The body is formed. In the manufacturing method of this aspect, the resist pattern 29 is removed from the laminate.
レジストパターン29の除去は、例えば、上述の現像工程に用いるアルカリ性水溶液よりもアルカリ性の強い水溶液を用いて行うことができる。この強アルカリ性の水溶液としては、1~10質量%水酸化ナトリウム水溶液、1~10質量%水酸化カリウム水溶液等が用いられる。中でも1~10質量%水酸化ナトリウム水溶液又は1~10質量%水酸化カリウム水溶液を用いてもよく、1~5質量%水酸化ナトリウム水溶液又は1~5質量%水酸化カリウム水溶液を用いてもよい。レジストパターンの剥離方式としては、浸漬方式、スプレー方式等が挙げられ、これらは単独で用いても併用してもよい。
The removal of the resist pattern 29 can be performed using, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step described above. As this strongly alkaline aqueous solution, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Among them, a 1 to 10% by mass sodium hydroxide aqueous solution or a 1 to 10% by mass potassium hydroxide aqueous solution may be used, and a 1 to 5% by mass sodium hydroxide aqueous solution or a 1 to 5% by mass potassium hydroxide aqueous solution may be used. . Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination.
図3(d)は、レジストパターン剥離後を示す図であり、図3(d)においては支持基材22上に、金属層26の残部及び透明導電層24の残部からなる積層パターンが形成されている。
FIG. 3D is a view showing the resist pattern after peeling. In FIG. 3D, a laminated pattern composed of the remainder of the metal layer 26 and the remainder of the transparent conductive layer 24 is formed on the support base material 22. ing.
第3の工程では、この積層パターンから、金属層26のうち金属配線を成すための一部分以外を除去して、金属層26の残部からなる金属配線と透明導電層24の残部からなる透明電極とを形成する。なお、本態様では、第3の工程で金属層26を除去する方法として、エッチングを行う方法を採用するが、第3の工程で金属層26を除去する方法は必ずしもエッチングに限定されない。
In the third step, a part of the metal layer 26 other than a part for forming the metal wiring is removed from the laminated pattern, and the metal wiring composed of the remaining part of the metal layer 26 and the transparent electrode composed of the remaining part of the transparent conductive layer 24 are formed. Form. In this aspect, an etching method is employed as a method of removing the metal layer 26 in the third step, but the method of removing the metal layer 26 in the third step is not necessarily limited to etching.
第3の工程では、まず、第2の工程を経た積層基材上に感光層30を形成する(図3(e))。次いで、感光層30の露光及び現像を経て、感光層30の光硬化物からなるレジスト31を形成する(図3(f))。なお、感光層は、上述の本実施形態に係る感光性樹脂組成物を用いて形成された層であってもよく、従来公知のエッチング用感光性樹脂組成物を用いて形成された層であってもよい。
In the third step, first, the photosensitive layer 30 is formed on the laminated substrate subjected to the second step (FIG. 3E). Next, a resist 31 made of a photocured product of the photosensitive layer 30 is formed through exposure and development of the photosensitive layer 30 (FIG. 3F). The photosensitive layer may be a layer formed using the above-described photosensitive resin composition according to the present embodiment, or a layer formed using a conventionally known photosensitive resin composition for etching. May be.
次に、エッチング処理により、積層パターンのうちレジスト31が形成されていない部分から、金属層26を除去する。このとき、エッチング処理液としては、上述の金属層を除去するためのエッチング液と同様のものを用いることができる。
Next, the metal layer 26 is removed from the portion of the laminated pattern where the resist 31 is not formed by an etching process. At this time, as the etching treatment liquid, the same one as the etching liquid for removing the metal layer can be used.
図3(g)はエッチング処理後を示す図であり、図3(g)においては、支持基材22上に、透明導電層24の残部からなる透明電極が形成され、また、一部の透明電極上に金属層26及びレジスト31からなる積層体が形成されている。この積層体から、レジスト31を除去することにより、図3(h)に示すように、支持基材22上に、透明導電層24の残部からなる透明電極と金属層26の残部からなる金属配線とが形成される。
FIG. 3G is a diagram showing the state after the etching process. In FIG. 3G, a transparent electrode composed of the remaining portion of the transparent conductive layer 24 is formed on the support base material 22, and a part of the transparent electrode is formed. A laminate composed of the metal layer 26 and the resist 31 is formed on the electrode. By removing the resist 31 from the laminated body, as shown in FIG. 3 (h), the transparent electrode composed of the remaining portion of the transparent conductive layer 24 and the metal wiring composed of the remaining portion of the metal layer 26 are formed on the support substrate 22. And are formed.
図4は、本発明を利用して得られるタッチパネルの一態様を示す上面図である。タッチパネル100においては、透明電極であるX電極52及びY電極54が交互に並設されており、長手方向の同列に設けられたX電極52同士が一つの引き出し配線56によってそれぞれ連結され、また、幅方向の同列に設けられたY電極54同士が一つの引き出し配線57によってそれぞれ連結されている。
FIG. 4 is a top view showing an aspect of a touch panel obtained by using the present invention. In the touch panel 100, X electrodes 52 and Y electrodes 54, which are transparent electrodes, are alternately arranged in parallel, and the X electrodes 52 provided in the same row in the longitudinal direction are connected to each other by a single lead wiring 56, The Y electrodes 54 provided in the same row in the width direction are connected to each other by one lead-out wiring 57.
以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。
The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.
以下、実施例により本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples.
(製造例1:バインダーポリマー(A-1)の製造)
重合性単量体(モノマー)であるメタクリル酸30g、メタクリル酸メチル35g及びメタクリル酸ブチル35g(質量比30/35/35)と、アゾビスイソブチロニトリル0.5gと、アセトン10gと、を混合して得た溶液を「溶液a」とした。アセトン30gにアゾビスイソブチロニトリル0.6gを溶解して得た溶液を「溶液b」とした。 (Production Example 1: Production of binder polymer (A-1))
A polymerizable monomer (monomer) 30 g of methacrylic acid, 35 g of methyl methacrylate and 35 g of butyl methacrylate (mass ratio 30/35/35), 0.5 g of azobisisobutyronitrile, and 10 g of acetone. The solution obtained by mixing was designated as “Solution a”. A solution obtained by dissolving 0.6 g of azobisisobutyronitrile in 30 g of acetone was designated as “Solution b”.
重合性単量体(モノマー)であるメタクリル酸30g、メタクリル酸メチル35g及びメタクリル酸ブチル35g(質量比30/35/35)と、アゾビスイソブチロニトリル0.5gと、アセトン10gと、を混合して得た溶液を「溶液a」とした。アセトン30gにアゾビスイソブチロニトリル0.6gを溶解して得た溶液を「溶液b」とした。 (Production Example 1: Production of binder polymer (A-1))
A polymerizable monomer (monomer) 30 g of methacrylic acid, 35 g of methyl methacrylate and 35 g of butyl methacrylate (
撹拌機、還流冷却器、温度計、滴下ロート及び窒素ガス導入管を備えたフラスコに、アセトン80g及びプロピレングリコールモノメチルエーテル20gの混合液(質量比4:1)100gを投入し、フラスコ内に窒素ガスを吹き込みつつ撹拌しながら加熱し、80℃まで昇温させた。
A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 100 g of a mixture of 80 g of acetone and 20 g of propylene glycol monomethyl ether (mass ratio 4: 1), and nitrogen was introduced into the flask. The mixture was heated with stirring while blowing gas, and the temperature was raised to 80 ° C.
フラスコ内の上記混合液に、上記溶液aを4時間かけて滴下速度を一定にして滴下した後、フラスコ内の溶液を80℃で2時間撹拌した。次いで、フラスコ内の溶液に、上記溶液bを10分間かけて滴下速度を一定にして滴下した後、フラスコ内の溶液を80℃で3時間撹拌した。更に、フラスコ内の溶液を30分間かけて90℃まで昇温させ、90℃にて2時間保温した後、冷却してバインダーポリマー(A-1)の溶液を得た。
The solution a was dropped into the mixed solution in the flask at a constant dropping rate over 4 hours, and then the solution in the flask was stirred at 80 ° C. for 2 hours. Next, the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 hours. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of binder polymer (A-1).
バインダーポリマー(A-1)の溶液の不揮発分(固形分)は42.8質量%であった。また、バインダーポリマー(A-1)の重量平均分子量は50000であり、酸価は195mgKOH/g、分散度は2.58であった。
The nonvolatile content (solid content) of the solution of the binder polymer (A-1) was 42.8% by mass. The weight average molecular weight of the binder polymer (A-1) was 50,000, the acid value was 195 mgKOH / g, and the degree of dispersion was 2.58.
なお、重量平均分子量及び分散度は、ゲルパーミエーションクロマトグラフィー法(GPC)によって測定し、標準ポリスチレンの検量線を用いて換算することにより導出した。GPCの条件を以下に示す。
(GPC条件)
ポンプ:日立/ L-6000型(株式会社日立製作所)
カラム:以下の計3本、カラム仕様:10.7mmφ×300mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M(以上、日立化成株式会社)
溶離液:テトラヒドロフラン(THF)
試料濃度:固形分が40質量%の樹脂溶液を120mg採取し、5mLのTHFに溶解して試料を調製した。
測定温度:40℃
注入量:200μL
圧力:49Kgf/cm2(4.8MPa)
流量:2.05mL/分
検出器:日立 L-3300型RI(株式会社日立製作所) The weight average molecular weight and degree of dispersion were determined by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. The GPC conditions are shown below.
(GPC conditions)
Pump: Hitachi / L-6000 (Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm 2 (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (Hitachi, Ltd.)
(GPC条件)
ポンプ:日立/ L-6000型(株式会社日立製作所)
カラム:以下の計3本、カラム仕様:10.7mmφ×300mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M(以上、日立化成株式会社)
溶離液:テトラヒドロフラン(THF)
試料濃度:固形分が40質量%の樹脂溶液を120mg採取し、5mLのTHFに溶解して試料を調製した。
測定温度:40℃
注入量:200μL
圧力:49Kgf/cm2(4.8MPa)
流量:2.05mL/分
検出器:日立 L-3300型RI(株式会社日立製作所) The weight average molecular weight and degree of dispersion were determined by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. The GPC conditions are shown below.
(GPC conditions)
Pump: Hitachi / L-6000 (Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm 2 (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (Hitachi, Ltd.)
また、酸価は、次のようにして測定した。まず、バインダーポリマーの溶液を130℃で1時間加熱し、揮発分を除去して、固形分を得た。そして、上記固形分のポリマー1gを精秤した後、このポリマーにアセトンを30g添加し、これを均一に溶解した。次いで、指示薬であるフェノールフタレインをその溶液に適量添加して、0.1NのKOH水溶液を用いて滴定を行った。そして、次式により酸価を算出した。
酸価=0.1×Vf×56.1/(Wp×I/100)
式中、VfはKOH水溶液の滴定量(mL)を示し、Wpは測定したポリマー溶液の質量(g)を示し、Iは測定したポリマー溶液中の不揮発分の割合(質量%)を示す。 Moreover, the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. And after precisely weighing 1 g of the polymer of the solid content, 30 g of acetone was added to the polymer, and this was uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured polymer solution, and I represents the ratio (mass%) of the non-volatile content in the measured polymer solution.
酸価=0.1×Vf×56.1/(Wp×I/100)
式中、VfはKOH水溶液の滴定量(mL)を示し、Wpは測定したポリマー溶液の質量(g)を示し、Iは測定したポリマー溶液中の不揮発分の割合(質量%)を示す。 Moreover, the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. And after precisely weighing 1 g of the polymer of the solid content, 30 g of acetone was added to the polymer, and this was uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured polymer solution, and I represents the ratio (mass%) of the non-volatile content in the measured polymer solution.
[実施例1~7及び比較例1~2]
実施例及び比較例は、以下の方法で行った。 [Examples 1 to 7 and Comparative Examples 1 and 2]
Examples and comparative examples were performed by the following methods.
実施例及び比較例は、以下の方法で行った。 [Examples 1 to 7 and Comparative Examples 1 and 2]
Examples and comparative examples were performed by the following methods.
<感光性樹脂組成物(塗布液)の調製>
表1及び表2に示す各成分を、同表に示す配合量(質量部)で混合することにより、実施例及び比較例の感光性樹脂組成物の塗布液を得た。表中の(A)成分の配合量は不揮発分の質量(固形分量)である。なお、「-」は未配合を意味する。表1及び表2に示す各成分の詳細は、以下のとおりである。 <Preparation of photosensitive resin composition (coating liquid)>
By mixing the components shown in Table 1 and Table 2 in the blending amounts (parts by mass) shown in the same table, coating solutions of the photosensitive resin compositions of Examples and Comparative Examples were obtained. The blending amount of the component (A) in the table is the mass (solid content) of the non-volatile content. “-” Means not blended. Details of each component shown in Table 1 and Table 2 are as follows.
表1及び表2に示す各成分を、同表に示す配合量(質量部)で混合することにより、実施例及び比較例の感光性樹脂組成物の塗布液を得た。表中の(A)成分の配合量は不揮発分の質量(固形分量)である。なお、「-」は未配合を意味する。表1及び表2に示す各成分の詳細は、以下のとおりである。 <Preparation of photosensitive resin composition (coating liquid)>
By mixing the components shown in Table 1 and Table 2 in the blending amounts (parts by mass) shown in the same table, coating solutions of the photosensitive resin compositions of Examples and Comparative Examples were obtained. The blending amount of the component (A) in the table is the mass (solid content) of the non-volatile content. “-” Means not blended. Details of each component shown in Table 1 and Table 2 are as follows.
((A)成分)
A-1:製造例1で得られたバインダーポリマー(A-1)。 ((A) component)
A-1: Binder polymer (A-1) obtained in Production Example 1.
A-1:製造例1で得られたバインダーポリマー(A-1)。 ((A) component)
A-1: Binder polymer (A-1) obtained in Production Example 1.
((B)成分)
FA-321M:2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン(日立化成株式会社、EO基の数:10(平均値))
FA-3200MY:ポリオキシアルキレン化ビスフェノールAジメタクリレート(日立化成株式会社、EO基の数:12(平均値)、PO基の数:4(平均値))
FA-MECH:γ-クロロ-β-ヒドロキシプロピル-β’-メタクリロイルオキシエチル-o-フタレート(日立化成株式会社)
UA-13:ポリオキシエチレン及びポリオキシプロピレンウレタンジメタクリレート(イソシアヌル環骨格を有さない化合物、新中村化学株式会社製、EO基の数:2(平均値)、PO基の数:18(平均値))
UA-21:トリス(メタクリロキシテトラエチレングリコールイソシアネート)ヘキサメチレンイソシアヌレート(イソシアヌル環骨格を有する化合物、新中村化学工業株式会社製、EO基の数:12(平均値))
DPEA-12:EO基を有するジペンタエリスリトールヘキサアクリレート(日本化薬株式会社、EO基の数:12(平均値)) ((B) component)
FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (Hitachi Chemical Co., Ltd., number of EO groups: 10 (average value))
FA-3200MY: polyoxyalkylenated bisphenol A dimethacrylate (Hitachi Chemical Co., Ltd., number of EO groups: 12 (average value), number of PO groups: 4 (average value))
FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (Hitachi Chemical Co., Ltd.)
UA-13: polyoxyethylene and polyoxypropylene urethane dimethacrylate (compound having no isocyanuric ring skeleton, manufactured by Shin-Nakamura Chemical Co., Ltd., number of EO groups: 2 (average value), number of PO groups: 18 (average value))
UA-21: Tris (methacryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate (compound having isocyanuric ring skeleton, manufactured by Shin-Nakamura Chemical Co., Ltd., number of EO groups: 12 (average value))
DPEA-12: Dipentaerythritol hexaacrylate having EO group (Nippon Kayaku Co., Ltd., number of EO groups: 12 (average value))
FA-321M:2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン(日立化成株式会社、EO基の数:10(平均値))
FA-3200MY:ポリオキシアルキレン化ビスフェノールAジメタクリレート(日立化成株式会社、EO基の数:12(平均値)、PO基の数:4(平均値))
FA-MECH:γ-クロロ-β-ヒドロキシプロピル-β’-メタクリロイルオキシエチル-o-フタレート(日立化成株式会社)
UA-13:ポリオキシエチレン及びポリオキシプロピレンウレタンジメタクリレート(イソシアヌル環骨格を有さない化合物、新中村化学株式会社製、EO基の数:2(平均値)、PO基の数:18(平均値))
UA-21:トリス(メタクリロキシテトラエチレングリコールイソシアネート)ヘキサメチレンイソシアヌレート(イソシアヌル環骨格を有する化合物、新中村化学工業株式会社製、EO基の数:12(平均値))
DPEA-12:EO基を有するジペンタエリスリトールヘキサアクリレート(日本化薬株式会社、EO基の数:12(平均値)) ((B) component)
FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (Hitachi Chemical Co., Ltd., number of EO groups: 10 (average value))
FA-3200MY: polyoxyalkylenated bisphenol A dimethacrylate (Hitachi Chemical Co., Ltd., number of EO groups: 12 (average value), number of PO groups: 4 (average value))
FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (Hitachi Chemical Co., Ltd.)
UA-13: polyoxyethylene and polyoxypropylene urethane dimethacrylate (compound having no isocyanuric ring skeleton, manufactured by Shin-Nakamura Chemical Co., Ltd., number of EO groups: 2 (average value), number of PO groups: 18 (average value))
UA-21: Tris (methacryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate (compound having isocyanuric ring skeleton, manufactured by Shin-Nakamura Chemical Co., Ltd., number of EO groups: 12 (average value))
DPEA-12: Dipentaerythritol hexaacrylate having EO group (Nippon Kayaku Co., Ltd., number of EO groups: 12 (average value))
((C)成分)
B-CIM:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール(常州強力電子新材料株式会社) ((C) component)
B-CIM: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Changzhou Power Electronics New Materials Co., Ltd.)
B-CIM:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール(常州強力電子新材料株式会社) ((C) component)
B-CIM: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Changzhou Power Electronics New Materials Co., Ltd.)
((D)成分:シランカップリング剤)
AY43-031:3-ウレイドプロピルトリエトキシシラン(東レ・ダウコーニング株式会社)
KBM-803:3-メルカプトプロピルトリメトキシシラン(信越化学工業株式会社)
SZ-6030:3-メタクリロキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社) ((D) component: silane coupling agent)
AY43-031: 3-Ureidopropyltriethoxysilane (Toray Dow Corning Co., Ltd.)
KBM-803: 3-Mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
SZ-6030: 3-methacryloxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd.)
AY43-031:3-ウレイドプロピルトリエトキシシラン(東レ・ダウコーニング株式会社)
KBM-803:3-メルカプトプロピルトリメトキシシラン(信越化学工業株式会社)
SZ-6030:3-メタクリロキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社) ((D) component: silane coupling agent)
AY43-031: 3-Ureidopropyltriethoxysilane (Toray Dow Corning Co., Ltd.)
KBM-803: 3-Mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
SZ-6030: 3-methacryloxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd.)
((E)成分:増感色素)
PZ-501D:1-フェニル-3-(4-メトキシスチリル)-5-(4-メトキシフェニル)ピラゾリン(株式会社日本化学工業所) ((E) component: sensitizing dye)
PZ-501D: 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline (Nippon Chemical Industry Co., Ltd.)
PZ-501D:1-フェニル-3-(4-メトキシスチリル)-5-(4-メトキシフェニル)ピラゾリン(株式会社日本化学工業所) ((E) component: sensitizing dye)
PZ-501D: 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline (Nippon Chemical Industry Co., Ltd.)
(その他の成分:(A)~(E)成分以外)
LCV:ロイコクリスタルバイオレット(山田化学工業株式会社)
TBC:4-t-ブチルカテコール(DIC株式会社、「DIC-TBC-5P」)
SF-808H:カルボキシベンゾトリアゾール、5-アミノ-1H-テトラゾール、メトキシプロパノールの混合物(サンワ化成株式会社、「SF-808H」)
AZCV-PW:[4-{ビス(4-ジメチルアミノフェニル)メチレン}-2,5-シクロヘキサジエン-1-イリデン](保土谷化学工業株式会社) (Other components: other than (A) to (E))
LCV: Leuco Crystal Violet (Yamada Chemical Co., Ltd.)
TBC: 4-t-butylcatechol (DIC Corporation, “DIC-TBC-5P”)
SF-808H: Mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (Sanwa Kasei Co., Ltd., “SF-808H”)
AZCV-PW: [4- {bis (4-dimethylaminophenyl) methylene} -2,5-cyclohexadiene-1-ylidene] (Hodogaya Chemical Co., Ltd.)
LCV:ロイコクリスタルバイオレット(山田化学工業株式会社)
TBC:4-t-ブチルカテコール(DIC株式会社、「DIC-TBC-5P」)
SF-808H:カルボキシベンゾトリアゾール、5-アミノ-1H-テトラゾール、メトキシプロパノールの混合物(サンワ化成株式会社、「SF-808H」)
AZCV-PW:[4-{ビス(4-ジメチルアミノフェニル)メチレン}-2,5-シクロヘキサジエン-1-イリデン](保土谷化学工業株式会社) (Other components: other than (A) to (E))
LCV: Leuco Crystal Violet (Yamada Chemical Co., Ltd.)
TBC: 4-t-butylcatechol (DIC Corporation, “DIC-TBC-5P”)
SF-808H: Mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (Sanwa Kasei Co., Ltd., “SF-808H”)
AZCV-PW: [4- {bis (4-dimethylaminophenyl) methylene} -2,5-cyclohexadiene-1-ylidene] (Hodogaya Chemical Co., Ltd.)
<感光性エレメントの作製>
上記で得られた感光性樹脂組成物の塗布液を、それぞれ厚み16μmのポリエチレンテレフタレートフィルム(東レ株式会社製、製品名「FB-40」)上に厚みが均一になるように塗布し、70℃及び110℃の熱風対流式乾燥器で順次乾燥処理して、乾燥後の膜厚が15μmである感光層を形成した。この感光層上に保護層(タマポリ株式会社製、製品名「NF-15A」)を貼り合わせ、ポリエチレンテレフタレートフィルム(支持体)と、感光層と、保護層とが順に積層された感光性エレメントを得た。 <Production of photosensitive element>
The coating solution of the photosensitive resin composition obtained above was applied on a polyethylene terephthalate film (product name “FB-40”, manufactured by Toray Industries, Inc.) having a thickness of 16 μm so as to have a uniform thickness, and 70 ° C. Then, a drying process was sequentially performed with a hot air convection dryer at 110 ° C. to form a photosensitive layer having a thickness of 15 μm after drying. A protective layer (product name “NF-15A”, manufactured by Tamapoly Co., Ltd.) is laminated on the photosensitive layer, and a photosensitive element in which a polyethylene terephthalate film (support), a photosensitive layer, and a protective layer are laminated in order. Obtained.
上記で得られた感光性樹脂組成物の塗布液を、それぞれ厚み16μmのポリエチレンテレフタレートフィルム(東レ株式会社製、製品名「FB-40」)上に厚みが均一になるように塗布し、70℃及び110℃の熱風対流式乾燥器で順次乾燥処理して、乾燥後の膜厚が15μmである感光層を形成した。この感光層上に保護層(タマポリ株式会社製、製品名「NF-15A」)を貼り合わせ、ポリエチレンテレフタレートフィルム(支持体)と、感光層と、保護層とが順に積層された感光性エレメントを得た。 <Production of photosensitive element>
The coating solution of the photosensitive resin composition obtained above was applied on a polyethylene terephthalate film (product name “FB-40”, manufactured by Toray Industries, Inc.) having a thickness of 16 μm so as to have a uniform thickness, and 70 ° C. Then, a drying process was sequentially performed with a hot air convection dryer at 110 ° C. to form a photosensitive layer having a thickness of 15 μm after drying. A protective layer (product name “NF-15A”, manufactured by Tamapoly Co., Ltd.) is laminated on the photosensitive layer, and a photosensitive element in which a polyethylene terephthalate film (support), a photosensitive layer, and a protective layer are laminated in order. Obtained.
<積層基材の作製>
ポリエチレンテレフタレート材の上層に結晶性のITOからなる透明導電層、更にその上層に銅からなる金属層が形成され、金属層の最表面には防錆処理を行ったフィルム基材を準備した。このフィルム基材(以下、「基材」という。)を加熱して80℃に昇温させた後、上記で作製した感光性エレメントを、基材の金属層表面にラミネート(積層)した。ラミネートは、保護層を除去しながら、感光性エレメントの感光層が基材の金属層表面に密着するようにして、温度110℃、ラミネート圧力4kgf/cm2(0.4MPa)の条件下で行った。このようにして、基材の金属層表面上に感光層及び支持体が積層された積層基材を得た。 <Preparation of laminated substrate>
A transparent conductive layer made of crystalline ITO was formed on the upper layer of the polyethylene terephthalate material, and a metal layer made of copper was formed on the upper layer of the polyethylene terephthalate material. After heating this film base material (henceforth a "base material") and heating up at 80 degreeC, the photosensitive element produced above was laminated (laminated | stacked) on the metal layer surface of the base material. Lamination is performed under conditions of a temperature of 110 ° C. and a lamination pressure of 4 kgf / cm 2 (0.4 MPa) so that the photosensitive layer of the photosensitive element is in close contact with the surface of the metal layer of the substrate while removing the protective layer. It was. In this way, a laminated substrate in which the photosensitive layer and the support were laminated on the surface of the metal layer of the substrate was obtained.
ポリエチレンテレフタレート材の上層に結晶性のITOからなる透明導電層、更にその上層に銅からなる金属層が形成され、金属層の最表面には防錆処理を行ったフィルム基材を準備した。このフィルム基材(以下、「基材」という。)を加熱して80℃に昇温させた後、上記で作製した感光性エレメントを、基材の金属層表面にラミネート(積層)した。ラミネートは、保護層を除去しながら、感光性エレメントの感光層が基材の金属層表面に密着するようにして、温度110℃、ラミネート圧力4kgf/cm2(0.4MPa)の条件下で行った。このようにして、基材の金属層表面上に感光層及び支持体が積層された積層基材を得た。 <Preparation of laminated substrate>
A transparent conductive layer made of crystalline ITO was formed on the upper layer of the polyethylene terephthalate material, and a metal layer made of copper was formed on the upper layer of the polyethylene terephthalate material. After heating this film base material (henceforth a "base material") and heating up at 80 degreeC, the photosensitive element produced above was laminated (laminated | stacked) on the metal layer surface of the base material. Lamination is performed under conditions of a temperature of 110 ° C. and a lamination pressure of 4 kgf / cm 2 (0.4 MPa) so that the photosensitive layer of the photosensitive element is in close contact with the surface of the metal layer of the substrate while removing the protective layer. It was. In this way, a laminated substrate in which the photosensitive layer and the support were laminated on the surface of the metal layer of the substrate was obtained.
<感度の評価>
得られた積層基材を23℃になるまで放冷した。次に、積層基材を3つの領域に分割し、そのうち一つの領域の支持体上に、濃度領域0.00~2.00、濃度ステップ0.05、タブレットの大きさ20mm×187mm、各ステップの大きさが3mm×12mmである41段ステップタブレットを有するフォトツールを密着させた。露光は、ショートアークUVランプ(株式会社オーク製作所製、製品名「AHD-5000R」)を光源とする平行光線露光機(株式会社オーク製作所製、製品名「EXM-1201」)を使用して、100mJ/cm2のエネルギー量(露光量)でフォトツール及び支持体を介して感光層に対して露光した。この際、使用しない他の領域は、ブラックシートで覆った。また、それぞれ別の領域に対して、同様の方法で個々に200mJ/cm2、400mJ/cm2のエネルギー量で露光した。なお、照度の測定は、405nm対応プローブを適用した紫外線照度計(ウシオ電機株式会社製、製品名「UIT-150」)を用いた。 <Evaluation of sensitivity>
The obtained laminated substrate was allowed to cool to 23 ° C. Next, the laminated substrate is divided into three regions, and on one of the regions, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm × 187 mm, each step. A phototool having a 41-step tablet having a size of 3 mm × 12 mm was adhered. For exposure, a parallel light exposure machine (product name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) using a short arc UV lamp (product name “AHD-5000R” manufactured by Oak Manufacturing Co., Ltd.) as a light source is used. The photosensitive layer was exposed through a photo tool and a support with an energy amount (exposure amount) of 100 mJ / cm 2 . At this time, other areas not used were covered with a black sheet. Moreover, it exposed with the energy amount of 200mJ / cm < 2 > and 400mJ / cm < 2 > separately with respect to each different area | region by the same method. The illuminance was measured using an ultraviolet illuminance meter (product name “UIT-150” manufactured by USHIO INC.) To which a 405 nm probe was applied.
得られた積層基材を23℃になるまで放冷した。次に、積層基材を3つの領域に分割し、そのうち一つの領域の支持体上に、濃度領域0.00~2.00、濃度ステップ0.05、タブレットの大きさ20mm×187mm、各ステップの大きさが3mm×12mmである41段ステップタブレットを有するフォトツールを密着させた。露光は、ショートアークUVランプ(株式会社オーク製作所製、製品名「AHD-5000R」)を光源とする平行光線露光機(株式会社オーク製作所製、製品名「EXM-1201」)を使用して、100mJ/cm2のエネルギー量(露光量)でフォトツール及び支持体を介して感光層に対して露光した。この際、使用しない他の領域は、ブラックシートで覆った。また、それぞれ別の領域に対して、同様の方法で個々に200mJ/cm2、400mJ/cm2のエネルギー量で露光した。なお、照度の測定は、405nm対応プローブを適用した紫外線照度計(ウシオ電機株式会社製、製品名「UIT-150」)を用いた。 <Evaluation of sensitivity>
The obtained laminated substrate was allowed to cool to 23 ° C. Next, the laminated substrate is divided into three regions, and on one of the regions, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm × 187 mm, each step. A phototool having a 41-step tablet having a size of 3 mm × 12 mm was adhered. For exposure, a parallel light exposure machine (product name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) using a short arc UV lamp (product name “AHD-5000R” manufactured by Oak Manufacturing Co., Ltd.) as a light source is used. The photosensitive layer was exposed through a photo tool and a support with an energy amount (exposure amount) of 100 mJ / cm 2 . At this time, other areas not used were covered with a black sheet. Moreover, it exposed with the energy amount of 200mJ / cm < 2 > and 400mJ / cm < 2 > separately with respect to each different area | region by the same method. The illuminance was measured using an ultraviolet illuminance meter (product name “UIT-150” manufactured by USHIO INC.) To which a 405 nm probe was applied.
露光後、積層基材から支持体を剥離し、感光層を露出させ、30℃の1質量%炭酸ナトリウム水溶液を16秒間スプレーすることにより、未露光部分を除去した。このようにして、基材の金属層表面上に感光性樹脂組成物の光硬化物からなるレジストパターンを形成した。各露光量におけるレジストパターン(硬化膜)として得られたステップタブレットの残存段数(ステップ段数)から、露光量とステップ段数との検量線を作成し、ステップ段数が17段となる露光量を求めることにより、感光性樹脂組成物の感度を評価した。感度は、検量線から求めたステップ段数が17段となる露光量により示され、この露光量が少ないほど感度が良好であることを意味する。結果を表3及び表4に示す。
After the exposure, the support was peeled off from the laminated base material, the photosensitive layer was exposed, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed for 16 seconds to remove unexposed portions. Thus, the resist pattern which consists of a photocured material of the photosensitive resin composition was formed on the metal layer surface of a base material. A calibration curve between the exposure amount and the step step number is created from the remaining step number (step step number) of the step tablet obtained as a resist pattern (cured film) at each exposure amount, and the exposure amount at which the step step number is 17 steps is obtained. Thus, the sensitivity of the photosensitive resin composition was evaluated. The sensitivity is indicated by the exposure amount at which the number of step steps obtained from the calibration curve is 17, and the smaller the exposure amount, the better the sensitivity. The results are shown in Tables 3 and 4.
<密着性の評価>
ライン幅(L)/スペース幅(S)(以下、「L/S」と記す。)が4/400~30/400(単位:μm)であるマスクパターンを用いて、41段ステップタブレットの残存段数が17段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行った。 <Evaluation of adhesion>
The remaining 41 step tablet using a mask pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 4/400 to 30/400 (unit: μm). The photosensitive layer of the laminated substrate was exposed with an energy amount of 17 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.
ライン幅(L)/スペース幅(S)(以下、「L/S」と記す。)が4/400~30/400(単位:μm)であるマスクパターンを用いて、41段ステップタブレットの残存段数が17段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行った。 <Evaluation of adhesion>
The remaining 41 step tablet using a mask pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 4/400 to 30/400 (unit: μm). The photosensitive layer of the laminated substrate was exposed with an energy amount of 17 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.
現像後、スペース部分(未露光部分)がきれいに除去され、且つライン部分(露光部分)が蛇行、剥がれ及び欠けを生じることなく形成されたレジストパターンにおけるライン幅/スペース幅の値のうちの最小値により、密着性を評価した。この数値が小さいほど密着性が良好であることを意味する。結果を表3及び表4に示す。
After development, the minimum value of the line width / space width values in the resist pattern in which the space portion (unexposed portion) is removed neatly and the line portion (exposed portion) is formed without causing meandering, peeling and chipping. Thus, the adhesion was evaluated. The smaller this value, the better the adhesion. The results are shown in Tables 3 and 4.
<解像性の評価>
L/Sが1/1~30/30(単位:μm)であるマスクパターンを用いて、41段ステップタブレットの残存段数が17段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行った。 <Evaluation of resolution>
Using a mask pattern having an L / S of 1/1 to 30/30 (unit: μm), the photosensitive layer of the laminated base material is exposed with an energy amount that makes the remaining number of steps of a 41-step step tablet 17 steps. did. After the exposure, the same development processing as in the sensitivity evaluation was performed.
L/Sが1/1~30/30(単位:μm)であるマスクパターンを用いて、41段ステップタブレットの残存段数が17段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行った。 <Evaluation of resolution>
Using a mask pattern having an L / S of 1/1 to 30/30 (unit: μm), the photosensitive layer of the laminated base material is exposed with an energy amount that makes the remaining number of steps of a 41-step step tablet 17 steps. did. After the exposure, the same development processing as in the sensitivity evaluation was performed.
現像後、スペース部分(未露光部分)がきれいに除去され、且つライン部分(露光部分)が蛇行、剥がれ及び欠けを生じることなく形成されたレジストパターンにおけるライン幅/スペース幅の値のうちの最小値により、解像度を評価した。この数値が小さいほど解像度が良好であることを意味する。結果を表3及び表4に示す。
After development, the minimum value of the line width / space width values in the resist pattern in which the space portion (unexposed portion) is removed neatly and the line portion (exposed portion) is formed without causing meandering, peeling and chipping. The resolution was evaluated. The smaller this value, the better the resolution. The results are shown in Tables 3 and 4.
<エッチング後の密着性の評価>
レジストパターンのエッチング後の密着性を以下のように評価した。L/Sが4/400~47/400(単位:μm)であるマスクパターンを用いて、41段ステップタブレットの残存段数が23段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行ってパターン形成された基材を得た。 <Evaluation of adhesion after etching>
The adhesion after etching of the resist pattern was evaluated as follows. Using a mask pattern having an L / S of 4/400 to 47/400 (unit: μm), the photosensitive layer of the laminated base material is exposed with an energy amount that makes the remaining number of steps of the 41-step tablet tablet 23. did. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a patterned substrate.
レジストパターンのエッチング後の密着性を以下のように評価した。L/Sが4/400~47/400(単位:μm)であるマスクパターンを用いて、41段ステップタブレットの残存段数が23段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行ってパターン形成された基材を得た。 <Evaluation of adhesion after etching>
The adhesion after etching of the resist pattern was evaluated as follows. Using a mask pattern having an L / S of 4/400 to 47/400 (unit: μm), the photosensitive layer of the laminated base material is exposed with an energy amount that makes the remaining number of steps of the 41-step tablet tablet 23. did. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a patterned substrate.
得られた基材に対し、ITO-4400Z(株式会社ADEKA製、商品名)を用いて40℃で30秒間エッチングを行い、その後、水洗、乾燥させた。
The obtained base material was etched at 40 ° C. for 30 seconds using ITO-4400Z (trade name, manufactured by ADEKA Corporation), and then washed and dried.
スペース部分(未露光部分)の金属層及び透明導電層がきれいに除去され、且つライン部分(露光部分)が蛇行、剥がれ及び欠けを生じることなく形成されたレジストパターンにおけるライン幅/スペース幅の値のうちの最小値により、エッチング後の密着性を評価した。
この数値が小さいほど耐エッチング液性が高く密着性が良好であることを意味する。結果を表3及び表4に示す。 The value of the line width / space width in the resist pattern in which the metal layer and the transparent conductive layer in the space portion (unexposed portion) are removed neatly and the line portion (exposed portion) is formed without causing meandering, peeling and chipping. The adhesion after etching was evaluated by the minimum value.
The smaller this value, the higher the etchant resistance and the better the adhesion. The results are shown in Tables 3 and 4.
この数値が小さいほど耐エッチング液性が高く密着性が良好であることを意味する。結果を表3及び表4に示す。 The value of the line width / space width in the resist pattern in which the metal layer and the transparent conductive layer in the space portion (unexposed portion) are removed neatly and the line portion (exposed portion) is formed without causing meandering, peeling and chipping. The adhesion after etching was evaluated by the minimum value.
The smaller this value, the higher the etchant resistance and the better the adhesion. The results are shown in Tables 3 and 4.
<エッチング後のライン形状の評価>
配線パターンのエッチング後のライン形状は、上記エッチング後の密着性の評価の際に、L/Sが47/400(単位:μm)のレジストパターンの下に形成された配線パターンについて、デジタルマイクロスコープVHX-2000(株式会社キーエンス製)を用いて観察した。また、レジストパターンのライン幅とエッチング後の回路パターンのライン幅との差からサイドエッチング幅を算出した。サイドエッチング幅の値とガタツキの有無とにより、配線パターンのエッチング後のライン形状を以下の基準にて評価を行った。結果を表3及び表4に示す。
A:配線パターンのエッチング後のライン形状にガタツキが見られず、サイドエッチング幅の値が5μm未満である。
B:配線パターンのエッチング後のライン形状にガタツキは見られないが、サイドエッチング幅の値が5μm以上8μm未満である。
C:配線パターンのエッチング後のライン形状にガタツキは見られないが、サイドエッチング幅の値が8μm以上である。
D:配線パターンのエッチング後のライン形状にガタツキが見られる。 <Evaluation of line shape after etching>
The line shape after the etching of the wiring pattern is the digital microscope for the wiring pattern formed under the resist pattern having L / S of 47/400 (unit: μm) in the evaluation of the adhesion after the etching. Observation was performed using VHX-2000 (manufactured by Keyence Corporation). Further, the side etching width was calculated from the difference between the line width of the resist pattern and the line width of the circuit pattern after etching. The line shape after etching the wiring pattern was evaluated according to the following criteria based on the value of the side etching width and the presence or absence of rattling. The results are shown in Tables 3 and 4.
A: There is no backlash in the line shape after etching the wiring pattern, and the value of the side etching width is less than 5 μm.
B: Although there is no backlash in the line shape after etching the wiring pattern, the value of the side etching width is 5 μm or more and less than 8 μm.
C: The line shape after the etching of the wiring pattern is not rattled, but the value of the side etching width is 8 μm or more.
D: Roughness is observed in the line shape after etching the wiring pattern.
配線パターンのエッチング後のライン形状は、上記エッチング後の密着性の評価の際に、L/Sが47/400(単位:μm)のレジストパターンの下に形成された配線パターンについて、デジタルマイクロスコープVHX-2000(株式会社キーエンス製)を用いて観察した。また、レジストパターンのライン幅とエッチング後の回路パターンのライン幅との差からサイドエッチング幅を算出した。サイドエッチング幅の値とガタツキの有無とにより、配線パターンのエッチング後のライン形状を以下の基準にて評価を行った。結果を表3及び表4に示す。
A:配線パターンのエッチング後のライン形状にガタツキが見られず、サイドエッチング幅の値が5μm未満である。
B:配線パターンのエッチング後のライン形状にガタツキは見られないが、サイドエッチング幅の値が5μm以上8μm未満である。
C:配線パターンのエッチング後のライン形状にガタツキは見られないが、サイドエッチング幅の値が8μm以上である。
D:配線パターンのエッチング後のライン形状にガタツキが見られる。 <Evaluation of line shape after etching>
The line shape after the etching of the wiring pattern is the digital microscope for the wiring pattern formed under the resist pattern having L / S of 47/400 (unit: μm) in the evaluation of the adhesion after the etching. Observation was performed using VHX-2000 (manufactured by Keyence Corporation). Further, the side etching width was calculated from the difference between the line width of the resist pattern and the line width of the circuit pattern after etching. The line shape after etching the wiring pattern was evaluated according to the following criteria based on the value of the side etching width and the presence or absence of rattling. The results are shown in Tables 3 and 4.
A: There is no backlash in the line shape after etching the wiring pattern, and the value of the side etching width is less than 5 μm.
B: Although there is no backlash in the line shape after etching the wiring pattern, the value of the side etching width is 5 μm or more and less than 8 μm.
C: The line shape after the etching of the wiring pattern is not rattled, but the value of the side etching width is 8 μm or more.
D: Roughness is observed in the line shape after etching the wiring pattern.
<可とう性の評価>
レジストパターンの可とう性は、マンドレル試験(JIS K5600-5-1)で評価した。ポリエチレンテレフタレート製ネガ(全面露光できるネガ)を用いて、41段ステップタブレットの残存段数が17段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行い、硬化膜を形成させた積層基材を得た。この硬化膜を形成させた積層基材を10mm×100mmに切り出すことでマンドレル試験用の試験片とした。直径2、3、4、5、6、8、10、12、16、20、25mmの円筒状の棒(マンドレル治具)の側面に沿わせて上記試験片を180°に折り曲げた後、試験片の両端を平行に保ちつつ交互に引くことで、マンドレル治具の側面に沿って試験片の3分の2の領域を一定の速度で5往復摺動させた。その後、基材とレジストパターンとの間に剥がれ及びクラックがない最小直径を求めた。最小直径が小さいほど、可とう性に優れることを表す。結果を表3及び表4に示す。 <Evaluation of flexibility>
The flexibility of the resist pattern was evaluated by a mandrel test (JIS K5600-5-1). Using a polyethylene terephthalate negative (a negative that can expose the entire surface), the photosensitive layer of the laminated base material was exposed with an energy amount such that the number of remaining stages of the 41-step tablet was 17. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a laminated base material on which a cured film was formed. The laminated base material on which this cured film was formed was cut out to 10 mm × 100 mm to obtain a test piece for a mandrel test. The test piece was bent at 180 ° along the side of a cylindrical rod (mandrel jig) having diameters of 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 25 mm, and then tested. By pulling alternately while keeping both ends of the pieces in parallel, the two-thirds of the test piece was slid 5 times at a constant speed along the side surface of the mandrel jig. Then, the minimum diameter which does not peel and crack between a base material and a resist pattern was calculated | required. The smaller the minimum diameter, the better the flexibility. The results are shown in Tables 3 and 4.
レジストパターンの可とう性は、マンドレル試験(JIS K5600-5-1)で評価した。ポリエチレンテレフタレート製ネガ(全面露光できるネガ)を用いて、41段ステップタブレットの残存段数が17段となるエネルギー量で上記積層基材の感光層に対して露光した。露光後、上記感度の評価と同様の現像処理を行い、硬化膜を形成させた積層基材を得た。この硬化膜を形成させた積層基材を10mm×100mmに切り出すことでマンドレル試験用の試験片とした。直径2、3、4、5、6、8、10、12、16、20、25mmの円筒状の棒(マンドレル治具)の側面に沿わせて上記試験片を180°に折り曲げた後、試験片の両端を平行に保ちつつ交互に引くことで、マンドレル治具の側面に沿って試験片の3分の2の領域を一定の速度で5往復摺動させた。その後、基材とレジストパターンとの間に剥がれ及びクラックがない最小直径を求めた。最小直径が小さいほど、可とう性に優れることを表す。結果を表3及び表4に示す。 <Evaluation of flexibility>
The flexibility of the resist pattern was evaluated by a mandrel test (JIS K5600-5-1). Using a polyethylene terephthalate negative (a negative that can expose the entire surface), the photosensitive layer of the laminated base material was exposed with an energy amount such that the number of remaining stages of the 41-step tablet was 17. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a laminated base material on which a cured film was formed. The laminated base material on which this cured film was formed was cut out to 10 mm × 100 mm to obtain a test piece for a mandrel test. The test piece was bent at 180 ° along the side of a cylindrical rod (mandrel jig) having diameters of 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 25 mm, and then tested. By pulling alternately while keeping both ends of the pieces in parallel, the two-thirds of the test piece was slid 5 times at a constant speed along the side surface of the mandrel jig. Then, the minimum diameter which does not peel and crack between a base material and a resist pattern was calculated | required. The smaller the minimum diameter, the better the flexibility. The results are shown in Tables 3 and 4.
光重合性化合物として、分子内に6つのエチレン性不飽和結合を有する(メタ)アクレートと、イソシアヌル環骨格を有する(メタ)アクリレートとを用いた実施例1~7は、比較例1~2と比較して、エッチング後の密着性、ライン形状をバランスよく向上させることが可能であるとともに、可とう性にも優れることが分かった。
Examples 1 to 7 in which (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton were used as the photopolymerizable compound and Comparative Examples 1 and 2 In comparison, it was found that the adhesion after etching and the line shape can be improved in a well-balanced manner and the flexibility is excellent.
2…支持体、4…感光層、6…保護層、10…感光性エレメント、12…支持基材、14…透明導電層、16…感光層、18…引き出し配線、22…支持基材、24…透明導電層、26…金属層、28…感光層、29…レジストパターン、30…感光層、31…レジスト、52…透明電極(X電極)、54…透明電極(Y電極)、56,57…引き出し配線、100…タッチパネル。
DESCRIPTION OF SYMBOLS 2 ... Support body, 4 ... Photosensitive layer, 6 ... Protective layer, 10 ... Photosensitive element, 12 ... Support base material, 14 ... Transparent conductive layer, 16 ... Photosensitive layer, 18 ... Lead-out wiring, 22 ... Support base material, 24 ... Transparent conductive layer, 26 ... Metal layer, 28 ... Photosensitive layer, 29 ... Resist pattern, 30 ... Photosensitive layer, 31 ... Resist, 52 ... Transparent electrode (X electrode), 54 ... Transparent electrode (Y electrode), 56, 57 ... drawer wiring, 100 ... touch panel.
Claims (6)
- (A)成分:バインダーポリマー、
(B)成分:光重合性化合物、及び、
(C)成分:光重合開始剤を含有し、
前記(B)成分が、分子内に6つのエチレン性不飽和結合を有する(メタ)アクリレートと、イソシアヌル環骨格を有する(メタ)アクリレートとを含む、感光性樹脂組成物。 (A) component: binder polymer,
(B) component: a photopolymerizable compound, and
(C) component: contains a photopolymerization initiator,
The photosensitive resin composition in which the said (B) component contains the (meth) acrylate which has six ethylenically unsaturated bonds in a molecule | numerator, and the (meth) acrylate which has an isocyanuric ring frame | skeleton. - 前記(B)成分が、(ポリ)オキシエチレン基を有するビスフェノールA型ジ(メタ)アクリレートを更に含む、請求項1に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the component (B) further comprises a bisphenol A type di (meth) acrylate having a (poly) oxyethylene group.
- 支持体と、該支持体の一面上に設けられた、請求項1又は2に記載の感光性樹脂組成物を用いて形成された感光層と、を備える、感光性エレメント。 A photosensitive element comprising: a support; and a photosensitive layer formed using the photosensitive resin composition according to claim 1 or 2 provided on one surface of the support.
- 基材上に、請求項1又は2に記載の感光性樹脂組成物又は請求項3に記載の感光性エレメントを用いて感光層を形成する感光層形成工程と、
前記感光層の一部の領域を活性光線の照射により硬化して、光硬化物領域を形成する露光工程と、
前記感光層の前記光硬化物領域以外の領域を前記基材上から除去して、前記光硬化物領域からなるレジストパターンを得る現像工程と、
を有する、レジストパターンの形成方法。 A photosensitive layer forming step of forming a photosensitive layer on the substrate using the photosensitive resin composition according to claim 1 or 2 or the photosensitive element according to claim 3,
An exposure step of curing a part of the photosensitive layer by irradiation with actinic rays to form a photocured product region;
A development step of removing a region other than the photocured product region of the photosensitive layer from the substrate to obtain a resist pattern composed of the photocured product region,
A method for forming a resist pattern. - 支持基材と該支持基材の一面上に設けられた酸化インジウムスズを含む透明導電層と該透明導電層上に設けられた金属層とを備える積層基材の、前記金属層上に、請求項1又は2に記載の感光性樹脂組成物の光硬化物からなるレジストパターンを形成する第1の工程と、
前記金属層及び前記透明導電層をエッチングして、前記透明導電層の残部及び前記金属層の残部からなる積層パターンを形成する第2の工程と、
前記積層パターンの一部から前記金属層を除去して、前記透明導電層の残部からなる透明電極と前記金属層の残部からなる金属配線とを形成する第3の工程と、
を有する、タッチパネルの製造方法。 On the metal layer of a laminated substrate comprising a support substrate, a transparent conductive layer containing indium tin oxide provided on one surface of the support substrate, and a metal layer provided on the transparent conductive layer, The 1st process of forming the resist pattern which consists of photocured material of the photosensitive resin composition of claim | item 1 or 2;
A second step of etching the metal layer and the transparent conductive layer to form a laminate pattern composed of the remainder of the transparent conductive layer and the remainder of the metal layer;
A third step of removing the metal layer from a part of the laminated pattern to form a transparent electrode made of the remainder of the transparent conductive layer and a metal wiring made of the remainder of the metal layer;
A method for manufacturing a touch panel. - 前記透明導電層が、結晶性の酸化インジウムスズを含み、
前記第2の工程におけるエッチングが、強酸によるエッチングである、請求項5に記載のタッチパネルの製造方法。 The transparent conductive layer comprises crystalline indium tin oxide;
The touch panel manufacturing method according to claim 5, wherein the etching in the second step is etching with a strong acid.
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2021039187A1 (en) * | 2019-08-27 | 2021-03-04 | 富士フイルム株式会社 | Transfer film, method for producing transfer film, method for producing laminate, laminate, touch panel sensor, and touch panel |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000112121A (en) * | 1998-10-06 | 2000-04-21 | Fuji Photo Film Co Ltd | Photosensitive resin composition |
JP2005010205A (en) * | 2003-06-16 | 2005-01-13 | Mitsui Chemicals Inc | Photosensitive composition and method for manufacturing printed circuit board using same |
JP2012048202A (en) * | 2010-07-30 | 2012-03-08 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, method for manufacturing resist pattern, method for manufacturing lead frame, method for manufacturing printed wiring board, and printed wiring board |
WO2014010345A1 (en) * | 2012-07-09 | 2014-01-16 | 東レ株式会社 | Photosensitive resin composition, conductive wire protection film, and touch panel member |
JP2014048428A (en) * | 2012-08-30 | 2014-03-17 | Jsr Corp | Radiation-sensitive composition, formation method of cured film for display element, cured film for display element, and display element |
WO2014050567A1 (en) * | 2012-09-27 | 2014-04-03 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing touch panel |
JP2015087429A (en) * | 2013-10-28 | 2015-05-07 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, and method for forming resist pattern |
JP2015175961A (en) * | 2014-03-14 | 2015-10-05 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing touch panel |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000112121A (en) * | 1998-10-06 | 2000-04-21 | Fuji Photo Film Co Ltd | Photosensitive resin composition |
JP2005010205A (en) * | 2003-06-16 | 2005-01-13 | Mitsui Chemicals Inc | Photosensitive composition and method for manufacturing printed circuit board using same |
JP2012048202A (en) * | 2010-07-30 | 2012-03-08 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, method for manufacturing resist pattern, method for manufacturing lead frame, method for manufacturing printed wiring board, and printed wiring board |
WO2014010345A1 (en) * | 2012-07-09 | 2014-01-16 | 東レ株式会社 | Photosensitive resin composition, conductive wire protection film, and touch panel member |
JP2014048428A (en) * | 2012-08-30 | 2014-03-17 | Jsr Corp | Radiation-sensitive composition, formation method of cured film for display element, cured film for display element, and display element |
WO2014050567A1 (en) * | 2012-09-27 | 2014-04-03 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing touch panel |
JP2015087429A (en) * | 2013-10-28 | 2015-05-07 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, and method for forming resist pattern |
JP2015175961A (en) * | 2014-03-14 | 2015-10-05 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing touch panel |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021039187A1 (en) * | 2019-08-27 | 2021-03-04 | 富士フイルム株式会社 | Transfer film, method for producing transfer film, method for producing laminate, laminate, touch panel sensor, and touch panel |
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