CN115685701A - Transfer film, method for manufacturing laminate having conductor pattern, and photosensitive composition - Google Patents
Transfer film, method for manufacturing laminate having conductor pattern, and photosensitive composition Download PDFInfo
- Publication number
- CN115685701A CN115685701A CN202210902364.3A CN202210902364A CN115685701A CN 115685701 A CN115685701 A CN 115685701A CN 202210902364 A CN202210902364 A CN 202210902364A CN 115685701 A CN115685701 A CN 115685701A
- Authority
- CN
- China
- Prior art keywords
- group
- resin
- structural unit
- photosensitive composition
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
-
- 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
- G03F7/30—Imagewise removal using liquid means
-
- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
Abstract
The invention provides a transfer film capable of forming a resist pattern and having excellent stripping performance of the formed resist pattern, a method for manufacturing a laminated body with a conductor pattern, and a photosensitive composition. A transfer film comprising a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer comprises a resin A, a polymerizable compound and a polymerization initiator, and the resin A comprises a structural unit a having a group which generates an alkali-soluble group by the action of an alkali and a structural unit b having an acid group.
Description
Technical Field
The present invention relates to a transfer film, a method for manufacturing a laminate having a conductor pattern, and a photosensitive composition.
Background
A method of disposing a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing the photosensitive composition layer is widely used because the number of steps for obtaining a predetermined pattern is small.
For example, patent document 1 describes a method for forming a resist pattern using a photosensitive resin composition for projection exposure containing (a) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator.
Patent document 1: japanese patent laid-open publication No. 2019-109543
The present inventors have attempted to form a conductor pattern using a transfer film having a photosensitive composition layer as described in patent document 1, and as a result, have found that it is difficult to peel off a resist pattern after an etching step or after a plating treatment step, although the resist pattern can be formed. It has been found that, particularly in the step of forming a conductor pattern by the semi-additive method, it is difficult to peel off the resist pattern after the plating treatment step.
Hereinafter, the resist pattern after the etching step or after the plating treatment step, which is difficult to be peeled, is also referred to as "excellent peelability".
Disclosure of Invention
Accordingly, an object of the present invention is to provide a transfer film which can form a resist pattern and is excellent in the peelability of the formed resist pattern.
Further, another object is to provide a method for producing a laminate having a conductor pattern, and a photosensitive composition.
As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configurations.
〔1〕
A transfer film having a temporary support and a photosensitive composition layer,
the photosensitive composition layer contains a resin A, a polymerizable compound and a polymerization initiator,
the resin a includes a structural unit a having a group that generates an alkali-soluble group by the action of an alkali and a structural unit b having an acid group.
〔2〕
The transfer sheet according to [ 1], wherein,
the structural unit a includes a structural unit having a basic decomposable group.
〔3〕
The transfer sheet according to [ 1] or [ 2], wherein,
the structural unit a includes a structural unit having a group that generates an acid group by the action of a base.
〔4〕
The transfer sheet according to any one of [ 1] to [ 3],
the structural unit a includes at least one selected from a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group.
〔5〕
The transfer film according to any one of [ 1] to [ 4],
the content of the structural unit a is 5 to 50% by mass based on all the structural units of the resin A,
the content of the structural unit b is 10 to 30% by mass based on the total structural units of the resin a.
〔6〕
A transfer film having a temporary support and a photosensitive composition layer,
the photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
the resin B contains a structural unit B having an acid group,
the above compound D has a group which generates an alkali-soluble group by the action of a base,
the content of the compound D is 5 to 50% by mass based on the total mass of the photosensitive composition layer.
〔7〕
The transfer film according to item [ 6], wherein,
the compound D contains a structural unit having a base-decomposable group.
〔8〕
The transfer sheet according to [ 6] or [ 7], wherein,
the compound D contains a structural unit having a group that generates an acid group by the action of a base.
〔9〕
The transfer film according to any one of [ 6] to [ 8],
the compound D contains at least one selected from a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group.
〔10〕
The transfer film according to any one of [ 1] to [ 9], further comprising an intermediate layer between the temporary support and the photosensitive composition layer.
〔11〕
The transfer film according to item [ 10], wherein,
the intermediate layer contains a water-soluble resin.
〔12〕
The transfer film according to [ 11], wherein,
the water-soluble resin includes at least one selected from the group consisting of polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins.
〔13〕
A method for manufacturing a laminate having a conductor pattern, comprising:
a bonding step of bonding the transfer film and the substrate so that the photosensitive composition layer side of the transfer film is in contact with the electroconductive layer of the substrate having an electroconductive layer on the surface thereof according to any one of [ 1] to [ 12 ];
an exposure step of exposing the photosensitive composition layer;
a resist pattern forming step of forming a resist pattern by performing a developing process on the exposed photosensitive composition layer;
an etching step of performing an etching process on the conductive layer located in a region where the resist pattern is not disposed, and a plating step of performing a plating process; and
a resist pattern stripping step of stripping the resist pattern,
the plating treatment step further comprises a removing step of removing the conductive layer exposed in the resist pattern stripping step and forming a conductor pattern on the substrate,
a temporary support peeling step of peeling off the temporary support is further provided between the bonding step and the exposure step or between the exposure step and the development step.
〔14〕
The method for producing a laminate having a conductor pattern according to item [ 13], wherein,
the resist pattern stripping step is a step of stripping the resist pattern with a stripping liquid,
the pH of the stripping solution is 13 or more.
〔15〕
The method for producing a laminate having a conductor pattern according to any one of [ 13] and [ 14], wherein,
the resist pattern forming step is a step of forming a resist pattern by performing a developing treatment using a developer,
the pH of the developing solution is less than 13.
〔16〕
The method for producing a laminate having a conductor pattern according to any one of [ 13] to [ 15], wherein,
the exposure method in the exposure step is any one of mask exposure, direct imaging exposure, and projection exposure.
〔17〕
The method for producing a laminate having a conductor pattern according to any one of [ 13] to [ 16 ], wherein,
the thickness of the temporary support is less than 16 μm.
〔18〕
The method for producing a laminate having a conductor pattern according to any one of [ 13] to [ 17], wherein,
the step of peeling off the temporary support is provided between the bonding step and the exposure step,
the exposed surface exposed in the temporary support peeling step is brought into contact with a mask to expose the photosensitive composition layer.
〔19〕
A photosensitive composition comprising a resin C, a polymerizable compound and a polymerization initiator,
the resin C contains a structural unit having a lactone group and a structural unit b having an acid group.
〔20〕
The photosensitive composition according to [ 19], wherein,
the content of the structural unit having a lactone group is 5 to 50% by mass with respect to all the structural units of the resin C, and the content of the structural unit b is 10 to 30% by mass with respect to all the structural units of the resin C.
〔21〕
A photosensitive composition comprising a resin B, a polymerizable compound, a polymerization initiator and a compound DA different from the resin B,
the resin B contains a structural unit B having an acid group,
the above-mentioned compound DA contains a group having a lactone group,
the content of the compound DA is 5 to 50 mass% based on the total solid content of the photosensitive composition.
Effects of the invention
According to the present invention, a transfer film can be provided in which a resist pattern can be formed and the formed resist pattern has excellent peelability.
Further, according to the present invention, a method for producing a laminate having a conductor pattern and a photosensitive composition can be provided.
Drawings
Fig. 1 is a schematic diagram showing an example of the structure of a transfer film.
Detailed Description
The present invention will be described in detail below.
The following symbols in the present specification are given their meanings.
The numerical range represented by the term "to" means a range including the numerical values before and after the term "to" as the lower limit and the upper limit.
In the numerical ranges recited in the stepwise manner, the upper limit or the lower limit recited in a certain numerical range may be replaced with the upper limit or the lower limit recited in another stepwise manner. In addition, in the numerical ranges described in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.
The "step" includes not only an independent step but also a step in a case where the step cannot be clearly distinguished from other steps as long as the intended purpose of the step can be achieved.
Unless otherwise specified, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700nm is 80% or more, preferably 90% or more.
The average transmittance of visible light is a value measured by a spectrophotometer, and can be measured, for example, by a spectrophotometer U-3310 (manufactured by Hitachi, ltd.).
The refractive index is a value measured at a wavelength of 550nm using an ellipsometer, unless otherwise specified.
Unless otherwise specified, the hue was a value measured by a color difference meter (CR-221, manufactured by MINOLTA).
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of polystyrene using a standard substance, which are measured by a Gel Permeation Chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by TOSOH corporation) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance.
The molecular weight of the compound having a molecular weight distribution is a weight average molecular weight (Mw) unless otherwise specified.
Unless otherwise specified, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP: inductively Coupled Plasma) spectroscopic analyzer.
"(meth) acryloyl group" is a concept including both an acryloyloxy group and a methacryloyloxy group.
The "alkali-soluble resin" refers to a resin having a solubility of 0.1g or more in 100g of a1 mass% aqueous solution of sodium carbonate at 22 ℃.
"Water-soluble" means that the solubility to 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more. That is, the "water-soluble resin" refers to a resin satisfying the above solubility.
The "solid component" of a composition (e.g., a photosensitive composition or the like) refers to a component that forms a composition layer (e.g., a photosensitive composition layer or the like) formed using the composition, and when the composition contains a solvent (e.g., an organic solvent, water or the like), refers to all components except the solvent. In addition, if the component is a component for forming a composition layer (for example, a photosensitive composition layer or the like), a liquid component is also considered as a solid component.
[ transfer film ]
< embodiment 1 >, a method for producing a semiconductor device, and a semiconductor device
Embodiment 1 of the transfer film is a transfer film having a temporary support and a photosensitive composition layer, wherein,
the photosensitive composition layer contains a resin A, a polymerizable compound and a polymerization initiator,
the resin a includes a structural unit a having a group that generates an alkali-soluble group by the action of an alkali (hereinafter, also referred to as a "specific group") and a structural unit b having an acid group.
Although the details of the mechanism of action of the transfer film of the present invention to exhibit the desired effects are not clear, the present inventors presume as follows.
When the resin a contained in the photosensitive composition layer contains the structural unit b, a dissolution contrast can be generated in an exposed portion and an unexposed portion, and a resist pattern can be formed. On the other hand, for example, when an alkaline stripping solution is used in stripping a resist pattern after an etching step or after a plating treatment step, the specific group of the structural unit a generates an alkali-soluble group by the alkaline stripping solution. As a result, it is estimated that the solubility of the resist pattern in the alkaline stripping solution is improved and the stripping property is excellent. In addition, when an alkaline developer and an alkaline stripper are used in the developing treatment and the resist pattern stripping step, it is preferable that the specific group does not generate an alkali-soluble group by the alkaline developer, and the specific group generates an alkali-soluble group by the alkaline stripper.
Hereinafter, the more excellent peelability is also referred to as "the more excellent effect of the present invention".
The transfer film may have other layers besides the temporary support and the photosensitive composition layer.
Examples of the other layer include an intermediate layer described later. The transfer film may have another member (e.g., a protective film) described later.
As an embodiment of the transfer film, for example, the following configuration (1) or (2) can be given, and the configuration (2) is preferable.
(1) "temporary support/photosensitive composition layer/protective film"
(2) "temporary support/intermediate layer/photosensitive composition layer/protective film"
The transfer film preferably has an intermediate layer.
The photosensitive composition layer in each of the above structures is preferably a negative photosensitive composition layer described later or a colored resin layer described later.
From the viewpoint of suppressing the generation of bubbles in the bonding step described later, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 60 μm or less. The lower limit is preferably 0 μm or more, more preferably 0.1 μm or more, and further preferably 1 μm or more.
The maximum width of the moire of the transfer film is a value measured by the following procedure.
The transfer film was cut in a direction perpendicular to the main surface into a size of 20cm in length by 20cm in width to prepare a test sample. In addition, when the transfer film has a protective film, the protective film is peeled from the transfer film. Next, the test sample was allowed to stand on a table having a smooth and horizontal surface so that the surface of the temporary support and the table were opposed to each other. After standing, the surface of the test sample is scanned by a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) to obtain a three-dimensional surface image in a range of 10 cm square from the center of the test sample, and the lowest concavity height is subtracted from the maximum convexity height observed in the obtained three-dimensional surface image. The above operation was performed on 10 test samples, and the arithmetic average value thereof was taken as the maximum width of the moire of the transfer film.
When another composition layer (for example, a photosensitive composition layer, an intermediate layer, or the like) is further provided on the surface of the photosensitive composition layer opposite to the temporary support, the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, based on the total thickness of the photosensitive composition layer.
From the viewpoint of more excellent adhesion, the transmittance of light having a wavelength of 365nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.
An example of an embodiment of the transfer film will be described.
The transfer film 10 shown in fig. 1 includes a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.
The transfer film 10 shown in fig. 1 has the intermediate layer 13 and the protective film 19, but may not have the intermediate layer 13 and the protective film 19.
In fig. 1, each layer (for example, a photosensitive composition layer, an intermediate layer, and the like) other than the protective film 19 which can be disposed on the temporary support 11 is also referred to as a "composition layer".
Hereinafter, the transfer film will be described in detail with respect to each member and each component.
Further, the following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
Hereinafter, embodiment 1 of the transfer film will be described in detail.
[ temporary support body ]
The transfer film has a temporary support.
The temporary support is a member for supporting the photosensitive composition layer, and is finally removed by a peeling treatment.
The temporary support may have a single-layer structure or a multi-layer structure.
The temporary support is preferably a film, and more preferably a resin film. Further, as the temporary support, a film which is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure or under pressure and heat, and a film which is free from deformation such as wrinkles or scratches is also preferable.
Examples of the film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film, and a polyethylene terephthalate film is preferable.
From the viewpoint of enabling pattern exposure via the temporary support, the temporary support preferably has high transparency. Specifically, the transmittance of the temporary support at a wavelength of 365nm is preferably 60% or more, and more preferably 70% or more. The upper limit is preferably less than 100%.
From the viewpoint of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the temporary support preferably has a low haze. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. The lower limit is preferably 0% or more.
From the viewpoints of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the number of particles, foreign substances, and defects in the temporary support is preferably small. Specifically, the number of particles (for example, particles having a diameter of 1 μm), foreign matters and defects in the temporary support is preferably 50 particles/10 mm 2 The number of cells per 10mm is preferably 10 or less 2 Hereinafter, more preferably 3/10 mm 2 Below, particularly preferably less than 1/10 mm 2 . The lower limit is preferably 0/10 mm 2 The above.
The thickness of the temporary support is preferably 5 μm or more, more preferably 6 μm or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, further preferably 50 μm or less, particularly preferably 25 μm or less, and most preferably less than 16 μm from the viewpoint of easy handling and versatility.
The thickness of the temporary support was calculated as an average value of arbitrary 5 points measured by cross-sectional observation based on SEM (Scanning Electron Microscope).
The temporary support may have a layer containing fine particles (lubricant layer) on one surface or both surfaces of the temporary support from the viewpoint of handling properties.
The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.
The thickness of the lubricant layer is preferably 0.05 to 1.0. Mu.m.
From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that is in contact with the photosensitive composition layer may be subjected to a surface modification treatment.
Examples of the surface modification treatment include treatments using UV irradiation, corona discharge, plasma, and the like.
The exposure amount in UV irradiation is preferably 10 to 2000mJ/cm 2 More preferably 50 to 1000mJ/cm 2 。
If the exposure amount is within the above range, the lamp output and the illuminance are not particularly limited.
Examples of the light source for UV irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and a Light Emitting Diode (LED) that emit light in a wavelength band of 150 to 450 nm.
Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.
Further, examples of the temporary support include paragraphs [0017] to [0018] of japanese patent application laid-open No. 2014-085643, paragraphs [0019] to [0026] of japanese patent application laid-open No. 2016-027363, paragraphs [0041] to [0057] of international publication No. 2012/081680, and paragraphs [0029] to [0040] of international publication No. 2018/179370, which are incorporated herein.
Examples of commercially available temporary supports include registered trademarks lumiror 16KS40 and lumiror 16FB40 (both of which are TORAY INDUSTRIES, inc.); cosmoshine a4100, cosmoshine a4300 and Cosmoshine a8300 (manufactured by Toyobo co.
[ photosensitive composition layer ]
The transfer film has a photosensitive composition layer.
The photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the resist pattern formed corresponds to the cured film.
The photosensitive composition layer preferably contains 10.0 to 90.0 mass% of the resin a, 5.0 to 70.0 mass% of the polymerizable compound, and 0.01 to 20.0 mass% of the polymerization initiator, based on the total mass of the photosensitive composition layer.
The thickness (film thickness) of the photosensitive composition layer is usually 0.1 to 300. Mu.m, preferably 0.2 to 100. Mu.m, more preferably 0.5 to 50 μm, still more preferably 0.5 to 30 μm, and particularly preferably 1 to 20 μm. This improves the developability of the photosensitive composition layer, and improves the resolution.
The photosensitive composition layer contains a resin A, a polymerizable compound and a polymerization initiator.
Hereinafter, each component that the photosensitive composition layer may contain will be described.
< resin A >
The resin a contains a structural unit a having a specific group and a structural unit b having an acid group.
The resin a is preferably an alkali-soluble resin containing the structural unit a and the structural unit b.
(structural unit a)
The structural unit a is a structural unit having a specific group (a group which generates an alkali-soluble group by the action of an alkali).
The "group which generates an alkali-soluble group by the action of a base" refers to a group which generates an alkali-soluble group by decomposition or the like by the action of a base.
However, a group derived from an alkyl (meth) acrylate (e.g., -COO-alkyl, etc.) is not included in the specific group. Therefore, a structural unit derived from an alkyl (meth) acrylate is not included in the structural unit a. The alkyl group may be linear, branched, or cyclic.
Examples of the monomer constituting the structural unit derived from the alkyl (meth) acrylate include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
In addition, the resin a is allowed to contain a group derived from an alkyl (meth) acrylate and/or a structural unit derived from an alkyl (meth) acrylate.
Examples of the alkali-soluble group which generates a specific group by the action of a base include acid groups such as a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, and a sulfonic acid group, and sulfonamide and sulfonimide groups, with acid groups being preferred and carboxyl groups being more preferred.
The structural unit a preferably contains a structural unit having a base-decomposable group, more preferably contains a structural unit having a group which generates an acid group by decomposition with a base, and from the viewpoint of reactivity and storage stability, more preferably contains at least one selected from the group consisting of a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group, particularly preferably contains at least one selected from the group consisting of a structural unit having a lactone group and a structural unit having an acid anhydride group, and most preferably contains a structural unit having a lactone group.
The "alkali-decomposable group" refers to a group which decomposes by the action of a base to produce an alkali-soluble group. For example, whether or not the base-decomposable group corresponds to can be determined by the following method.
A compound for verification having a group to be measured is prepared. Examples of the verification compound include γ -butyrolactone methacrylate as a verification compound having a lactone group and phenylsuccinic anhydride as a verification compound having an acid anhydride group.
Next, the compound for verification is dissolved in a solvent (e.g., acetonitrile) and a certain amount of an aqueous alkaline solution is added at room temperature to perform a hydrolysis reaction. Then, an acid is added to the obtained solution to make the solution acidic. The solution was judged by measuring the remaining amount of the compound for confirmation by HPLC (high performance liquid chromatography).
Specifically, if the residual amount of the verification compound measured by the above method is 80% by mass or less with respect to the total mass of the verification compound before hydrolysis, the verification compound is regarded as corresponding to a compound having an alkali-decomposable group. The remaining amount of the verification compound is preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit is usually 0 mass% or more.
Whether or not an alkali-soluble group is formed can be confirmed by isolating a compound produced by alkali decomposition and using Nuclear Magnetic Resonance (NMR) or the like.
Structural units having lactone groups
The lactone group may be any group having a lactone structure, and may be either a lactone group itself or a group having a lactone group.
The lactone group is preferably a group having a lactone structure of 5 to 7-membered ring, and more preferably a group having another ring structure such as a bicyclic structure or spiro structure condensed on the lactone structure of 5 to 7-membered ring.
In the structural unit having a lactone group, the lactone group may be directly bonded to the main chain of the resin a or may form a part of the main chain of the resin a.
The lactone group is preferably a group obtained by removing 1 or 2 or more hydrogen atoms from a lactone compound.
The lactone compound is preferably a compound represented by any one of formulae (LC 1-1) to (LC 1-17), more preferably a compound represented by any one of formulae (LC 1-1), (LC 1-4), (LC 1-5), (LC 1-6), (LC 1-13), (LC 1-14) and (LC 1-17), and still more preferably a compound represented by any one of formulae (LC 1-1), (LC 1-4) and (LC 1-17).
In the case of the above compound, the pattern shape becomes good, and the resist pattern releasability improves.
Also, lactone compounds generally exist as optical isomers.
Any optical isomer may be used for the lactone compound. The lactone compound may be used alone or in combination of two or more. In other words, a mixture of optical isomers may be used. When one optical isomer is used, the optical purity (ee) of the lactone compound is preferably 90 or more, more preferably 95 or more.
[ chemical formula 1]
In the formulae (LC 1-1) to (LC 1-17), rb 2 Represents a substituent. n is 2 Represents an integer of 0 or more.
As Rb 2 Examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group and a cyano group.
When n is 2 When it is 2 or more, rb is plural 2 May be the same or different, and there are a plurality of Rb 2 May be bonded to each other to form a ring.
As the structural unit having a lactone group, the structural unit represented by the formula (AI) is preferable.
[ chemical formula 2]
In formula (AI), rb 0 Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Ab represents an alkylene group, a 2-valent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a 2-valent group formed by combining these groups, or a single bond. V represents a group formed by removing 1 hydrogen atom from the compound represented by any one of formulae (LC 1-1) to (LC 1-17).
Rb 0 Represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
As Rb 0 Examples of the substituent which the alkyl group which may have a substituent may have include a hydroxyl group and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As Rb 0 Preferably a hydrogen atom or a methyl group.
Ab represents an alkylene group, a 2-valent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a 2-valent group formed by combining these groups, or a single bond.
As Ab, a single bond or-Ab is preferred 1 -CO 2 -。Ab 1 Represents a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group. As Ab 1 Preferably a methylene, ethylene, cyclohexyl, adamantyl or norbornyl group.
V represents a group obtained by removing 1 hydrogen atom from the compound represented by any one of formulas (LC 1-1) to (LC 1-17).
The compounds represented by any one of formulae (LC 1-1) to (LC 1-17) are as described above.
Specific examples of the structural unit having a lactone group are described below, but the present invention is not limited to these. Wherein Rx represents a hydrogen atom, a methyl group or-CH 2 OH or-CF 3 。
[ chemical formula 3]
[ chemical formula 4]
The structural units having a lactone group may be used singly or in combination of two or more.
The content of the structural unit having a lactone group is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 7 to 30% by mass, based on all the structural units of the resin a.
Structural units having an acid anhydride group
The acid anhydride group may be any acid anhydride group itself or a group having an acid anhydride group, as long as it is a group having an acid anhydride structure.
As the acid anhydride group, a carboxylic anhydride group (-C (= O) -O-C (= O) -), and more preferably a cyclic carboxylic anhydride group (a ring group including-C (= O) -O-C (= O) -).
The carboxylic anhydride group may be linear, branched or cyclic, but is preferably cyclic.
The number of ring members constituting the ring of the cyclic carboxylic anhydride group is preferably 5 to 7, more preferably 5 or 6, and still more preferably 5.
As the acid anhydride group, a group having a structure derived from an acid anhydride is preferable.
Examples of the acid anhydride include maleic anhydride, itaconic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, phthalic anhydride, and benzoic anhydride, and maleic anhydride or itaconic anhydride is preferable.
As the acid anhydride, a compound represented by the formula (P-1) is preferable.
[ chemical formula 5]
In the formula (P-1), R A1a Represents a substituent. Z is a linear or branched member 1a Represents (n) forming a ring containing-C (= O) -O-C (= O) - 1a + 2) valent groups. n is 1a Represents an integer of 0 or more.
As R A1a Examples of the substituent include an alkyl group.
When Z is 1a When a group having a valence of 2 is represented, as Z 1a The alkylene group having 2 to 4 carbon atoms is preferable, the alkylene group having 2 or 3 carbon atoms is more preferable, and the alkylene group having 2 carbon atoms is further preferable.
n 1a Represents an integer of O or more.
n 1a An integer of 0 to 4 is preferable, an integer of 0 to 2 is more preferable, and 0 is further preferable.
When n is 1a When an integer of 2 or more is represented, a plurality of R's are present A1a May be the same or different. And, there are a plurality of R A1a The ring may be bonded to each other to form a ring, and preferably the ring is not bonded to each other to form a ring.
The structural unit having an acid anhydride group is also preferably a structural unit represented by the formula (AII) or a structural unit represented by the formula (AIII).
[ chemical formula 6]
In the formulae (AII) and (AIII), RIII independently represents a hydrogen atom or a substituent. As RIII, a hydrogen atom is preferred.
ahd 1 Represents a group formed by removing 1 hydrogen atom from each of adjacent ring-member atoms of the compound represented by the formula (P-1).
ahd 2 Represents a group formed by removing 2 hydrogen atoms from 1 ring member atom of the compound represented by the formula (P-1).
The structural unit having an acid anhydride group is preferably a structural unit derived from an unsaturated carboxylic acid anhydride, more preferably a structural unit derived from a compound represented by the formula (P-1), and still more preferably a structural unit represented by the formula (AII) or a structural unit represented by the formula (AIII).
Specific examples of the structural unit having an acid anhydride group are described below, but the structural unit hasThe structural unit of the acid anhydride group is not limited to these specific examples. Rx represents a hydrogen atom, a methyl group, or-CH 2 OH or-CF 3 。
[ chemical formula 7]
The structural units a may be used singly or in combination of two or more.
The content of the structural unit a is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, even more preferably 5 to 40% by mass, particularly preferably 5 to 30% by mass, and even more preferably 5 to 20% by mass, based on all the structural units of the resin a.
(structural unit b)
The structural unit b is a structural unit having an acid group.
Examples of the acid group of the structural unit b include a carboxyl group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxyl group is preferable.
As the structural unit b, a structural unit derived from the 1 st monomer is preferable, and a structural unit derived from (meth) acrylic acid is more preferable.
The 1 st monomer is a monomer having a carboxyl group. Examples of the 1 st monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and 4-vinylbenzoic acid, and (meth) acrylic acid is preferable.
The structural unit B is preferably a structural unit represented by the formula (B).
[ chemical formula 8]
In the formula (B), rb represents a hydrogen atom, a methyl group or-CH 2 OH or-CF 3 。
The structural units b may be used singly or in combination of two or more.
The content of the structural unit b is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 30% by mass, and particularly preferably 14 to 25% by mass, based on all the structural units of the resin a.
In the resin a, the content of the structural unit a is preferably 5 to 50% by mass and the content of the structural unit b is 10 to 30% by mass with respect to all the structural units of the resin a, and more preferably the content of the structural unit a is 7 to 30% by mass and the content of the structural unit b is 14 to 25% by mass with respect to all the structural units of the resin a.
(other structural units)
The resin a may contain other structural units in addition to the structural unit a and the structural unit b.
From the viewpoint of suppressing the thickness of the line width and the deterioration of the resolution when the focal position shifts during exposure, the resin a preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group.
Examples of the aromatic hydrocarbon group include an optionally substituted phenyl group and an optionally substituted aralkyl group.
The content of the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more, based on all the structural units of the resin a. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less, with respect to all the structural units of the resin a. When the photosensitive composition layer contains two or more resins a, the mass average value of the content of the structural units derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.
Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like), preferably a monomer having an aralkyl group or styrene, and more preferably styrene.
When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and still more preferably 25 to 55% by mass, based on all the structural units of the resin a. When the photosensitive composition layer contains two or more kinds of the resins a, the mass average value of the content of the structural units derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.
Examples of the aralkyl group include a phenylalkyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.
Examples of the monomer containing a phenylalkyl group which may have a substituent include phenylethyl (meth) acrylate.
Examples of the monomer containing a benzyl group which may have a substituent include (meth) acrylates having a benzyl group such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; the vinyl monomer having a benzyl group such as vinylbenzyl chloride or vinylbenzyl alcohol is preferably a (meth) acrylate having a benzyl group, and more preferably benzyl (meth) acrylate.
When the monomer having an aromatic hydrocarbon group is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and further preferably 25 to 55% by mass, based on all the structural units of the resin a.
As another constitutional unit, a constitutional unit derived from the 2 nd monomer can be also mentioned.
The 2 nd monomer is a monomer which is not acidic (has no acid group) and has a polymerizable group in the molecule.
The meaning of the polymerizable group is the same as that of the polymerizable group of the polymerizable compound described later, and the preferable embodiment is also the same.
Examples of the second monomer include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile, and the like.
Among them, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.
The content of the structural unit derived from the 2 nd monomer is preferably 1 to 80% by mass, more preferably 1 to 60% by mass, and still more preferably 1 to 50% by mass, based on the whole structural units of the resin a.
The resin may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain.
By using a monomer having a group having a branched structure in a side chain or a monomer having a group having an alicyclic structure in a side chain, the branched structure or the alicyclic structure can be introduced into the side chain of the resin. The group having an alicyclic structure may be either a monocyclic ring or a polycyclic ring.
"side chain" refers to a group of atoms branching from the main chain. The "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin.
Examples of the monomer containing a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate.
Among them, isopropyl (meth) acrylate, isobutyl (meth) acrylate, or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.
Examples of the monomer containing a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms can be mentioned.
More specific examples thereof include (bicyclo [ 2.2.1 ] heptyl-2) acrylate, (meth) acrylic acid 1-adamantyl ester, (meth) acrylic acid 2-adamantyl ester, (meth) acrylic acid 3-methyl-1-adamantyl ester, (meth) acrylic acid 3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid 3-ethyl adamantyl ester, (meth) acrylic acid 3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid 3,5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid 3, 5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid 2-methyl-2-adamantyl ester, (meth) acrylic acid 2-ethyl-2-adamantyl ester, (meth) acrylic acid 3-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4, 7-methylindene (methandene) -5-yl ester, (meth) acrylic acid octahydro-4, 7-methylindene-1-yl methyl ester, (meth) acrylic acid tricyclo-menthyl ester, 3-hydroxy-2, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Among the above, cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate), 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate, and tricyclodecane (meth) acrylate are preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, and tricyclodecane (meth) acrylate are more preferable.
Examples of the other structural unit include a structural unit having a polymerizable group.
The polymerizable group includes a polymerizable group of a polymerizable compound described later, preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
The polymerizable group is also preferably a polymerizable group capable of undergoing a polymerization reaction with the polymerizable group of the polymerizable compound.
The resin containing a structural unit having a polymerizable group is preferably obtained by reacting a resin containing a structural unit derived from the 1 st monomer with the 3 rd monomer.
The 3 rd monomer is a monomer having 2 or more polymerizable groups in the molecule, and preferably a monomer having 2 polymerizable groups in the molecule.
Examples of the polymerizable group include polymerizable groups of polymerizable compounds described later. Among these, the 3 rd monomer preferably has two polymerizable groups, more preferably has an ethylenically unsaturated group and a cationic polymerizable group, and further preferably has an acryloyl group or a methacryloyl group and an epoxy group.
Examples of the 3 rd monomer include glycidyl (meth) acrylate.
The structural unit having a polymerizable group is preferably a structural unit represented by the formula (P).
[ chemical formula 9]
In the formula (P), R P Represents a hydrogen atom or a methyl group. L is P Represents a 2-valent linking group. P represents a polymerizable group.
R P Represents a hydrogen atom or a methyl group.
As R P Preferably a hydrogen atom.
L P Represents a 2-valent linking group.
As the above-mentioned linking group having a valence of 2, examples thereof include-CO-, -O-,; -S-, -SO-, -S0 2 -、-NR N A 2-valent hydrocarbon group, and a 2-valent group formed by combining these. R N Represents a substituent.
Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.
The alkylene group may be linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms. The above alkylene group may have a hetero atom, and a methylene group in the above alkylene group may be substituted with a hetero atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.
The cycloalkylene group may be any of a monocyclic ring and a polycyclic ring. The carbon number of the cycloalkylene group is preferably 3 to 20, more preferably 5 to 10, and still more preferably 6 to 8.
The arylene group may be a single ring or a polycyclic ring. The arylene group preferably has 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10 carbon atoms. As the above arylene group, a phenylene group is preferable.
The cycloalkylene group and the arylene group may have a hetero atom as a ring member. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.
The hydrocarbon group may have a substituent.
Examples of the substituent include a halogen atom (e.g., fluorine atom), a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group, and a hydroxyl group is preferable.
As L P Alkylene groups which may have hetero atoms are preferred.
P represents a polymerizable group.
The polymerizable group is as described above.
Examples of the structural unit having a polymerizable group include the following structural units.
Wherein Rx and Ry each independently represent a hydrogen atom or a methyl group.
[ chemical formula 10]
The content of the structural unit having a polymerizable group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, further preferably 15 to 40% by mass, and particularly preferably 20 to 40% by mass, based on the total structural units of the resin a.
Examples of the method for introducing a polymerizable group into the resin a include a method in which an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride are reacted with a group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group of the resin a.
Preferred examples of the method for introducing a polymerizable group into the resin a include the following methods: after a polymer having a carboxyl group is synthesized by a polymer reaction, a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the obtained polymer to introduce a (meth) acryloyloxy group into the polymer. Another method includes the following steps: after synthesizing a polymer having a hydroxyl group by a polymer reaction, (meth) acryloyloxy group is introduced into the polymer by reacting a part of the hydroxyl group of the obtained polymer with (meth) acrylate having an isocyanate group.
By these methods, a resin a having a (meth) acryloyloxy group in a side chain can be obtained.
The reaction temperature of the polymer reaction is preferably 80 to 110 ℃. The polymer reaction is preferably carried out using a catalyst, and more preferably using an ammonium salt (tetraethylammonium bromide).
The reaction temperature of the polymerization reaction is preferably 70 to 100 ℃ and more preferably 80 to 90 ℃. The polymerization reaction preferably uses a polymerization initiator, more preferably an azo initiator, and further preferably V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) or V-65 (manufactured by FUJIFILM Wako Pure Chemical Corporation).
The resin a is preferably the following.
(mode 1): comprises a structural unit a, a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from styrene or a structural unit derived from benzyl methacrylate.
(mode 2): comprises a structural unit a, a structural unit derived from methacrylic acid, a structural unit having a polymerizable group, and a structural unit derived from styrene or a structural unit derived from benzyl methacrylate.
In the above-described preferred embodiments, the content of each constituent unit is preferably set to the above-described preferred embodiments. Preferred embodiments of the structural unit a are as described above.
The photosensitive composition layer may contain other resins in addition to the resin a.
Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylene imines, polyallylamines, and polyalkylene glycols.
The glass transition temperature Tg of the resin A is preferably from 30 to 135 ℃. By using the resin a having a Tg of 135 ℃ or less, deterioration in line width and resolution at the time of focus shift during exposure can be suppressed. From this viewpoint, the Tg of the resin A is more preferably 130 ℃ or lower, still more preferably 120 ℃ or lower, and particularly preferably 110 ℃ or lower. Further, by using the resin a having a Tg of 30 ℃ or higher, the edge melting resistance can be improved. From this viewpoint, the Tg of the resin A is more preferably 40 ℃ or higher, still more preferably 50 ℃ or higher, particularly preferably 60 ℃ or higher, most preferably 70 ℃ or higher.
The acid value of the resin A is preferably 250mgKOH/g or less, more preferably 200mgKOH/g or less, still more preferably 190mgKOH/g or less, and particularly preferably 180mgKOH/g or less. The lower limit is preferably 10mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 60mgKOH/g or more, particularly preferably 80mgKOH/g or more, most preferably 90mgKOH/g or more.
The "acid value (mgKOH/g)" means the mass (mg) of potassium hydroxide required for neutralizing 1g of the sample. The acid value can be determined, for example, in accordance with JIS K0070: 1992.
The acid value of the resin a can be adjusted depending on the kind of the structural unit contained in the resin and/or the content of the structural unit containing an acid group.
The acid value of the carboxyl group-derived resin A is preferably 60 to 250mgKOH/g, more preferably 80 to 200mgKOH/g, and still more preferably 90 to 180mgKOH/g. The acid value derived from the carboxyl group does not include a carboxyl group which generates a specific group by the action of a base.
The acid value of the alkali-soluble group derived from the resin A to form a specific group by the action of an alkali is preferably 5 to 200mgKOH/g, more preferably 20 to 100mgKOH/g, and still more preferably 20 to 80mgKOH/g.
The acid value of the resin a derived from an alkali-soluble group which generates a specific group by the action of an alkali can be calculated from the theoretical acid value of the resin. Specifically, when the resin a has a lactone group, the theoretical acid value can be calculated from the structure of the resin in which all of the lactone groups are opened to generate an alkali-soluble group.
The weight average molecular weight of the resin A is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, further preferably 10,000 to 60,000, particularly preferably 10,000 to 50,000.
When the weight average molecular weight is 500,000 or less, the resolution and the developability can be improved. When the weight average molecular weight is 5,000 or more, the properties of the developed aggregates and the properties of the unexposed film such as the edge meltability and the chipping property of the transfer film can be controlled. The "edge-meltability" refers to how easily the photosensitive composition layer overflows from the end face of the roll when the transfer film is wound into a roll. The swarf property is the ease with which swarf can be scattered when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the transfer film, etc., the chips are transferred to the mask in the subsequent exposure step, etc., and become a cause of defective products.
The degree of dispersion of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.
The resin a may be used alone or in combination of two or more.
The content of the resin a is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the photosensitive composition layer. When the content of the resin a is 90 mass% or less with respect to the total mass of the photosensitive composition layer, the development time can be controlled. When the content of the resin a is 10 mass% or more with respect to the total mass of the photosensitive composition layer, the edge melt resistance can be improved.
As a method for synthesizing the resin a, for example, the above-mentioned single or plural monomers are polymerized using a radical polymerization initiator such as a peroxide polymerization initiator (e.g., benzoyl peroxide) or an azo polymerization initiator (e.g., azobisisobutyronitrile). The polymerization method is preferably performed by adding the monomer solution and the radical polymerization initiator solution dropwise under a nitrogen stream to a heated solvent (preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, or isopropyl alcohol) and heating and stirring the mixture. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As a method for synthesizing the resin a, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
< polymerizable Compound >
The photosensitive composition layer contains a polymerizable compound.
The "polymerizable compound" is a compound having a polymerizable group and different from the resin a, which is polymerized by a polymerization initiator described later.
The polymerizable group of the polymerizable compound may be a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; the group having a cationically polymerizable group such as an epoxy group or an oxetanyl group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups in the molecule (hereinafter, also referred to as "ethylenically unsaturated compound"), and more preferably a compound having 2 or more ethylenically unsaturated groups in the molecule (hereinafter, also referred to as "polyfunctional ethylenically unsaturated compound"), from the viewpoint of more excellent photosensitivity of the photosensitive composition layer.
In addition, the number of ethylenically unsaturated groups in the molecule of the ethylenically unsaturated compound is 1 or more, preferably 1 to 6, more preferably 1 to 3, and further preferably 2 to 3, from the viewpoint of further excellent resolution and peelability.
The polymerizable compound may have an alkyleneoxy group.
The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of addition of alkyleneoxy groups to the polymerizable compound is preferably 2 to 30, more preferably 2 to 20 per 1 molecule.
The polymerizable compound preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in the molecule, from the viewpoint of more excellent balance between the photosensitivity of the photosensitive composition layer and the resolution and peelability.
The content of the 2-functional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably 40.0% by mass or more, and further preferably 50.0% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less. That is, all of the polymerizable compounds contained in the photosensitive composition layer may be 2-functional ethylenically unsaturated compounds.
The content of the 3-functional ethylenically unsaturated compound is preferably 10.0% by mass or more, and more preferably 15.0% by mass or more, based on the total mass of the polymerizable compound. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less, and further preferably 50.0% by mass or less. That is, all of the polymerizable compounds contained in the photosensitive composition layer may be 3-functional ethylenically unsaturated compounds.
The ethylenically unsaturated compound is preferably a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group.
(polymerizable Compound B1)
The polymerizable compound also preferably contains a polymerizable compound B1 having 1 or more aromatic rings and 2 ethylenically unsaturated groups.
The polymerizable compound B1 includes a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings among the polymerizable compounds.
Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; aromatic heterocycles such as a thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring; the condensed ring formed by combining these is preferably an aromatic hydrocarbon ring, and more preferably a benzene ring. The aromatic ring may have a substituent.
The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive composition layer by the developer.
Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and the bisphenol a structure is preferred.
Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.
The two ends of the bisphenol structure may be directly bonded to the polymerizable group or may be bonded via 1 or more alkyleneoxy groups.
The alkyleneoxy group capable of being added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of addition of alkyleneoxy groups (preferably ethyleneoxy groups) to the bisphenol structure is preferably 2 to 30, more preferably 2 to 20 per 1 molecule.
The polymerizable compound B1 having a bisphenol structure includes, for example, paragraphs [0072] to [0080] of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated herein by reference.
The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloyloxyalkyloxy) phenyl) propane.
Examples of the 2, 2-bis (4- ((meth) acryloyloxyalkyloxy polyalkoxy) phenyl) propane include ethoxylated bisphenol a dimethacrylate (BPE series, shin-Nakamura Chemical Co., ltd. Manufactured), such as 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324m, hitachi Chemical Co., ltd. Manufactured), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane and 2, 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (fan-Nakamura Chemical Co., ltd. Manufactured), 2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200my, hitachi Chemical Co., ltd. Manufactured), and ethoxylated (10) bisphenol a diacrylate (NK Ester a-BPE-10, n-Nakamura Co., ltd. Manufactured).
The polymerizable compound B1 is also preferably a compound represented by the formula (B1).
[ chemical formula 11]
In the formula (B1), R 1 And R 2 Each independently represents a hydrogen atom or a methyl group. A represents an ethylene group. B represents a propylene group. n1 and n3 each independently represent an integer of 1 to 39. n1+ n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29. n2+ n4 represents an integer of 0 to 30.
Of structural units of- (A-O) -and- (B-O) -the arrangement may be random or block. In the case of a block, either one of- (A-O) -and- (B-O) -may be on the biphenyl (bispheny 1) side.
N1+ n2+ n3+ n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. N2+ n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, particularly preferably 0.
From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 is preferably 10.0 mass% or more, more preferably 20.0 mass% or more, and still more preferably 25.0 mass% or more, with respect to the total mass of the photosensitive composition layer. From the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive composition bleeds out from the end of the transfer member), the upper limit is preferably 70.0% by mass or less, and more preferably 60.0% by mass or less, with respect to the total mass of the photosensitive composition layer.
From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, further preferably 55.0% by mass or more, and particularly preferably 60.0% by mass or more, based on the total mass of the polymerizable compounds. From the viewpoint of peelability, the upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, further preferably 95.0% by mass or less, particularly preferably 90.0% by mass or less, and most preferably 85.0% by mass or less, based on the total mass of the polymerizable compound.
(other polymerizable Compound)
The photosensitive composition layer may contain other polymerizable compounds in addition to the above.
Examples of the other polymerizable compound include known polymerizable compounds.
Specifically, there may be mentioned a compound having 1 ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.
Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.
Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
Examples of the alkylene glycol di (meth) acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., ltd.), 1, 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., ltd.), ethylene glycol dimethacrylate, 1, 10-decanediol diacrylate and neopentyl glycol di (meth) acrylate.
Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di (meth) acrylate.
Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Further, examples of commercially available urethane di (meth) acrylate include 8UX-015A (manufactured by Taisei Fine Chemical Co., ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., ltd.).
Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide-modified products thereof.
"(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. Also, "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., kaya RAD (registered trademark) DPCA-20 and Shin-Nakamura Chemical Co., ltd., A-9300-1CL, manufactured by Ltd.), alkylene oxide-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., kaya RAD (registered trademark) 135, manufactured by Ltd.), kayaRAD RP-1040, shin-Nakamura Chemical Co., ltd., ATM-35E and A-9300, manufactured by Ltd., and DAICEL-ALLNEX LTD. Manufactured by Ltd.), ethoxylated glycerin trimethacrylate esters (e.g., shin-Nakamura Co., shin-GLY-9E, manufactured by Ltd.), ARONIX (registered trademark) series (e.g., TOOSOSOSOSCO., manufactured by Ltd., A-520, LTM, LTEI, and the like).
The polymerizable compound may be a polymerizable compound having an acid group (e.g., a carboxyl group). The acid group may form a group derived from an acid anhydride.
Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI co., ltd.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI co., ltd.).
Examples of the polymerizable compound having an acid group include polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of Japanese patent application laid-open No. 2004-239942.
The molecular weight of the polymerizable compound is preferably 3,000 or less, more preferably 200 to 3,000, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
One kind of the polymerizable compound may be used alone or two or more kinds may be used.
The content of the polymerizable compound is preferably 10.0 to 70.0% by mass, more preferably 15.0 to 70.0% by mass, and still more preferably 20.0 to 70.0% by mass, based on the total mass of the photosensitive composition layer.
< polymerization initiator >
The photosensitive composition layer contains a polymerization initiator.
As the polymerization initiator, for example, a known polymerization initiator can be used depending on the form of the polymerization reaction. Specifically, a thermal polymerization initiator and a photopolymerization initiator can be mentioned.
The polymerization initiator may be any of radical polymerization initiators and cationic polymerization initiators.
The photosensitive composition layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that initiates polymerization of the polymerizable compound upon receiving an active light such as ultraviolet light, visible light, and X-ray. Examples of the photopolymerization initiator include known photopolymerization initiators.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.
Examples of the photo radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylphenone structure, a photopolymerization initiator having an α -hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.
From the viewpoint of photosensitivity, visibility and resolution of exposed portions and non-exposed portions, the photo radical polymerization initiator preferably contains at least one selected from 2,4, 5-triarylimidazole dimers and derivatives thereof. In addition, 2,4, 5-triarylimidazole dimers and derivatives thereof may have the same or different 2,4, 5-triarylimidazole structures.
Examples of the derivatives of the 2,4, 5-triarylimidazole dimer include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.
Examples of the photo-radical polymerization initiator include those described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-095716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783.
Examples of the photo radical polymerization initiator include ethyl Dimethylaminobenzoate (DBE), benzoin methyl ether, (p, p '-dimethoxybenzyl) anise ester, TAZ-110 (Midori Kagaku co., ltd.), benzophenone, 4' -bis (diethylamino) benzophenone, TAZ-111 (Midori Kagaku co., ltd., ltd.), 1- [4- (phenylthio) ] -1, 2-octanedione-2- (O-benzoyloxime) (IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (0-acetyloxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (Omnirad 379EG, manufactured by IGM Resins B.V), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Omnirad 907, IGM Resins B.V), 2-hydroxy-1- [4- (4-methylpropionyl) -2-hydroxypropionyl-2- (2-methylpropionyl-oxime-0-02, IRGACURE (registered trademark), IRGACURE OXE-01, manufactured by BASF), IRGACURE-4- (4-morpholino) methyl-2- (4-methylpropionyl) -1-2- (2-hydroxy-2-propionyl-2- (2-methyl-2-methyl-butanone, omnirad) ) Benzyl group ] phenyl group } -2-methylpropan-1-one (Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins B.V.), 2-dimethoxy-1, 2-diphenylethan-1-one (Omnirad 651, manufactured by IGM Resins B.V.), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, IGM Resins B.V., inc.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Omnirad 819, IGM Resins B.V., inc.), oxime ester type photopolymerization initiators (Lunar 6, DKSH Japan K.K., inc.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbiimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (B-CIM, hampford), 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (BCTB, tokyo Chemical Industry Co., ltd.), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane -1, 2-dione-2- (O-benzoyl oxime) (TR-PBG-305, changzzhou Tronly New Electronic Materials CO., ltd., manufactured), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (0-acetyloxime) (TR-PBG-326, changzzhou Tronly New Electronic Materials CO., ltd., manufactured) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (TR-PBG-391, changzhou Tronly New Electronic Materials CO., ltd., manufactured).
The photo cation polymerization initiator (photo acid generator) is a compound that generates an acid upon receiving an activating light. As the photo cation polymerization initiator, a compound which generates an acid by being induced by an activating light having a wavelength of 300nm or more (preferably 300 to 450 nm) is preferable. The photo cation polymerization initiator that is not directly sensitive to the activation light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound that generates an acid by being sensitive to the activation light having a wavelength of 300nm or more.
As the photo cation polymerization initiator, a photo cation polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photo cation polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photo cation polymerization initiator that generates an acid having a pKa of 2 or less is even more preferable. The lower limit is preferably-10.0 or more.
Examples of the photo cation polymerization initiator include ionic photo cation polymerization initiators and nonionic photo cation polymerization initiators.
Examples of the ionic photo-cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
Examples of the ionic photo-cationic polymerization initiator include ionic photo-cationic polymerization initiators described in paragraphs [0114] to [0133] of Japanese patent application laid-open Nos. 2014-085643.
Examples of the nonionic photo cation polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds.
Examples of the trichloromethyl-s-triazine, diazomethane compound and imide sulfonate compound include compounds described in paragraphs [0083] to [0088] of Japanese patent laid-open No. 2011-221494.
Examples of the oxime sulfonate compound include compounds described in paragraphs [0084] to [0088] of international publication nos. 2018/179640.
One polymerization initiator may be used alone, or two or more polymerization initiators may be used.
The content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, with respect to the total mass of the photosensitive composition layer.
< coloring matter >
The photosensitive composition layer may contain a dye (hereinafter, also referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical, from the viewpoints of visibility of an exposed portion and a non-exposed portion, and visibility and resolution of a pattern after development.
The maximum absorption wavelength of the pigment is preferably changed by an acid or a radical. The dye is a compound different from the compound D.
When the dye N is contained, although the detailed mechanism is not clear, the adhesion with an adjacent layer (for example, an intermediate layer) is improved and the resolution is further excellent.
The "maximum absorption wavelength of the pigment is changed by an acid, an alkali, or a radical" may refer to any one of a method in which a pigment in a colored state is decolored by an acid, an alkali, or a radical, a method in which a pigment in a decolored state is colored by an acid, an alkali, or a radical, and a method in which a pigment in a colored state is changed to a colored state of another color.
Specifically, the dye N may be either a compound that develops color by changing its decolorized state upon exposure or a compound that develops color by changing its colored state upon exposure. In the above case, the dye may be one in which an acid, a base, or a radical is generated in the photosensitive composition layer by exposure and acts to change the state of coloration or decolorization, or one in which the state (for example, pH or the like) in the photosensitive composition layer is changed by a change in acid, base, or radical. Further, the dye may be one which changes its color development or decoloration state by being directly stimulated by an acid, an alkali, or a radical without exposure.
Among them, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.
From the viewpoint of visibility and resolution of the exposed portions and the unexposed portions, the photosensitive composition layer preferably contains a dye whose maximum absorption wavelength changes by a radical as both the dye N and the photo radical polymerization initiator. The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, from the viewpoint of visibility of the exposed portion and the unexposed portion.
Examples of the color developing mechanism of the dye N include a system in which a radical reactive dye, an acid reactive dye, or a base reactive dye (for example, leuco dye) is developed by adding a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator), or a photo base generator to a photosensitive composition layer, followed by exposure to light, and then by radicals, acids, or bases generated by the photo radical polymerization initiator, the photo cation polymerization initiator, or the photo base generator.
From the viewpoint of visibility of the exposed portion and the non-exposed portion, the maximum absorption wavelength in the wavelength range of 400 to 780nm in the color development of the dye N is preferably 550nm or longer, more preferably 550 to 700nm, and still more preferably 550 to 650nm.
The dye N may have 1 or 2 or more maximum absorption wavelengths in a wavelength range of 400 to 780nm in the case of color development. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.
The maximum absorption wavelength of the pigment N can be measured by using a spectrophotometer in an atmospheric environment: UV3100 (manufactured by Shimadzu Corporation) measures the transmission spectrum of a solution containing a dye N (liquid temperature 25 ℃) in the wavelength range of 400 to 780nm and detects the wavelength at which the intensity of light becomes extremely small (maximum absorption wavelength).
Examples of the dye that develops color or decolors by exposure include colorless compounds.
Examples of the coloring matter decolorized by exposure to light include a leuco compound, diarylmethane-based coloring matter, oxazine-based coloring matter, xanthene-based coloring matter, iminonaphthoquinone-based coloring matter, azomethine-based coloring matter, and anthraquinone-based coloring matter.
The dye N is preferably a colorless compound from the viewpoint of visibility of an exposed portion and a non-exposed portion.
Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolylphthalein skeleton (indolylphthalein-based dye), and a colorless compound having a leuco auramine skeleton (leuco auramine-based dye).
Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.
From the viewpoint of visibility of the exposed portion and the non-exposed portion, the colorless compound preferably has a lactone ring, a sulfinolactone ring (sultone ring), or a sultone ring. Thus, the lactone ring, sulfinolactone ring or sultone ring of the colorless compound can be reacted with the radical generated by the photo radical polymerization initiator or the acid generated by the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolorize the colorless compound, or the colorless compound can be changed into an open ring state and develop the color. The colorless compound is preferably a compound having a lactone ring, a sulfinolactone ring, or a sultone ring and developing a color by radical or acid ring opening, and more preferably a compound having a lactone ring and developing a color by radical or acid ring opening.
Examples of the pigment N include dyes and leuco compounds.
Examples of the dye include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metanil yellow (metanil yellow), thymolsulfonephthalein (thymol sulfonphthalein), xylenol blue (xylenol blue), methyl orange, p-methyl red, congo red, benzopurpurin (benzopurpurine) 4B, a-naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), parafuchsin (parafuchsine), victoria pure blue (victoria blue) -naphthalene sulfonate, victoria pure blue h (bodoya black co, oil blue #603, inc., ltrie blue # co, inc. Ltd., manufactured), oil pink #312 (organic Chemical Industries co., ltd., manufactured), oil red 5B (organic Chemical Industries co., manufactured by ltd.), oil scarlet #308 (organic scarlet) 308 (organic Chemical Industries co., manufactured by ltd., manufactured), oil red OG (organic Chemical Industries co., manufactured by ltd.), oil red RR (organic Chemical Industries co., manufactured by ltd.), oil green #502 (organic Chemical Industries co., manufactured by ltd.), stegano red (spilon red) BEH (hodoga Chemical co., manufactured by ltd.), cresol purple, cresol red cresol, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminoquinone, 2-carboxy-p-phenyliminophenyl group 4-p-diethylaminophenylquinonyl-naphthoquinone, 2-carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenylimino-naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1- β -naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.
Examples of the colorless compound include p, p' -hexamethyltriaminotriphenylmethane (colorless crystal violet), pergascript Blue SRB (Ciba-Geigy Co., ltd.), crystal violet lactone, malachite green lactone, benzoyl leuco methylene Blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-chlorofluoran, 3- (N, N-diethylamino) -6-methoxy-7-aminofluoran, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluoran, 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3-piperidinyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (3-diethylamino) -4-ethylaminophenyl) -3 ' -diphenylspiro (1-methyl-1-2-methylindol) phthalide, and 3' -diphenylspiro (1H-ethyl-2-methylindol-3 ' -diphenylamino) phthalide, 9' - [9H ] xanthen-3-one.
The dye N is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye whose color is developed by a radical, from the viewpoint of excellent visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution.
As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate is preferable.
One or more kinds of the pigment N may be used alone.
The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of excellent visibility of the exposed portion and the unexposed portion, and pattern visibility and resolution after development.
The content of the pigment N is a content of the pigment when all the pigments N contained in the total mass of the photosensitive composition layer are in a colored state. Hereinafter, a method for quantifying the content of pigment N will be described by taking a pigment that develops color by a radical as an example.
A solution prepared by dissolving dye N (0.001 g) in methyl ethyl ketone (100 mL) and a solution prepared by dissolving dye N (0.01 g) were prepared. To each of the obtained solutions, a photo radical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan ltd.) was added, and light having a wavelength of 365nm was irradiated, thereby generating radicals to bring all the pigments N into a colored state. Then, the absorbance of each solution having a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV 3100, manufactured by Shimadzu Corporation) under an atmospheric environment, and a calibration curve was prepared.
Next, the absorbance of the solution in which all the dyes were developed was measured by the same method as described above except that the photosensitive composition layer (3 g) was dissolved in methyl ethyl ketone instead of the dye N. The content of the pigment N contained in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer on the basis of the calibration curve. The meaning of the "photosensitive composition layer (3 g)" is the same as that of 3g of the total solid content in the photosensitive composition.
< thermally crosslinkable Compound >
The photosensitive composition layer may contain a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
The thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound but treated as a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds, and the blocked isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when the resin and/or the polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film is lowered, and the function tends to be enhanced when the film obtained by curing the photosensitive composition layer is used as a cured film.
The "blocked isocyanate compound" refers to a compound having a structure in which an isocyanate group of an isocyanate is protected by a blocking agent.
The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160 ℃ and more preferably 130 to 150 ℃.
Examples of the method for measuring the dissociation temperature of the blocked isocyanate compound include a method of measuring the dissociation degree by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter (for example, DSC6200, manufactured by Seiko Instruments inc.) and using the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound.
Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound such as malonic diester and an oxime compound.
Examples of the malonic diester include dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate.
Examples of the oxime compound include compounds having a structure represented by — C (= N-OH) -in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime.
Among them, an oxime compound is preferable as a capping agent having a dissociation temperature of 100 to 160 ℃ from the viewpoint of storage stability.
From the viewpoint of improving the brittleness of the film and enhancing the adhesion force with the transferred object, it is preferable that the blocked isocyanate compound has an isocyanurate structure.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating hexamethylene diisocyanate to protect it.
Among these, a blocked isocyanate compound having an isocyanurate structure is preferably a compound having an oxime structure in which an oxime compound is used as a blocking agent, from the viewpoint that the dissociation temperature can be easily adjusted in a preferred range and the development residue can be reduced as compared with a compound having no oxime structure.
The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is, for example, the same as the polymerizable group contained in the polymerizable compound, and preferred embodiments thereof are also the same.
Examples of the blocked isocyanate compound include Karenz series (registered trademark) (manufactured by SHOWA DENKO K.K.) such as AOI-BM, MOI-BM and MOI-BP; the end-capped Duranate series (registered trademark) such as TPA-B80E and WT32-B75P (manufactured by Asahi Kasei Chemicals Corporation).
The blocked isocyanate compound is preferably the following compound.
[ chemical formula 12]
The thermally crosslinkable compound may be used alone or in combination of two or more.
The content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.
< pigments >
The photosensitive composition layer may contain a pigment.
When the photosensitive composition layer contains a pigment, the photosensitive composition layer corresponds to the colored resin layer.
In recent years, a cover glass (cover glass) having a black frame-shaped light shielding layer formed on a peripheral edge portion of a back surface of a transparent glass substrate or the like is sometimes attached to a liquid crystal display window included in an electronic device in order to protect the liquid crystal display window. In order to form such a light-shielding layer, a colored resin layer may be used.
The pigment may be appropriately selected depending on the desired hue, and examples thereof include a black pigment, a white pigment, and a color pigment other than black and white, and when a black-based pattern is formed, the pigment is preferably a black pigment.
(Black pigment)
Examples of the black pigment include known black pigments (for example, organic pigments and inorganic pigments).
Among them, from the viewpoint of optical density, carbon black, titanium oxide, titanium carbide, iron oxide, or graphite is preferable as the black pigment, and carbon black is more preferable. As the carbon black, surface-modified carbon black in which at least a part of the surface is coated with a resin is preferable from the viewpoint of surface resistance.
From the viewpoint of dispersion stability, the particle diameter (number average particle diameter) of the black pigment is preferably 0.001 to 0.1. Mu.m, more preferably 0.01 to 0.08. Mu.m.
The "particle diameter" refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken with an electron microscope and the circle having the same area as the area of the pigment particle is considered. The "number average particle diameter" refers to an average value obtained by obtaining the above particle diameter for any 100 particles and averaging the obtained 100 particle diameters.
Examples of the white pigment include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of Japanese patent application laid-open No. 2005-007765.
As the inorganic pigment, titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, alumina, aluminum hydroxide, or barium sulfate is preferable, titanium oxide or zinc oxide is more preferable, titanium oxide is further preferable, rutile-type or anatase-type titanium oxide is particularly preferable, and rutile-type titanium oxide is most preferable.
The surface of the titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic matter treatment, or two or more of these treatments may be performed. This suppresses the catalytic activity of titanium oxide, and improves the heat resistance and the light fading property.
From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, at least one of the alumina treatment and the zirconia treatment is preferably performed as the surface treatment of the surface of the titanium oxide, and more preferably both of the alumina treatment and the zirconia treatment are performed.
When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability.
The particle diameter (number average particle diameter) of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility. The lower limit is preferably 10nm or more.
Examples of the Color pigment include victoria pure blue B0 (Color Index) (hereinafter, also known as "c.i.") 42595), auramine (c.i. 41000), fat black (fatbreak) HB (c.i. 26150), monellin yellow (monolithe yellow) GT (c.i. pigment yellow 12), permanent yellow (permanent yellow) GR (c.i. pigment yellow 17), permanent yellow HR (c.i. pigment yellow 83), permanent carmine (permanent carmine) FBB (c.i. pigment red 146), hastam red (hostaperm red) ESB (c.i. pigment violet 19), permanent ruby red (permanen t ruby) FBH (c.i. pigment red 11), aester pink (pastel pink) B spera (subpura) (c.i. pigment red 81), monatin blue (asfast) (168) (c.i. pigment red 149), fant blue (c.i. pigment red) B september (subpura) (c.i. pigment red 215), c.i. pigment red (c.i. pigment red) 15, c.i. pigment red (c.i. pigment red 177, c.i. pigment red 15, c.i. pigment red (c.i. pigment red) 122, c.i. pigment red 177, c.i. pigment red: 1. c.i. pigment blue 15: 4. c.i. pigment blue 22, c.i. pigment blue 60, c.i. pigment blue 64 and c.i. pigment violet 23, preferably c.i. pigment red 177.
One pigment may be used alone, or two or more pigments may be used.
The content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, further preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass, based on the total mass of the photosensitive composition layer.
When the photosensitive composition layer contains a pigment other than a black pigment (for example, a white pigment, a color pigment, or the like), the content of the pigment other than the black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and further preferably 3 to 15% by mass, relative to the total mass of the black pigment.
When the photosensitive composition layer contains a black pigment, the black pigment (preferably, carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.
The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant may be used.
The "vehicle" refers to a medium portion for dispersing the pigment when the pigment dispersion is prepared. The vehicle is in a liquid state and includes a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.
Examples of the dispersing machine include known dispersing machines such as a kneader, roll mill, attritor, super mill, dissolver, homomixer, and sand mill.
Further, the fine grinding may be performed by mechanical grinding and utilizing a frictional force. Examples of the dispersing machine and the fine pulverization include a "pigment dictionary" (written by shanghao, first edition, shoji bookshop, 2000, 438, and 310 pages).
< other additives >
The photosensitive composition layer may contain other additives as needed, in addition to the above components.
Examples of the other additives include resins other than resin a, a compound D described later, a radical polymerization inhibitor, an antioxidant (e.g., phenidone), a rust inhibitor (e.g., benzotriazoles and carboxybenzotriazoles), a sensitizer, a surfactant, a plasticizer, a heterocyclic compound (e.g., triazole), a pyridine (e.g., isonicotinamide), and a purine base (e.g., adenine).
Examples of the other additives include metal oxide particles, a chain transfer agent, an antioxidant, a dispersant, an acid amplifier, a development accelerator, conductive fibers, an ultraviolet absorber, a thickener, a crosslinking agent, an organic or inorganic anti-settling agent, and paragraphs [0165] to [0184] of jp 2014-085643 a, which are incorporated herein.
The other additives may be used singly or in combination of two or more.
< radical polymerization inhibitor >
Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph [0018] of japanese patent No. 4502784, and phenothiazine, phenoxazine, or 4-methoxyphenol is preferable.
Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine, and nitrosophenylhydroxylamine aluminum salt is preferred from the viewpoint of not impairing the sensitivity of the photosensitive composition layer.
The content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.02 to 2.0% by mass, based on the total mass of the photosensitive composition layer.
The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compounds.
(benzotriazoles)
Examples of the benzotriazoles include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.
(carboxybenzotriazoles)
Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole.
Examples of commercially available carboxybenzotriazoles include CBT-1 (manufactured by JOOOKU CHEMICAL CO., LTD.).
The total content of the radical polymerization inhibitor, the benzotriazole compound and the carboxybenzotriazole compound is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the total content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the total content is 3% by mass or less, the maintenance of sensitivity and the inhibition of discoloration of the dye are more excellent.
(sensitizer)
Examples of the sensitizer include known sensitizers, dyes, and pigments.
Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthene ketone (xanthone) compounds, thioxanthone (thioxanthone) compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2, 4-triazole, etc.), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.
The content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of improving the sensitivity to a light source and improving the curing rate by the balance between the polymerization rate and the chain transfer.
(surfactant)
Examples of the surfactant include those described in paragraph [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application laid-open No. 2009-237362.
The surfactant is preferably a nonionic surfactant, a fluorine surfactant or a silicone surfactant.
Examples of the fluorine-based surfactant include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94 and DS-21 (manufactured by Corporation); flu orad FC430, FC431, and FC171 (manufactured by Sumitomo 3M Limited above); surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (manufactured by AGC Inc.); polyFox PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Solutions inc.); ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by Neos Corporation, supra).
Further, as the fluorine-based surfactant, an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, in which a functional group part containing a fluorine atom is cleaved when heat is applied and the fluorine atom is volatilized, is also preferable.
Examples of such fluorine-based surfactants include MEGAFACE DS series (chemical industry daily news (2016: 2/22 d) and Japanese Industrial news (2016: 2/23 d)) manufactured by DIC Corporation.
Further, as the fluorine-based surfactant, a copolymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used.
As the fluorine-based surfactant, a terminal-capped polymer can also be used.
The fluorine-based surfactant is also preferably a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
Further, examples of the fluorine-based surfactant include fluoropolymers having an ethylenically unsaturated group in a side chain, such as MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (manufactured by DIC Corporation).
From the viewpoint of improving environmental compatibility, preferred fluorine-based surfactants are surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, ethoxylates and propoxylates thereof (e.g., glycerin propoxylate and glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; pluronic L10, L31, L61, L62, 10R5, 17R2 and 25R2 (BASF corporation); tetronic 304, 701, 704, 901, 904 and 150R1 (made by BASF corporation); solsperse 20000 (manufactured by Lubrizol Japan Limited.); NCW-101, NCW-1001, and NCW-1002 (both manufactured by FUJIFILM Wako Pure Chemical Corporation); PIONIN D-6112, D-6112-W and D-6315 (manufactured by Takemoto Oil & Fat co., ltd.); olfine E1010, surfynol 104, 400 and 440 (manufactured by Nissin Chemical co.
Examples of the silicone surfactant include linear polymers formed by siloxane bonds and modified silicone polymers having organic groups introduced into side chains and/or terminals thereof.
Specific examples of the Silicone surfactant include DOWSIL 8032 addition, toray Silicone DC3PA, toray Silicone SH7PA, toray Silicone DC11PA, toray Silicone SH21PA, toray Silicone SH28PA, toray Silicone SH29PA, toray Silicone SH30PA, and Toray Silicone SH8400 (manufactured by Dow Corning Toray co., ltd.); x-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (manufactured by Shin-Etsu Silicone Co., ltd.); f-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials Inc.); BYK307, BYK323, and BYK330 (BYK Chemie, inc., mentioned above).
The content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.8% by mass, based on the total mass of the photosensitive composition layer.
Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of International publication No. 2018/179640.
< impurities >
The photosensitive composition layer sometimes contains impurities.
Examples of the impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.
(Metal impurities and halide ions)
Examples of the metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions and halide ions thereof.
Among them, from the viewpoint of easy incorporation, sodium ions, potassium ions, and halide ions are preferably contained in the following amounts.
The metal impurities are compounds different from the particles (for example, metal oxide particles) that can be contained in the transfer film.
The content of the metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, with respect to the total mass of the photosensitive composition layer.
Examples of the method of adjusting the content of the impurity include a method of selecting a raw material having a small content of the impurity as a raw material of the photosensitive composition layer, a method of preventing the impurity from being mixed in when the photosensitive composition layer is formed, and a method of cleaning and removing the impurity.
The content of the impurities can be quantified by a known method such as ICP emission spectrometry, atomic absorption spectrometry, or ion chromatography.
(residual organic solvent)
Examples of the residual organic solvent include benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane.
The content of the residual organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 10 ppb by mass or more, more preferably 100 ppb by mass or more, with respect to the total mass of the photosensitive composition layer.
As a method for adjusting the content of the residual organic solvent, a method for adjusting drying conditions in a method for producing a transfer film described later can be given. The content of the residual organic solvent can be quantified by a known method such as gas chromatography.
(residual monomer)
The photosensitive composition layer sometimes contains residual monomers derived from each structural unit of the resin a.
The content of the residual monomer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and still more preferably 500 mass ppm or less, with respect to the total mass of the resin a, from the viewpoint of patterning property and reliability. The lower limit is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, with respect to the total mass of the resin a.
From the viewpoint of patterning property and reliability, the residual monomer derived from each structural unit of the resin a is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, with respect to the total mass of the photosensitive composition layer.
The residual amount of the monomer in synthesizing the alkali-soluble resin by a high molecular reaction is also preferably set within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set within the above range.
Examples of the method for adjusting the content of the residual monomer include a method for adjusting the content of the above-mentioned impurities.
The residual monomer content can be measured by a known method such as liquid chromatography or gas chromatography.
The photosensitive composition layer sometimes contains water.
From the viewpoint of improving reliability and laminatability, the content of water in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%.
[ intermediate layer ]
The transfer film may have an intermediate layer between the temporary support and the photosensitive composition layer.
Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in japanese patent laid-open No. 5-072724.
The intermediate layer is preferably an oxygen barrier layer, and more preferably an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkaline solution (1 mass% aqueous solution of sodium carbonate at 22 ℃), from the viewpoint of improving productivity by improving sensitivity at the time of exposure and reducing the time load of the exposure machine.
Hereinafter, each component that the intermediate layer may contain will be described.
< Water-soluble resin >
The intermediate layer may contain a water-soluble resin.
Examples of the water-soluble resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, polyether resins, gelatin, and polyamide resins.
The water-soluble resin preferably contains at least one selected from the group consisting of polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins.
Examples of the cellulose resin include water-soluble cellulose derivatives.
Examples of the water-soluble cellulose derivative include hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose.
Examples of the polyether resin include polyethylene glycol, polypropylene glycol, and alkylene oxide adducts thereof, and vinyl ether resins.
Examples of the polyamide resin include acrylamide resins, vinyl amide resins, and allyl amide resins.
Examples of the water-soluble resin include a copolymer of (meth) acrylic acid and a vinyl compound, preferably a copolymer of (meth) acrylic acid and allyl (meth) acrylate, and more preferably a copolymer of methacrylic acid and allyl methacrylate.
When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the composition ratio (% by mol of (meth) acrylic acid/% by mol of vinyl compound) is preferably 90/10 to 20/80, more preferably 80/20 to 30/70.
The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and further preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 50,000 or less.
The dispersibility of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
The water-soluble resin may be used singly or in combination of two or more.
From the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability, the content of the water-soluble resin is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more, with respect to the total mass of the intermediate layer. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less, with respect to the total mass of the intermediate layer.
< other ingredients >
The intermediate layer may contain other components in addition to the above-described water-soluble resin.
As the other component, a polyhydric alcohol, an alkylene oxide adduct of a polyhydric alcohol, a phenol derivative, or an amide compound is preferable, and a polyhydric alcohol, a phenol derivative, or an amide compound is more preferable.
Further, as other components, for example, a known surfactant can be cited.
Examples of the polyhydric alcohols include glycerin, diglycerin, and diethylene glycol.
The number of hydroxyl groups in the polyhydric alcohol is preferably 2 to 10.
Examples of the alkylene oxide adduct of a polyhydric alcohol include compounds obtained by adding an ethyleneoxy group, a propyleneoxy group, or the like to the polyhydric alcohol.
The average addition number of alkyleneoxy groups is preferably 1 to 100, more preferably 2 to 50, and still more preferably 2 to 20.
Examples of the phenol derivative include bisphenol a and bisphenol S.
Examples of the amide compound include N-methylpyrrolidone.
The intermediate layer preferably contains at least one selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyether resins, phenol derivatives, and amide compounds.
The molecular weight of the other component is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.
One or more of the other components may be used alone or in combination.
The content of the other component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, based on the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and further preferably 5% by mass or less.
< impurities >
The intermediate layer may contain impurities.
Examples of the impurities include impurities contained in the photosensitive composition layer.
The thickness of the intermediate layer is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not lowered and the interlayer mixing suppression ability is excellent. Further, the time for removing the intermediate layer during development can be further shortened.
[ other details ]
The transfer film may have other members in addition to the above-described members.
Examples of the other member include a protective film.
Examples of the protective film include a resin film having heat resistance and solvent resistance. Specifically, there may be mentioned polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films and polystyrene films. As the protective film, a resin film made of the same material as the temporary support may be used.
Among these, as the protective film, a polyolefin film is preferable, and a polypropylene film or a polyethylene film is more preferable.
The thickness of the protective film is preferably 1 to 100. Mu.m, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.
The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of relatively low cost.
The number of fish eyes (fisherye) with a diameter of 80 μm or more contained in the protective film is preferably 5/m 2 The following. The lower limit is preferably 0/m 2 The above.
The term "fish eye" refers to a phenomenon in which foreign matter, undissolved matter, oxidized and degraded matter of a material are taken into a film when the film is produced by a method such as biaxial stretching or casting, in which the material is melted by heat, kneaded, and extruded.
The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm 2 Hereinafter, more preferably 10 pieces/mm 2 Hereinafter, it is more preferably 5/mm 2 The following. The lower limit is preferably 0/mm 2 The above. When the amount is within the above range, defects caused by transfer of the unevenness due to the particles contained in the protective film to the photosensitive composition layer or the conductive layer can be suppressed.
From the viewpoint of imparting winding properties, the arithmetic average roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive composition layer or the surface in contact therewith is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. The upper limit is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and still more preferably 0.30 μm or less.
< embodiment 2 >
Embodiment 2 of the transfer film is a transfer film having a temporary support and a photosensitive composition layer, wherein,
the photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
the resin B contains a structural unit B having an acid group,
compound D has a group that generates an alkali-soluble group by the action of a base,
the content of the compound D is 5 to 50% by mass based on the total mass of the photosensitive composition layer.
The temporary support, the polymerizable compound, and the polymerization initiator have the same meanings as described in embodiment 1 of the transfer film, and preferred embodiments thereof are also the same. Embodiment 2 of the transfer film may further include, in addition to the above, components that can be contained in the photosensitive composition layer of embodiment 1 of the transfer film, an intermediate layer that can be included in embodiment 1 of the transfer film, and other members.
Embodiment 1 of the transfer film is an embodiment in which the same resin contains a structural unit a having a specific group and a structural unit b having an acid group. On the other hand, embodiment 2 of the transfer film is an embodiment in which a compound D different from the resin containing the structural unit b having an acid group has a specific group.
< resin B >
The photosensitive composition layer contains a resin B.
The resin B contains a structural unit B having an acid group.
The structural unit b has the same meaning as the structural unit b in the resin a, and the preferred embodiment is also the same.
The resin B may contain other structural units in the resin a.
The resin B preferably does not contain the specific group and the structural unit a.
< Compound D >
The photosensitive composition layer contains a compound D.
Compound D is a different compound from resin B.
The compound D is a compound having a group (specific group) which generates an alkali-soluble group by the action of an alkali. The meaning of the group which forms an alkali-soluble group by the action of an alkali is the same as that of the above-mentioned specific group, and the preferable mode is the same.
The compound D may have other groups in addition to the specific groups described above. In addition, the compound D preferably does not contain a structural unit b having an acid group.
The compound D may be any of a low molecular weight compound and a resin.
As the compound D, a compound having a lactone group or an acid anhydride group is preferable, and a low-molecular compound having a lactone group or an acid anhydride group or a resin having a lactone group or an acid anhydride group is more preferable. Further, as the compound D, a compound having 2 or more lactone groups or acid anhydride groups in the molecule is preferable, and a resin having 2 or more lactone groups or acid anhydride groups in the molecule is more preferable.
The lactone group and the acid anhydride group are the same as those in the structural unit a contained in the resin a, for example, and preferred embodiments are also the same.
When the compound D is a resin, the compound D may contain other structural units that the resin a may contain. The other structural unit is preferably derived from at least one structural unit selected from styrene, styrene derivatives, alkyl (meth) acrylates, and alicyclic methacrylates.
Examples of the compound D include resins such as a styrene/maleic anhydride copolymer (SMA EF-40, manufactured by Cray Valley Co., ltd.), a methyl methacrylate/γ -butyrolactone methacrylate copolymer, and a reaction product of a polycarboxylic acid and bromobutyrolactone (for example, a reaction product of adipic acid and bromobutyrolactone) which is a low molecular weight compound having 2 or more lactone groups in the molecule. Further, it is preferable to remove the resin of the structural unit b from the resin a.
When the compound D is a low-molecular compound, the molecular weight of the compound D is preferably from 80 to 2,000, more preferably from 100 to 1,500, and further preferably from 150 to 1,000.
When the compound D is a resin, the molecular weight of the compound D is preferably 5,000 to 100,000, more preferably 8000 to 80,000, further preferably 10,000 to 50,000.
One compound D may be used alone or two or more compounds may be used.
The content of the compound D is 5 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 5 to 20% by mass, based on the total mass of the photosensitive composition layer.
[ photosensitive composition ]
The photosensitive composition preferably contains the components contained in the photosensitive composition layer and a solvent. The content of each component contained in the photosensitive composition layer is as described above.
Specific embodiments of the photosensitive composition will be described in detail below.
< embodiment 1 >
Embodiment 1 of the photosensitive composition comprises a resin A, a polymerizable compound and a polymerization initiator,
the resin a includes a structural unit a having a group that generates an alkali-soluble group by the action of an alkali and a structural unit b having an acid group.
The resin a, the polymerizable compound, the polymerization initiator, the structural unit a, and the structural unit b are the same as the components that can be contained in the photosensitive composition layer, and the preferable embodiment is also the same.
< embodiment 2 >
In the embodiment 2 of the photosensitive composition,
the photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
the resin B contains a structural unit B having an acid group,
compound D has a group that generates an alkali-soluble group by the action of a base,
the content of the compound D is 5 to 50% by mass based on the total mass of the photosensitive composition layer.
The meanings of the resin B, the polymerizable compound, the polymerization initiator, the compound D, the structural unit B, and the group that generates an alkali-soluble group by the action of an alkali are the same as those of the components that can be contained in the photosensitive composition layer, and preferred embodiments are also the same.
< embodiment 3 >
Embodiment 3 of the photosensitive composition comprises a resin C, a polymerizable compound and a polymerization initiator,
the resin C contains a structural unit having a lactone group and a structural unit b having an acid group.
The polymerizable compound and the polymerization initiator each have the same meaning as a component that can be contained in the photosensitive composition layer, and the preferable embodiment is also the same.
< resin C >
The resin C contains a structural unit having a lactone group and a structural unit b having an acid group.
The structural unit having a lactone group and the structural unit b having an acid group are the same as those of the structural unit that can be contained in the resin a, and the preferred embodiments are the same.
Examples of the resin C include a resin containing a structural unit having a lactone group and a structural unit b having an acid group in the resin a.
The resin C may contain other structural units in addition to the above structural units. Examples of the other structural unit include other structural units that the resin a may contain.
The resin C may be used alone or in combination of two or more.
The content of the structural unit having a lactone group is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, further preferably 5 to 40% by mass, and particularly preferably 7 to 30% by mass, based on the total structural units of the resin C.
The content of the structural unit b having an acid group is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, further preferably 10 to 30% by mass, and particularly preferably 14 to 25% by mass, based on the total structural units of the resin C.
In the resin C, the content of the structural unit having a lactone group is preferably 5 to 50% by mass with respect to all the structural units of the resin C and the content of the structural unit b is 10 to 30% by mass with respect to all the structural units of the resin C, and more preferably the content of the structural unit having a lactone group is 7 to 30% by mass with respect to all the structural units of the resin C and the content of the structural unit b is 14 to 25% by mass with respect to all the structural units of the resin C.
< 4 th embodiment >
The photosensitive composition of embodiment 4 of the photosensitive composition comprises a resin B, a polymerizable compound, a polymerization initiator, and a compound DA different from the resin B,
the resin B contains structural units B having an acid group,
the compound DA contains a group having a lactone group,
the content of the compound DA is 5 to 50% by mass based on the total solid content of the photosensitive composition.
The resin B, the polymerizable compound, the polymerization initiator, and the structural unit B are each as defined above, and preferably are the same as defined above for components that can be contained in the photosensitive composition layer.
< Compound DA >
The compound DA is a different compound from the resin B.
The compound DA is a compound containing a group having a lactone group.
Examples of the group having a lactone group include groups having a lactone group which may be contained in the compound D.
Examples of the compound DA include compounds containing a group having a lactone group among the compounds D.
The compound DA may have other groups in addition to the group having a lactone group described above. In addition, the compound DA preferably does not contain a structural unit b having an acid group.
The compound DA may be used singly or in combination of two or more.
The content of the compound DA is 5 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 5 to 20% by mass based on the total solid content of the photosensitive composition.
The photosensitive composition preferably further contains a solvent.
The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used. Specifically, for example, an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (methanol, ethanol, etc.), a ketone solvent (acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (toluene, etc.), an aprotic polar solvent (N, N-dimethylformamide, etc.), a cyclic ether solvent (tetrahydrofuran, etc.), an ester solvent (N-propyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent containing two or more of them can be mentioned.
The solvent preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these solvents, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least 3 of an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, and a ketone solvent is further preferable.
Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc.), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.
Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone.
Examples of the solvent that can be used include the solvents described in paragraphs 0092 to 0094 of international publication No. 2018/179640 and the solvents described in paragraph 0014 of japanese patent application laid-open No. 2018-177889, and these are incorporated herein.
One solvent may be used alone, or two or more solvents may be used.
The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 1200 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.
[ method for producing transfer film ]
The method for producing the transfer film is not particularly limited, and known methods can be used.
Examples of the method for producing the transfer film 10 include a method including the steps of: a step of applying the intermediate layer-forming composition to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the intermediate layer 13; and a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive composition layer 15.
When the transfer film 10 has the protective film 19, the protective film 19 may be pressure-bonded to the composition layer 17 of the transfer film 10 manufactured by the above-described manufacturing method.
As a method for producing the transfer film 10, it is preferable to produce the transfer film 10 including the temporary support 11, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19 by including a step of providing the protective film 19 so as to be in contact with a surface of the composition layer 17 on the side opposite to the temporary support 11 side.
After the transfer film 10 is manufactured by the above-described manufacturing method, the transfer film 10 can be wound to manufacture and store a roll-shaped transfer film. The transfer film 10 in the roll form can be supplied as it is to a step of bonding the substrate in a roll-to-roll manner, which will be described later.
The transfer film 10 may be manufactured by forming the composition layer 17 on the protective film 19.
< method for Forming Water-soluble resin composition and intermediate layer (Water-soluble resin layer) >
The water-soluble resin composition preferably contains various components and solvents for forming the above-described intermediate layer (water-soluble resin layer). In the water-soluble resin composition, the preferable range of the content of each component with respect to the total solid content of the composition is the same as the preferable range of the content of each component with respect to the total mass of the water-soluble resin layer.
The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and is preferably at least one selected from water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and water-miscible organic solvents.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol and glycerol, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.
One solvent may be used alone, or two or more solvents may be used.
The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition.
The method for forming the water-soluble resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components, and examples thereof include known coating methods (for example, slit coating, spin coating, curtain coating, inkjet coating, and the like).
< photosensitive composition and method for Forming photosensitive composition layer >
From the viewpoint of excellent productivity, it is preferable to form the photosensitive composition layer by a coating method using a photosensitive composition containing components (for example, the resin a, the polymerizable compound, the polymerization initiator, and the like) constituting the photosensitive composition layer and a solvent.
Specifically, a method of forming a photosensitive composition layer by applying a photosensitive composition to an intermediate layer to form a coating film and drying the coating film at a predetermined temperature is preferable as a method of producing a transfer film.
The photosensitive composition is as described above.
Examples of the method of applying the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).
The coating film of the photosensitive composition is preferably dried by heating or drying under reduced pressure.
The drying temperature is preferably 80 ℃ or higher, more preferably 90 ℃ or higher. The upper limit is preferably 130 ℃ or lower, more preferably 120 ℃ or lower.
The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit is preferably 600 seconds or less, more preferably 300 seconds or less.
Further, the transfer film can be manufactured by bonding a protective film to the photosensitive composition layer.
As a method for bonding the protective film to the photosensitive composition layer, for example, a known method can be cited.
Examples of the means for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an automatic cutting laminator.
The laminator is preferably provided with an optional heatable roller such as a rubber roller and can be pressurized and heated.
[ method for producing laminate having conductor Pattern ]
By using the transfer film, a laminate having a conductor pattern can also be manufactured.
The method for producing the laminate having a conductor pattern is not particularly limited as long as it is a method for producing the laminate having a conductor pattern using the transfer film.
Among them, the method for producing a laminate having a conductor pattern according to the present invention is preferably a method for producing a laminate having a conductor pattern, the method including:
a bonding step of bonding the transfer film and the substrate so that the photosensitive composition layer side of the transfer film is in contact with the conductive layer of the substrate having the conductive layer on the surface thereof;
an exposure step of exposing the photosensitive composition layer;
a resist pattern forming step of forming a resist pattern by performing a developing process on the exposed photosensitive composition layer;
any one of an etching step of performing etching treatment on the conductive layer located in the region where the resist pattern is not arranged and a plating treatment step of performing plating treatment; and
a resist pattern stripping step of stripping the resist pattern,
when the plating treatment step is provided, a removing step of removing the conductive layer exposed in the resist pattern stripping step and forming a conductive pattern on the substrate,
a temporary support stripping step of stripping the temporary support is also provided between the bonding step and the exposure step or between the exposure step and the development step.
The method for producing a laminate having a conductor pattern preferably includes the bonding step, the exposure step, the resist pattern formation step, the etching step or the plating step, the resist pattern peeling step, and the removal step (when the plating step is provided) in this order.
The respective steps of the method for producing a laminate having a conductor pattern will be described below.
< bonding step >
The bonding process comprises the following steps: the transfer film having the temporary support and the photosensitive composition layer is bonded to the substrate so that the photosensitive composition layer is in contact with the conductive layer of the substrate having the conductive layer on the surface thereof.
When the transfer film has a protective film described later, the bonding step is preferably performed after the protective film is peeled off.
The transfer film preferably further includes an intermediate layer between the temporary support and the photosensitive composition layer.
The transfer film is as described above.
In the bonding, it is preferable that the photosensitive composition layer side (the surface opposite to the temporary support side) of the transfer film is brought into contact with the conductive layer on the substrate and pressure-bonded.
As the pressure bonding method, for example, a known transfer method and a laminating method are cited, and a method of superposing the surface of the photosensitive composition layer of the transfer film on the side opposite to the temporary support side on the substrate, and applying pressure and heat by a roller or the like is preferable.
Examples of the bonding method include a method using a known laminator such as a vacuum laminator and an automatic cutting laminator.
The lamination temperature is preferably 70 to 130 ℃.
A substrate having a conductive layer on a surface thereof (a substrate with a conductive layer) includes a substrate and a conductive layer disposed on a surface of the substrate.
The substrate with a conductive layer may have any layer other than the conductive layer formed thereon as necessary. That is, the substrate with a conductive layer preferably has at least a substrate and a conductive layer disposed on a surface of the substrate.
Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate, and the substrate described in paragraph 0140 of international publication No. 2018/155193 is preferred.
As a material of the resin substrate, polyethylene terephthalate, cycloolefin polymer, or polyimide is preferable.
The thickness of the resin substrate is preferably 5 to 200. Mu.m, more preferably 10 to 100. Mu.m.
The conductive layer is preferably at least one layer selected from a metal layer, a conductive metal oxide layer, a graphite layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and thin line formability.
Further, only 1 conductive layer may be disposed on the substrate, or 2 or more conductive layers may be disposed on the substrate. When 2 or more conductive layers are arranged, conductive layers having different materials are preferable.
A preferred embodiment of the conductive layer is described in, for example, paragraph 0141 of international publication No. 2018/155193, the contents of which are incorporated in the present specification.
The conductive layer is preferably a metal layer.
The metal layer is a layer containing a metal, and the metal is not particularly limited, and a known metal can be used. The metal layer is preferably a conductive layer.
Examples of the main component (so-called main metal) of the metal layer include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The "main metal" refers to the metal contained in the metal layer in the largest amount.
The thickness of the conductive layer is not particularly limited, but is preferably 50nm or more, and more preferably 100nm or more. The upper limit is preferably 2 μm or less.
The method for forming the metal layer is not particularly limited, and examples thereof include a method of applying a dispersion liquid in which metal fine particles are dispersed and sintering the coating film, and known methods such as a sputtering method and a vapor deposition method.
The thickness of the metal layer is not particularly limited, but is preferably 50nm or more, more preferably 100nm or more. The upper limit is preferably 2 μm or less.
The substrate may have 1 or 2 or more conductive layers disposed thereon.
When 2 or more conductive layers are arranged, the 2 or more conductive layers may be the same or different from each other, and preferably, conductive layers of different materials are arranged.
The substrate having the conductive layer may be a substrate having at least one of a transparent electrode and a wiring. The substrate described above can be preferably used as a substrate for a touch panel.
The transparent electrode can preferably function as an electrode for a touch panel.
The transparent electrode is preferably formed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), and a thin metal wire such as a metal mesh or a metal nanowire.
Examples of the thin metal wires include silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.
As a material for the wiring, a metal is preferable.
Examples of the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys of these metals in combination, with copper, molybdenum, aluminum, or titanium being preferred, and copper being more preferred.
< Exposure Process >
The exposure step is a step of exposing the photosensitive composition layer, and is preferably a step of performing pattern exposure.
The "pattern exposure" is a pattern-like exposure method, and refers to exposure in which an exposed portion and an unexposed portion are present.
The positional relationship between the exposed portion (exposed region) and the unexposed portion (unexposed region) in the pattern exposure can be appropriately adjusted.
The exposure direction may be from the photosensitive composition layer side or the side opposite to the photosensitive composition layer side (substrate side).
Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, and mask exposure is preferable.
When a temporary support peeling step described later is performed between the bonding step and the exposure step, the exposure step is preferably an exposure step in which the surface of the laminate from which the temporary support obtained in the temporary support peeling step has been peeled, on the side opposite to the substrate side, is brought into contact with a mask to perform pattern exposure. In other words, it is preferable to perform an exposure step of exposing the photosensitive composition layer in a pattern by bringing an exposed surface (a surface of the photosensitive composition layer, a surface of the intermediate layer, or the like) of the laminate from which the temporary support has been peeled, which is exposed by peeling the temporary support, into contact with a mask. In addition, as the exposed surface, when the transfer film has a 2-layer structure of the temporary support and the photosensitive composition layer, the surface of the photosensitive composition layer corresponds to this, and when the transfer film has a 3-layer structure of the temporary support, the intermediate layer, and the photosensitive composition layer, the surface of the intermediate layer corresponds to this.
By adopting such an exposure process, a higher-definition resist pattern can be obtained, and finally a higher-definition conductor pattern can be obtained.
In particular, when a temporary support peeling step described later is performed between the bonding step and the exposure step, such an exposure step is preferably employed.
In the exposure step of performing the pattern exposure, there is a possibility that a curing reaction of the components contained in the photosensitive composition layer occurs in an exposed region (a region corresponding to an opening of the mask) of the photosensitive composition layer. By performing a developing process after exposure, an unexposed area of the photosensitive composition layer is removed to form a pattern.
It is also preferable to have a mask peeling step of peeling off a mask used in the exposure step between the exposure step and the development treatment.
As the mask stripping step, for example, a known stripping step can be cited.
The light source for pattern exposure may be any light source that can irradiate light in a wavelength region (for example, wavelength 365nm and wavelength 405 nm) capable of curing at least the photosensitive composition layer, and the wavelength 365nm is preferred. "dominant wavelength" refers to the wavelength at which the intensity is highest.
Examples of the light source include various lasers, light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps.
The exposure amount is preferably 5 to 200mJ/cm 2 More preferably 10 to 200mJ/cm 2 。
Examples of the light source, the exposure amount, and the exposure method include paragraphs [0146] to [0147] of international publication No. 2018/155193, which are incorporated herein by reference.
< step of detaching temporary support >
The temporary support peeling step is performed between the bonding step and the exposure step or between the exposure step and the development step.
Among these, a peeling step is preferably provided between the bonding step and the exposure step.
The peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the conductive layer.
Examples of the method for peeling off the temporary support include a known peeling method. Specifically, there is a cover film peeling mechanism described in paragraphs [0161] to [0162] of japanese patent application laid-open No. 2010-072589.
< resist Pattern Forming Process >
The resist pattern forming step is a step of forming a resist pattern by performing a developing process on the exposed photosensitive composition layer.
The development treatment is preferably carried out using a developer.
By developing with the developer, the unexposed area of the photosensitive composition layer is removed to form a resist pattern having an opening of the mask as a convex portion.
As the developer, an alkaline aqueous solution containing an alkali metal salt is preferable.
The alkali metal salt contained in the developer is preferably a compound which is dissolved in water and exhibits alkalinity.
Examples of the alkali metal salt include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate.
The developer may contain a compound other than the alkali metal salt, which is dissolved in water and exhibits alkalinity. Examples of the compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
The liquid temperature of the developer in the development treatment is preferably 10 to 50 ℃, more preferably 15 to 40 ℃, and still more preferably 20 to 35 ℃.
The pH of the developer in the development treatment is preferably 9 or more, more preferably 10 or more, and further preferably 11 or more. The upper limit is preferably 14 or less, more preferably less than 13. The pH can be measured by a method in accordance with JIS Z8802-1984 using a known pH meter. The measurement temperature of pH was set to 25 ℃.
In the developer, the content of water is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass, relative to the total mass of the developer.
The content of the alkali metal salt in the developer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developer.
Examples of the developing method include known developing methods.
Specifically, spin immersion development, shower development, spin development, and immersion development can be given.
The development method is preferably the development method described in paragraph [0195] of International publication No. 2015/093271.
It is also preferable to perform a rinsing process for removing the developer remaining on the substrate with the conductive layer after the development and before the transfer to the next step. Water or the like can be used for the rinsing treatment.
After the development and/or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the conductive layer.
The position and size of the resist pattern formed on the substrate with the conductive layer are not particularly limited, but a fine line shape is preferable.
Specifically, the line width of the resist pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is usually 1.0 μm or more.
< post-exposure step and post-baking step >
A step of further exposing the resist pattern obtained on the substrate with the conductive layer (hereinafter, also referred to as "post-exposure step") and/or a step of heating (hereinafter, also referred to as "post-baking step") may be provided between the developing step and the etching step described later.
When both the post-exposure step and the post-baking step are provided, it is preferable to perform the post-baking step after performing the post-exposure step.
Post exposure toolThe exposure dose in the sequence is preferably 100 to 5000mJ/cm 2 More preferably 200 to 3000mJ/cm 2 。
The temperature of the post-baking in the post-baking step is preferably 80 to 250 ℃, more preferably 90 to 160 ℃.
The time for the post-baking in the post-baking step is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.
< etching Process >
The etching step is a step of etching the conductive layer located in a region where the resist pattern is not arranged.
Specifically, the method comprises the following steps: in the etching step, the conductive layer is etched using the resist pattern obtained up to the above step as an etching resist.
When the etching step is performed, the conductive layer is removed in the opening of the resist pattern, and the conductive layer has the same pattern shape as the resist pattern.
Examples of the etching method include a known etching method.
Specifically, there are a method described in paragraphs [0209] to [0210] of Japanese patent application laid-open No. 2017-120435, a method described in paragraphs [0048] to [0054] of Japanese patent application laid-open No. 2010-152155, and dry etching such as wet etching and plasma etching by immersing in an etching solution.
The etching solution used for wet etching can be appropriately selected from acidic or alkaline etching solutions according to the object to be etched.
Examples of the acidic etching solution include an acidic aqueous solution containing at least one acidic compound and an acidic mixed aqueous solution of an acidic compound and at least one selected from the group consisting of ferric chloride, ammonium fluoride and potassium permanganate.
The acidic compound (compound which is dissolved in water and exhibits acidity) contained in the acidic aqueous solution is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, fluoric acid, oxalic acid, and phosphoric acid.
Examples of the alkaline etching solution include an alkaline aqueous solution containing at least one alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (e.g., potassium permanganate).
As the basic compound (a compound which is dissolved in water and exhibits basicity) contained in the basic aqueous solution, for example, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (for example, tetramethylammonium hydroxide) is preferable.
The etching solution preferably does not dissolve the resist pattern.
The developing solution used in the developing step may also serve as an etching solution for the etching treatment. In this case, the developing step and the etching step may be performed simultaneously.
It is also preferable to perform a rinsing process for removing the etching solution remaining on the substrate with the conductive layer after the etching process and before the transfer to the next step. Water or the like can be used for the rinsing treatment.
After the etching process and/or rinsing process, a drying process may be performed to remove excess liquid from the substrate with the conductive layer.
< plating treatment step >
The plating treatment step is as follows; a plating layer is formed by plating treatment on the conductive layer (the conductive layer exposed to the surface in the developing step) located in the region where the resist pattern is not arranged.
Examples of the plating method include an electrolytic plating method and an electroless plating method, and the electrolytic plating method is preferred from the viewpoint of productivity.
When the plating step is performed, a plated layer having the same pattern shape as a region where the resist pattern is not arranged (an opening of the resist pattern) can be obtained on the substrate with the conductive layer.
Examples of the metal contained in the plating layer include known metals.
Specifically, metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals can be mentioned.
Among them, the plating layer preferably contains copper or an alloy thereof from the viewpoint of more excellent conductivity of the conductive pattern. Further, from the viewpoint of more excellent conductivity of the conductive pattern, the plating layer preferably contains copper as a main component.
The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm or more. The upper limit is preferably 20 μm or less.
< protective layer Forming step >
It is also preferable to have a protective layer forming step between the plating treatment step and a resist pattern stripping step described later.
The protective layer forming step is a step of forming a protective layer on the plating layer.
As a material of the protective layer, a material having resistance to a stripping liquid and/or an etching liquid in the resist pattern stripping step and/or the removal step is preferable. Examples thereof include metals such as nickel, chromium, tin, zinc, magnesium, gold, and silver, alloys thereof, and resins thereof, with nickel or chromium being preferred.
Examples of the method for forming the protective layer include an electroless plating method and an electroplating method, and the electroplating method is preferable.
The thickness of the protective layer is preferably 0.3 μm or more, more preferably 0.5 μm or more. The upper limit is preferably 3.0 μm or less, more preferably 2.0 μm or less.
< resist Pattern Release step >
The resist pattern stripping step is a step of removing the resist pattern remaining after the etching step.
As a method of removing the remaining resist pattern, for example, a method of removing by a chemical treatment is cited, and a method of removing by using a stripping liquid is preferable.
Examples of a method for removing the remaining resist pattern include a method of removing the resist pattern by a known method such as a spray method, a shower method, or a spin-on immersion method using a stripping liquid.
Examples of the stripping solution include a stripping solution obtained by dissolving a basic compound in at least one selected from water, dimethyl sulfoxide and N-methylpyrrolidone.
Examples of the basic compound (a compound which is dissolved in water and exhibits basicity) include basic inorganic compounds such as sodium hydroxide and potassium hydroxide, and basic organic compounds such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. As the basic organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferable.
As a method for removing the resist pattern, a method of immersing the substrate having the residual resist pattern in a stripping liquid under stirring at a liquid temperature of 30 to 80 ℃ (preferably 50 to 80 ℃) for 1 to 30 minutes can be mentioned.
The stripping liquid also preferably does not dissolve the conductive layer.
The pH of the stripping solution in the stripping treatment is preferably 11 or more, more preferably 12 or more, and still more preferably 13 or more. The upper limit is preferably 14 or less, more preferably 13.8 or less. The pH can be measured by a method in accordance with JIS Z8802-1984 using a known pH meter. The measurement temperature of pH was set to 25 ℃.
The liquid temperature of the stripping liquid at the time of the stripping treatment is preferably higher than the liquid temperature of the developing liquid at the time of the developing treatment. Specifically, the value obtained by subtracting the liquid temperature of the developing solution from the liquid temperature of the stripping solution (the liquid temperature of the stripping solution-the liquid temperature of the developing solution) is preferably 10 ℃ or higher, and more preferably 20 ℃ or higher. The upper limit is preferably 100 ℃ or lower, more preferably 80 ℃ or lower.
The pH of the stripping solution when the stripping treatment is performed is preferably higher than the pH of the developing solution when the developing treatment is performed. Specifically, the value obtained by subtracting the pH of the developing solution from the pH of the stripping solution (the pH of the stripping solution — the pH of the developing solution) is preferably 1 or more, and more preferably 1.5 or more. The upper limit is preferably 5 or less, more preferably 4 or less.
It is also preferable to perform a rinsing process for removing the stripping liquid remaining on the substrate after the resist pattern is stripped by the stripping liquid. Water or the like can be used for the rinsing treatment.
After the stripping and/or rinsing treatment of the resist pattern by the stripping liquid, a drying treatment for removing an excess liquid from the substrate may be performed.
< removal step >
When the method for manufacturing a laminate having a conductor pattern has a plating treatment step, the method for manufacturing a laminate having a conductor pattern has a removal step.
The removing step is a step of removing the conductive layer exposed in the resist pattern stripping step to obtain a conductor pattern on the substrate.
In the removing step, etching treatment of the conductive layer located in the non-pattern-formed region (in other words, the region not protected by the plating layer) is performed using the plating layer formed in the plating step as an etching resist.
The method for removing a part of the conductive layer is not particularly limited, and a known etching solution is preferably used.
Examples of known etching solutions include ferric chloride solution, cupric chloride solution, ammonia-soda solution, sulfuric acid-hydrogen peroxide mixed solution, phosphoric acid-hydrogen peroxide mixed solution, and the like.
When the removing step is performed, the conductive layer exposed on the surface is removed from the substrate, and the plating layer (conductive pattern) having the pattern shape remains, whereby a laminate having the conductive pattern can be obtained.
The line width of the conductor pattern to be formed is preferably 8 μm or less, and more preferably 6 μm or less. The lower limit is usually 1 μm or more.
< other step >
The method for producing a laminate having a conductor pattern may have other steps in addition to the above steps.
Examples of the other steps include a step of reducing the visible light reflectance described in paragraph [0172] of international publication No. 2019/022089 and a step of forming a new conductive layer on the surface of the insulating film described in paragraph [0172] of international publication No. 2019/022089.
(step of decreasing reflectance of visible ray)
The method for producing a laminate having a conductor pattern may include a step of performing a treatment for reducing the visible light reflectance of a part or all of the conductor patterns included in the laminate.
As the treatment for reducing the reflectance of visible light, for example, oxidation treatment is given. When the laminate has a conductor pattern containing copper, the visible light reflectance of the laminate can be reduced by oxidizing copper to form copper oxide and blackening the conductor pattern.
Examples of the treatment for reducing the visible light reflectance include paragraphs [0017] to [0025] in jp 2014-150118 a and paragraphs [0041], [0042], [0048] and [0058] in jp 2013-206315 a, which are incorporated herein.
(step of Forming insulating film, step of Forming New conductive layer on surface of insulating film)
The method for producing a laminate having a conductor pattern may include a step of forming an insulating film on the surface of the laminate having a conductor pattern and a step of forming a new conductive layer (such as a conductor pattern) on the surface of the insulating film.
Through the above steps, the 1 st electrode pattern and the insulated 2 nd electrode pattern can be formed.
The step of forming the insulating film may be, for example, a method of forming a known permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive composition having an insulating property.
As a step of forming a new conductive layer on the surface of the insulating film, for example, a photosensitive composition having conductivity is used to form a new conductive layer having a desired pattern by photolithography.
In the method for producing a laminate having a conductor pattern, it is also preferable to use a substrate having a plurality of conductive layers (metal layers or the like) on both surfaces of the laminate, and to form the conductor pattern sequentially or simultaneously by the conductive layers formed on both surfaces of the base material.
With the above configuration, it is possible to form the circuit wiring for a touch panel in which the 1 st conductive pattern is formed on the surface of one substrate and the 2 nd conductive pattern is formed on the surface of the other substrate. Further, it is also preferable that the circuit wiring for a touch panel having the above-described configuration is formed from both surfaces of the substrate in a roll-to-roll manner.
[ use of laminate having conductor Pattern ]
The laminate having a conductor pattern manufactured by the above-described manufacturing method is preferably used for a manufacturing process film of, for example, a semiconductor package, a printed circuit board, and an interposer (interposer) rewiring layer.
Examples of a device including the laminate having a conductor pattern manufactured by the above-described manufacturing method include an input device, preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.
[ examples ]
The present invention will be described in further detail below with reference to examples.
The materials, the amounts used, the ratios, the contents of the processes, the steps of the processes, and the like described in the following examples can be appropriately modified without departing from the spirit of the present invention. The scope of the invention should therefore not be construed in a limiting sense by the examples presented below. Unless otherwise specified, "part" and "%" are based on mass.
The weight average molecular weight of the resin is the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn) determined in terms of polystyrene by the Gel Permeation Chromatography (GPC). Also, the acid value used is the theoretical acid value.
[ Components ]
[ resin ]
< Synthesis of resin A1-1 >
Propylene glycol monomethyl ether (9.7 g) and propylene glycol monomethyl ether acetate (9.7 g) were charged into a flask, and the flask was heated to 90 ℃ under a nitrogen stream. To this liquid, a solution prepared by dissolving styrene (26.9 g), methyl methacrylate (6.7 g), methacrylic acid (11.9 g), gamma-butyrolactone methacrylate (GBLMA manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) (6.2 g) and a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure CHEMICAL Corporation) (1.7 g) in propylene glycol monomethyl ether (5 g) and propylene glycol monomethyl ether acetate (5 g), and a solution prepared by dissolving a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure CHEMICAL Corporation) (1.7 g) in propylene glycol monomethyl ether (9.7 g) and propylene glycol monomethyl ether acetate (9.7 g) were added dropwise over a period of 2 hours. After completion of the dropwise addition, V-601 (0.6 g) was added 3 times per 1 hour. Then, it was further reacted for 3 hours. Then, the resulting mixture was diluted with propylene glycol monomethyl ether acetate to obtain a solution of the resin A1-1 having a solid content of 30%. The weight average molecular weight in terms of polystyrene based on GPC was 23000, the degree of dispersion was 2.2, and the acid value of the polymer was 150mgKOH/g. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass in any of the monomers relative to the solid content of the polymer.
Resins A1-2 to A1-5, A1-7 to A1-9, A2-1 and A2-2 were synthesized in the same manner. Any of the resins was obtained as a solution having a solid content concentration of 30%. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass in any of the monomers relative to the solid content of the polymer.
< Synthesis of resin A1-6 >
Propylene glycol monomethyl ether (17.2 g) was charged into a flask and heated to 90 ℃ under a nitrogen stream. To this liquid, a solution obtained by dissolving styrene (15.3 g), gamma-butyrolactone methacrylate (GBLMA manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) (10.6 g), methacrylic acid (16.4 g), and a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure CHEMICAL Corporation) (3.7 g) in propylene glycol monomethyl ether (13.3 g) was added dropwise over 3 hours. After completion of the dropwise addition, V-601 (0.5 g) was added 3 times per 1 hour. Then, it was further reacted for 3 hours. Then, propylene glycol monomethyl ether acetate (23.8 g) and propylene glycol monomethyl ether (33.9 g) were diluted. The reaction mixture was warmed to 100 ℃ under a stream of air, and tetraethylammonium bromide (0.24 g) and p-methoxyphenol (0.11 g) were added. To this, glycidyl methacrylate (BLEMMER G manufactured by NOF CORP ORATION) (10.5G) was added dropwise over a period of 20 minutes. After allowing the reaction to proceed at 100 ℃ for 7 hours, the reaction mixture was diluted with propylene glycol monomethyl ether acetate to obtain a solution of the resin A1-6 having a solid content of 30%. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass in any of the monomers relative to the solid content of the polymer.
Resins A2-3 and A2-4 were synthesized in the same manner. Any of the resins was obtained as a solution having a solid content concentration of 30%. The amount of residual monomer measured by gas chromatography was less than 0.1% by mass in any of the monomers relative to the solid content of the polymer.
The resins A1-1 to A1-9 and the resins A2-1 to A2-4 are shown below.
In the formula, the composition ratio is a mass ratio.
[ chemical formula 13]
In the following table, the column "acid value before hydrolysis" shows the acid value (theoretical acid value) (mgKOH/g) before hydrolysis of a specific group of each resin.
The column of "acid value increased by hydrolysis" shows the theoretical acid value (mgKOH/g) in the amount increased from the theoretical acid value (mgKOH/g) before hydrolyzing the specific group of each resin when hydrolyzing the specific group of each resin. Specifically, the theoretical acid value (mgKOH/g) derived from an acid group (for example, a carboxyl group or the like) generated when a specific group of each resin is hydrolyzed is obtained by "the acid value increased by hydrolysis = the amount of a carboxyl group (mmol/g) × the molecular weight of KOH generated by hydrolysis".
[ Table 1]
[ photosensitive composition ]
Each photosensitive composition was prepared according to the components and formulation shown in the table described later.
In the table, the numerical values shown in the columns of the respective components indicate the contents (parts by mass) of the respective components.
< Compound (D) >
SMA EF-40: styrene/maleic anhydride copolymer (mol ratio 80/20) (manufactured by Cray Valley Co., ltd.)
MMA/GBLMA: methyl methacrylate/gamma-butyrolactone methacrylate copolymer (60/40 by mass, 12000 by weight, 2.2 by degree of dispersion, synthesized with reference to the method of synthesis of resin A1-1)
ADBL: a compound having the following structure (synthesized by reacting adipic acid with bromobutyrolactone under basic conditions)
[ chemical formula 14]
< polymerizable Compound >
SR454: ethoxylated (3) trimethylolpropane trimethacrylate, TOMOE Engineering co., ltd
BPE-500: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd
BPE-100: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd
M270: ARONIX M-270, polypropylene glycol diacrylate (n. About.12), TOAGOSEI co., ltd
4G: NK Ester 4G, polyethylene glycol #200 dimethacrylate, shin-Nakamura Chemical Co., ltd
< polymerization initiator >
2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer
< sensitizer >
4,4' -bis (diethylamino) benzophenone
< polymerization inhibitor >
Phenothiazine (I)
< antioxidant >
Phenidone (Tabanzo)
< coloring Material >
Colorless crystal violet, manufactured by Tokyo Chemical Industry co., ltd
< anticorrosive agent >
CBT-1: carboxy benzotriazole, joohoku CHEMICAL co
< surfactant >
F552: MEGAFACE F-552, DIC Corporation
< solvent >
MMPGAc: 1-methoxy-2-propyl acetate
MEK: methyl Ethyl Ketone
[ Components of the composition for Forming an intermediate layer ]
The intermediate layer included in the transfer film was formed using the intermediate layer-forming composition prepared by the components and the formulation shown in the table.
< resin >
PVA: polyvinyl alcohol, product name "KURARAAY POVAL PVA-205", manufactured by Kuraray Co., ltd
PVP: polyvinylpyrrolidone, product name "polyvinylpyrrolidone K-30", NIPPON SHOK UBAI CO., LTD
HPMC: hydroxypropyl methylcellulose, product name "METOLOSE 60SH-03", manufactured by Shin-Etsu Chemical Co., ltd
< surfactant >
F444: MEGAFACE F444, fluorine-based surfactant, manufactured by DIC Corporation
< solvent >
Methanol (E)
Water
[ evaluation ]
[ evaluation of hydrolyzability ]
The hydrolyzability was evaluated by the following procedure using a compound for verification using γ -butyrolactone methacrylate as the compound having a lactone group and a compound for verification using phenylsuccinic anhydride as the acid anhydride.
The compounds for verification were dissolved in acetonitrile, respectively, and a 10 mass% KOH aqueous solution (pH 14) was mixed so that KOH was 2mol equivalent to each compound for verification. After stirring for 1 minute, acetic acid was added to adjust to pH6. The remaining amount of each verification compound was measured for the obtained solution by HPLC, and as a result, it was confirmed that the remaining amount of γ -butyrolactone methacrylate and phenyl succinic anhydride was 1 mass% or less with respect to the total mass (with respect to the charged mass%) of each verification compound before KOH was added, and that the compound having a lactone group and the acid anhydride showed hydrolyzability. It was also confirmed that a carboxyl group was formed in each of the compounds for verification after addition of KOH.
[ transfer printing film production ]
Each transfer film composed of a temporary support, an intermediate layer, and a photosensitive composition layer was produced. The specific steps are shown below.
First, an intermediate layer-forming composition was applied onto a temporary support (a polyethylene terephthalate film (lumiror 169s40, toray industries, inc.) having a thickness of 16 μm) by using a bar coater so that the dried thickness became 1.0 μm, and dried at 90 ℃ using an oven to form an intermediate layer.
Further, a photosensitive composition was applied onto the intermediate layer using a bar coater so that the thickness after drying became 3.0 μm, and dried at 80 ℃ using an oven to form a photosensitive composition layer (negative photosensitive layer).
A polyethylene terephthalate (169440, produced by TORAY INDUSTRIES, INC.) having a thickness of 16 μm was pressure-bonded to the obtained photosensitive composition layer as a protective film, to prepare a transfer film used in each example or each comparative example.
[ production of a laminate having a conductor Pattern ]
A PET substrate with a copper layer was used, in which a copper layer having a thickness of 500nm was formed on a 188 μm thick PET film (polyethylene terephthalate film) by sputtering.
The transfer film thus produced was cut into a 50cm square, and the protective film was peeled off, and the film was laminated on the PET substrate having the copper layer under lamination conditions of a roll temperature of 90 ℃, a line pressure of 0.8MPa, and a line speed of 3.0m/min, so that the photosensitive composition layer was in contact with the copper layer on the surface of the PET substrate, to obtain a laminate. In this case, the laminate had a structure of "PET film-copper layer-photosensitive composition layer-intermediate layer-temporary support".
Next, the temporary support is peeled from the obtained laminate, and the intermediate layer is exposed on the surface of the laminate. A mask having a line width of 1-10 [ mu ] m in 1 [ mu ] m steps and a line width of 1-1 [ mu ] m at a ratio of 1/1 of line (mum)/space (mum) is brought into close contact with an intermediate layer exposed on the surface of the laminate.
Light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, japan Science Engineering Co., ltd., dominant wavelength: 365 nm). The exposure amount was an exposure amount at which the resist pattern obtained after development was reproduced in a line and space shape of 5 μm.
Then, development was carried out using a 1.0% sodium carbonate aqueous solution (pH 11.4) at 28 ℃ as a developer. Specifically, the developing solution was thrown off by performing a 30-second shower treatment and an air knife (AirKnife) treatment, and then, the developing solution was further subjected to an air knife treatment by performing a 30-second shower treatment with pure water. The 1 st pattern forming stage is set up until now.
Thus, a laminate of a resist pattern having a line-to-space shape with a line width to space width = 1: 1 was obtained. The laminate at this point had a structure of "PET film-copper layer-resist pattern".
< minimum resolving line width >
In the 1 st pattern formation stage, the minimum line width that can be formed without causing development residue, pattern collapse, or the like is set to the minimum resolution line width μm.
< resist Pattern shape >
The cross-sectional shape of the resist pattern obtained in the 1 st pattern formation stage was observed with a Scanning Electron Microscope (SEM), and the resist pattern shape (curl in the minimum resolution line width) was evaluated based on the following evaluation criteria.
A: pattern shape without curling
B: slightly in the shape of a turned edge
C: edge curl shape
< evaluation of resist Pattern Release >
The laminate obtained in the 1 st pattern formation stage was placed in a Copper sulfate plating solution (75 g/L Copper sulfate, 190g/L sulfuric acid, 50 ppm by mass chloride ion, "Copper glass PCM", manufactured by Meltex Inc., 5 mL/L) at a concentration of 1A/dm 2 Copper plating treatment was performed under the conditions of (1).
After the laminate after the copper plating treatment was washed with water and dried, it was immersed in a1 mass% potassium hydroxide aqueous solution (ph 13.5) at 50 ℃, whereby the resist pattern was peeled off. The peeling was performed while changing the peeling time, and the time at which the resist pattern was peeled in the line and space pattern of 5 μm was evaluated in the following manner. In addition, the shorter the time, the better the peelability.
A: less than 30 seconds
B:30 seconds or more and less than 60 seconds
C:60 seconds or more and less than 120 seconds
D: over 120 seconds
< evaluation of copper Pattern shape >
The copper layer (seed layer) of the laminate after [ evaluation of resist pattern peelability ] was removed with an aqueous solution containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide to obtain a copper wiring pattern. The cross-sectional shape of the copper wiring pattern was observed with a Scanning Electron Microscope (SEM), and the presence or absence of undercut (under cut) at the bottom of the copper pattern was evaluated in a pattern of 5 μm.
A: shape without undercut
B: slightly undercut shape
C: undercut shape
< evaluation of conductor Pattern formation and conductor Pattern Linearity (LWR) by etching >
The same procedure was carried out up to the pattern formation stage 1 to obtain a substrate having a resist pattern formed thereon (a laminate having a resist pattern).
A substrate having a resist pattern formed thereon (a laminate having a resist pattern) was etched with a copper etching solution (Cu-02.
The line widths of the portions selected at random from the copper wiring patterns of 5 μm lines and spaces were measured at 100 portions. The standard deviation (unit: nm) of the obtained Line Width was obtained, and the value of the standard deviation was defined as LWR (Line Width Roughness).
The obtained values of LWR were classified according to the following classification, and conductor pattern Linearity (LWR) was evaluated. Further, the smaller LWR is, the smaller the line width variation is, which is preferable.
A: LWR less than 150nm
B: LWR is more than 150nm and less than 200nm
C: LWR is more than 200nm and less than 300nm
D: LWR is above 300nm
[ Table 2]
[ Table 3]
As is clear from the results in the table, the transfer film of the present invention can form a resist pattern and the formed resist pattern has excellent peelability.
It was confirmed that the effect of the present invention is more excellent when the amount of the acid value increased by hydrolysis (the acid value of the resin A or the compound D derived from the alkali-soluble group generated from the specific group by the action of the base) is 20 to 100mgKOH/g (preferably 20 to 80 mgKOH/g) (comparison of examples 1,5 and 7, etc.).
Transfer films were produced using the photosensitive compositions of examples 1 to 17 in the same manner as in [ production of transfer film ] above except that the polyester film (thickness: 6.9 μm) described in example 1 of Japanese unexamined patent publication No. 2000-309650 was used as a temporary support. The minimum resolution line width, the resist pattern shape, the resist pattern peelability, the copper pattern shape, and the LWR of each transfer film obtained were evaluated in the same manner as described above, and any of the evaluation results was good as the results of examples 1 to 17.
Description of the symbols
10-transfer film, 11-temporary support, 13-intermediate layer, 15-photosensitive composition layer, 17-composition layer, 19-protective film.
Claims (21)
1. A transfer film having a temporary support and a photosensitive composition layer,
the photosensitive composition layer contains a resin A, a polymerizable compound and a polymerization initiator,
the resin a includes a structural unit a having a group that generates an alkali-soluble group by the action of an alkali and a structural unit b having an acid group.
2. The transfer film according to claim 1,
the structural unit a includes a structural unit having a base-decomposable group.
3. The transfer film according to claim 1 or 2,
the structural unit a includes a structural unit having a group that generates an acid group by the action of a base.
4. The transfer film according to claim 1 or 2,
the structural unit a includes at least one selected from a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group.
5. The transfer film according to claim 1 or 2,
the content of the structural unit a is 5 to 50 mass% with respect to all the structural units of the resin A,
the content of the structural unit b is 10 to 30% by mass based on the total structural units of the resin a.
6. A transfer film having a temporary support and a photosensitive composition layer,
the photosensitive composition layer contains a resin B, a polymerizable compound, a polymerization initiator, and a compound D different from the resin B,
the resin B contains a structural unit B having an acid group,
the compound D has a group which generates an alkali-soluble group by the action of a base,
the content of the compound D is 5 to 50% by mass based on the total mass of the photosensitive composition layer.
7. The transfer film according to claim 6,
the compound D contains a structural unit having a base-decomposable group.
8. The transfer film according to claim 6 or 7,
the compound D contains a structural unit having a group which generates an acid group by the action of a base.
9. The transfer film according to claim 6 or 7,
the compound D contains at least one member selected from the group consisting of a structural unit having a lactone group, a structural unit having an acid anhydride group, and a structural unit having a lactone group and an acid anhydride group.
10. The transfer film according to claim 1,2, 6, or 7, further comprising an intermediate layer between the temporary support and the photosensitive composition layer.
11. The transfer film according to claim 10,
the intermediate layer comprises a water-soluble resin.
12. The transfer film according to claim 11,
the water-soluble resin contains at least one selected from polyvinyl alcohol resin, polyvinylpyrrolidone resin, cellulose resin, acrylamide resin, polyethylene oxide resin, gelatin, vinyl ether resin and polyamide resin.
13. A method for manufacturing a laminate having a conductor pattern, comprising:
a bonding step of bonding the transfer film and the substrate so that the photosensitive composition layer side of the transfer film according to any one of claims 1 to 12 is in contact with the conductive layer of the substrate having a conductive layer on the surface thereof;
an exposure step of exposing the photosensitive composition layer;
a resist pattern forming step of forming a resist pattern by performing a developing treatment on the exposed photosensitive composition layer;
any one of an etching step of performing etching treatment on the conductive layer located in a region where the resist pattern is not arranged and a plating treatment step of performing plating treatment; and
a resist pattern stripping step of stripping the resist pattern,
the plating treatment step further comprises a removing step of removing the conductive layer exposed in the resist pattern stripping step and forming a conductor pattern on the substrate,
a temporary support peeling step of peeling off the temporary support is further provided between the bonding step and the exposure step or between the exposure step and the development step.
14. The method for manufacturing a laminate having a conductor pattern according to claim 13,
the resist pattern stripping step is a step of stripping the resist pattern using a stripping liquid,
the pH of the stripping solution is 13 or more.
15. The method for manufacturing a laminate having a conductor pattern according to claim 13,
the resist pattern forming step is a step of forming a resist pattern by performing a developing treatment using a developer,
the pH of the developer is less than 13.
16. The method for manufacturing a laminate having a conductor pattern according to claim 13,
the exposure method in the exposure step is any one of mask exposure, direct imaging exposure, and projection exposure.
17. The method for manufacturing a laminate having a conductor pattern according to claim 13,
the thickness of the temporary support is less than 16 μm.
18. The method for producing a laminate having a conductor pattern according to any one of claims 13 to 17, which comprises the step of peeling off the temporary support between the bonding step and the exposure step,
the exposed surface exposed in the temporary support peeling step is brought into contact with a mask to expose the photosensitive composition layer.
19. A photosensitive composition comprising a resin C, a polymerizable compound and a polymerization initiator,
the resin C contains a structural unit having a lactone group and a structural unit b having an acid group.
20. The photosensitive composition according to claim 19, wherein,
the content of the structural unit having a lactone group is 5 to 50 mass% with respect to all the structural units of the resin C, and the content of the structural unit b is 10 to 30 mass% with respect to all the structural units of the resin C.
21. A photosensitive composition comprising a resin B, a polymerizable compound, a polymerization initiator and a compound DA different from the resin B,
the resin B contains a structural unit B having an acid group,
the compound DA contains a group having a lactone group,
the content of the compound DA is 5 to 50% by mass based on the total solid content of the photosensitive composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021125198A JP2023020049A (en) | 2021-07-30 | 2021-07-30 | Transfer film, method for producing laminate having conductor pattern, and photosensitive composition |
| JP2021-125198 | 2021-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115685701A true CN115685701A (en) | 2023-02-03 |
Family
ID=85060640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210902364.3A Pending CN115685701A (en) | 2021-07-30 | 2022-07-28 | Transfer film, method for manufacturing laminate having conductor pattern, and photosensitive composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2023020049A (en) |
| KR (1) | KR20230019050A (en) |
| CN (1) | CN115685701A (en) |
| TW (1) | TW202309205A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10520816B2 (en) | 2014-05-23 | 2019-12-31 | Hitachi Chemical Company, Ltd. | Method for forming resist pattern, method for manufacturing printed wiring board, photosensitive resin composition for projection exposure and photosensitive element |
-
2021
- 2021-07-30 JP JP2021125198A patent/JP2023020049A/en active Pending
-
2022
- 2022-07-27 TW TW111128043A patent/TW202309205A/en unknown
- 2022-07-28 CN CN202210902364.3A patent/CN115685701A/en active Pending
- 2022-07-28 KR KR1020220093743A patent/KR20230019050A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230019050A (en) | 2023-02-07 |
| TW202309205A (en) | 2023-03-01 |
| JP2023020049A (en) | 2023-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7479487B2 (en) | Photosensitive transfer material, resin pattern manufacturing method, etching method, and electronic device manufacturing method | |
| JP7342246B2 (en) | Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method | |
| CN115485623A (en) | Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, method for producing touch panel, and polyethylene terephthalate film | |
| CN115685701A (en) | Transfer film, method for manufacturing laminate having conductor pattern, and photosensitive composition | |
| JP7416910B2 (en) | Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and temporary support for photosensitive transfer material | |
| WO2022181455A1 (en) | Transfer film, and method for manufacturing conductor pattern | |
| WO2022181485A1 (en) | Method for manufacturing laminate and method for manufacturing circuit wiring | |
| WO2022181456A1 (en) | Transfer film and method for manufacturing conductor pattern | |
| WO2022163301A1 (en) | Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method | |
| WO2022054374A1 (en) | Photosensitive transfer material, production method for resin pattern, production method for circuit wiring, and production method for electronic device | |
| WO2022138493A1 (en) | Method for manufacturing laminate, method for manufacturing circuit wiring, and transfer film | |
| WO2022138154A1 (en) | Method for manufacturing laminate, method for manufacturing circuit wiring, and transfer film | |
| WO2022181611A1 (en) | Production method for laminate having conductor pattern | |
| WO2023182092A1 (en) | Transfer film, laminate, method for producing laminate having resist pattern, and method for producing laminate having conductor pattern | |
| WO2024004430A1 (en) | Transfer film, pattern forming method, and circuit wiring manufacturing method | |
| CN115685684A (en) | Photosensitive composition, photosensitive composition layer, transfer film, and method for producing laminate having conductor pattern | |
| CN115685672A (en) | Transfer film and method for manufacturing laminate having conductor pattern | |
| CN115729036A (en) | Transfer film and method for manufacturing laminate having conductor pattern | |
| CN115729045A (en) | Method for manufacturing laminate having conductor pattern, and transfer film | |
| CN115729044A (en) | Method for manufacturing laminate having conductor pattern, and transfer film | |
| JP2023035807A (en) | Method for producing laminate having conductive pattern and transfer film | |
| JP2023043527A (en) | Photosensitive composition, transfer film, and manufacturing method of laminate having conductor pattern | |
| JP2023020993A (en) | Method for manufacturing laminate including transparent conductive pattern, and, method for manufacturing touch panel | |
| CN115485621A (en) | Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel | |
| JP2022184732A (en) | Laminate, transparent conductive layer-bearing substrate, and patterning method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |