CN115729044A - Method for manufacturing laminate having conductor pattern, and transfer film - Google Patents

Method for manufacturing laminate having conductor pattern, and transfer film Download PDF

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Publication number
CN115729044A
CN115729044A CN202210958155.0A CN202210958155A CN115729044A CN 115729044 A CN115729044 A CN 115729044A CN 202210958155 A CN202210958155 A CN 202210958155A CN 115729044 A CN115729044 A CN 115729044A
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photosensitive composition
composition layer
resin
transfer film
conductor pattern
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石坂壮二
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from JP2022072448A external-priority patent/JP2023035807A/en
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Publication of CN115729044A publication Critical patent/CN115729044A/en
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    • 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
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a method for manufacturing a laminated body with a conductor pattern, which is easy to form a finer conductor pattern with suppressed poor shape even in the condition of plating treatment. A method for manufacturing a laminate having a conductor pattern, comprising: a step of bonding a transfer film having a temporary support and a photosensitive composition layer to a substrate; a step of pattern-exposing the photosensitive composition layer; a step of forming a resist pattern by performing a development treatment; a step of performing plating treatment; a step of stripping the resist pattern; removing the exposed metal layer to form a conductor pattern; and a step of peeling off the temporary support, wherein the photosensitive composition layer contains a resin having a crosslinkable group, the weight average molecular weight of the resin is 3000 or more, and the mass ratio of a polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.

Description

Method for manufacturing laminate having conductor pattern, and transfer film
Technical Field
The present invention relates to a method for manufacturing a laminate having a conductor pattern and a transfer film.
Background
A method of disposing a photosensitive composition layer on an arbitrary substrate using a transfer film, pattern-exposing the photosensitive composition layer, and then developing the photosensitive composition layer has been widely used because the number of steps for obtaining a predetermined pattern is small.
The resulting pattern is sometimes used as a resist pattern for pattern plating in a portion not covered with the pattern.
For example, patent document 1 discloses a photosensitive resin composition containing an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, a sensitizer, and an additive at a predetermined mass ratio, and also discloses a photosensitive resin laminate (transfer film) using the photosensitive resin composition.
Patent document 1: japanese patent laid-open publication No. 2016-139154
As electronic devices have been miniaturized and densified to reduce the line width of conductive patterns such as wiring patterns, there is a high demand for reducing the line width of plating resist patterns.
The present inventors have studied on the transfer film described in patent document 1 to form a conductive pattern, and as a result, have found that a pattern as designed cannot be obtained in the obtained conductive pattern, such as deformation and meandering of a thin line portion and formation of a conductive portion in a useless portion, and have required improvement.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a method for manufacturing a laminate having a conductor pattern, in which a conductor pattern having a finer size and a shape defect is suppressed is easily formed even when plating is performed.
Another object of the present invention is to provide a transfer film.
The present inventors have conducted extensive studies to solve the above problems, and as a result, the present invention has been completed. That is, the following configuration was found to solve the above problems.
[ 1] A method for manufacturing a laminate having a conductor pattern, comprising:
a bonding step of bonding a transfer film having a temporary support and a photosensitive composition layer to a substrate having a metal layer on a surface thereof so that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate having the metal layer on the surface thereof;
an exposure step of pattern-exposing the photosensitive composition layer;
a developing step of performing a developing treatment on the exposed photosensitive composition layer to form a resist pattern;
a plating step of performing plating treatment on the metal layer located in a region where the resist pattern is not arranged;
a stripping step of stripping the resist pattern; and
a removing step of removing the metal layer exposed in the peeling step to form a conductor pattern on the substrate,
a temporary support stripping step of stripping the temporary support between the bonding step and the exposure step or between the exposure step and the development step,
the photosensitive composition layer contains a resin having a crosslinkable group,
the weight average molecular weight of the resin is 3000 or more,
the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.
[ 2] A method for producing a laminate having a conductor pattern according to [ 1], wherein,
the total double bond content in the photosensitive composition layer is more than 1.00mmol/g relative to the total mass of the photosensitive composition layer.
[ 3] the method for producing a laminate having a conductor pattern according to [ 1] or [ 2], wherein,
the content of double bonds derived from the resin is more than 0.20mmol/g based on the total mass of the photosensitive composition layer.
[ 4] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 3], wherein,
the double bond content derived from the above resin is more than 1.00mmol/g with respect to the total mass of the photosensitive composition layer.
[ 5] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 4], wherein,
exposure at 20mJ/cm using i-ray 2 The glass transition temperature of the photosensitive composition layer after exposure is 30 ℃ or higher.
[ 6] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 5], wherein,
the glass transition temperature of a film formed only of the above resin is 50 ℃ or higher.
[ 7] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 6], wherein,
the above resin comprises a structural unit containing a group having a double bond,
the content of the structural unit is 10 mass% or more with respect to the total mass of the resin.
[ 8] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 7], wherein,
the resin contains a structural unit derived from a monomer having an alicyclic structure or polycyclic structure.
[ 9] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 8], wherein,
the resin contains a structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms.
[ 10 ] the method for producing a laminate having a conductor pattern according to [ 9], wherein,
the hydrocarbon group has a branched chain.
[ 11 ] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 10 ], wherein,
the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer.
[ 12 ] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 11 ], wherein,
the exposure step is a step of performing pattern exposure through a photomask.
[ 13 ] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 11 ], wherein,
the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using an activating light beam on which an image of a photomask is projected.
[ 14] the method for producing a laminate having a conductor pattern according to any one of [ 1] to [ 12 ], wherein,
a step of peeling off the temporary support between the bonding step and the exposure step,
the exposure step is a step of exposing a pattern by bringing the surface exposed by peeling the temporary support into contact with a photomask.
[ 15] A transfer film having a temporary support and a photosensitive composition layer,
the photosensitive composition layer contains a resin having a crosslinkable group,
the weight average molecular weight of the resin is 3000 or more,
the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less,
the temporary support has a haze of 1.0% or less.
[ 16 ] the transfer film according to [ 15], wherein,
the double bond content derived from the resin is more than 0.55mmol/g relative to the total mass of the photosensitive composition layer,
the resin contains a structural unit derived from a monomer having an alicyclic structure or polycyclic structure.
[ 17] the transfer film according to [ 15] or [ 16 ], wherein,
the double bond content derived from the resin is more than 0.55mmol/g relative to the total mass of the photosensitive composition layer,
the resin contains a structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms.
[ 18] the transfer film according to (17),
the hydrocarbon group has a branched chain.
[ 19] the transfer film according to any one of [ 15] to [ 18], wherein,
the weight average molecular weight of the resin is 3000-18000.
The transfer film according to any one of [ 15] to [ 19], wherein,
the thickness of the temporary support is 50 μm or less.
[ 21] the transfer film according to any one of [ 15] to [ 20 ], wherein,
the photosensitive composition layer further comprises a sensitizer,
the sensitizer is selected from distyrylbenzene derivatives, styrylpyridine derivatives and anthracene derivatives.
The transfer film according to any one of [ 15] to [ 21], wherein,
the photosensitive composition layer further contains a polymerizable compound,
the polymerizable compound contains an alkylene oxide-modified bisphenol structure.
The transfer film according to any one of [ 15] to [ 22 ], which has an intermediate layer between the temporary support and the photosensitive composition layer.
[ 24 ] the transfer film according to [ 23 ], wherein,
the intermediate layer is a water-soluble resin layer.
The transfer film according to any one of [ 15] to [ 24 ], which is a transfer film comprising the temporary support, the photosensitive composition layer, and a protective film in this order,
the surface of the protective film opposite to the surface in contact with the photosensitive composition layer has an arithmetic average roughness Ra of 0.05 [ mu ] m or more.
[ 26] the transfer film according to any one of [ 15] to [ 25], which is a transfer film comprising the temporary support, the photosensitive composition layer, and a protective film in this order,
the protective film is a polypropylene film.
Effects of the invention
According to the present invention, a method for manufacturing a laminate having a conductor pattern, in which a conductor pattern having a desired shape can be easily formed, can be provided.
Further, according to the present invention, a transfer film can be provided.
Drawings
Fig. 1 is a schematic diagram showing an example of the structure of a transfer film used in the production method of the present invention.
Detailed Description
The present invention will be described in detail below.
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.
The meanings of the respective descriptions in the present specification are shown below.
In the present specification, a numerical range expressed by "to" means a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value.
In the present specification, in the numerical ranges described in the stepwise manner, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value described in another stepwise manner. 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.
In the present specification, the term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when it cannot be clearly distinguished from other steps.
In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700nm is 80% or more, preferably 90% or more.
In the present invention, 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.
In the present specification, 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, or 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.
In the present specification, the molecular weight of the compound having a molecular weight distribution is a weight average molecular weight (Mw) unless otherwise specified.
In the present specification, unless otherwise specified, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP) spectroscopic analyzer.
In the present specification, the refractive index is a value measured at a wavelength of 550nm using an ellipsometer, unless otherwise specified.
In the present invention, the hue is a value measured by a colorimeter (CR-221, minolta Co., ltd.) unless otherwise specified.
In the present specification, "(meth) acrylic group" is a concept including both acrylic group and methacrylic group, and "(meth) acryloyloxy group" is a concept including both acryloyloxy group and methacryloyloxy group.
In the present specification, "alkali-soluble" means that the solubility of 100g of a1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more.
In the present specification, "water-soluble" means that the solubility with respect to 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the solubility conditions described above.
In the present specification, "solid component" of the composition means a component forming a composition layer formed using the composition, and when the composition contains a solvent (an organic solvent, water, or the like), it means all components except the solvent. In addition, if the component is a component forming the composition layer, the liquid component is also considered as a solid component.
< method for producing laminate having conductor Pattern >
The method for manufacturing a laminate having a conductor pattern according to the present invention includes:
a bonding step of bonding the transfer film having the temporary support and the photosensitive composition layer to the substrate so that a surface of the transfer film opposite to the temporary support is in contact with a metal layer of the substrate having the metal layer on a surface thereof;
an exposure step of pattern-exposing the photosensitive composition layer;
a developing step of forming a resist pattern by performing a developing process on the exposed photosensitive composition layer;
a plating step of plating the metal layer located in the region where the resist pattern is not disposed;
a stripping step of stripping the resist pattern; and
a removing step of removing the metal layer exposed by the peeling step and forming a conductor pattern on the substrate,
a temporary support stripping step of stripping the temporary support is provided between the bonding step and the exposure step or between the exposure step and the development step.
The present invention is characterized by the following points: the photosensitive composition layer of the transfer film contains a resin having a crosslinkable group, the weight average molecular weight of the resin is 3000 or more, and the mass ratio of a polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.
Although the mechanism by which a conductor pattern having a desired shape can be obtained when plating treatment is performed by the above-described method for producing a laminate having a conductor pattern is not necessarily clear, the present inventors presume as follows.
It is considered that the photosensitive composition layer of the transfer film has the above-described characteristic points, and the plating solution used in the plating treatment step is less likely to penetrate into the formed resist pattern, and the resist pattern is less likely to swell even if it penetrates. As a result, it is considered that deformation, meandering, and the like of the thin line portion are less likely to occur. Further, it is considered that the resist pattern formed is not easily peeled off in the plating step due to the above-described characteristics of the photosensitive composition layer, and as a result, the conductive portion is not easily formed in a useless portion.
A method for producing a laminate having a conductor pattern according to the present invention will be described below. The transfer film will be described in detail in the following section.
In addition, a conductor pattern that is easily formed into a desired shape when subjected to plating treatment is hereinafter also referred to as "excellent conductor pattern formability".
[ bonding Process ]
The bonding step is a step of bonding the transfer film having the temporary support and the photosensitive composition layer to the substrate so that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate having the metal layer on the surface. By performing the bonding step, a substrate with a photosensitive composition layer, which includes a substrate, a metal layer, a photosensitive composition layer, and a temporary support in this order, can be obtained.
In the case where the transfer film to be described later has a structure having a protective film, the protective film is peeled off and then the bonding step is performed.
A substrate having a metal layer on a surface thereof (a substrate with a metal layer) includes a substrate and a metal layer disposed on a surface of the substrate.
The substrate with a metal layer may have any layer other than the metal layer formed thereon as necessary. That is, the substrate with a metal layer preferably has at least a substrate and a metal 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 preferable.
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 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 component" refers to the metal contained in the metal layer in the largest amount.
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 10 μm or less, more preferably 2 μm or less.
1 or 2 or more metal layers may be disposed on the substrate.
When 2 or more metal layers are disposed, the 2 or more metal layers may be the same or different from each other, and preferably, metal layers of different materials are disposed.
In the above 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 metal layer on the substrate and pressure-bonded.
The method of pressure bonding is not particularly limited, and a known transfer method and lamination method can be used. Among them, it is preferable to laminate the surface of the photosensitive composition layer on a substrate having a conductive portion and to apply pressure and heat by a roller or the like.
For bonding, a known laminator such as a vacuum laminator and an automatic cutting laminator can be used.
The lamination temperature is not particularly limited, and is preferably 70 to 130 ℃.
[ Exposure Process ]
The exposure step is a step of pattern-exposing the photosensitive composition layer.
By performing the exposure step and the developing step described later, a resist pattern for protecting at least a part of the metal layer can be formed on the metal layer on the substrate.
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 pattern exposure can be appropriately adjusted. The exposure is preferably performed from the photosensitive composition layer side.
Examples of the exposure method in the exposure step include mask exposure, direct imaging exposure, and projection exposure, and mask exposure and projection exposure are preferable.
That is, as the exposure step, a step of performing exposure through a photomask is preferable.
In addition, as the exposure step, a step of exposing the photosensitive composition layer through a lens by using an active light beam on which an image of the photomask is projected is also preferably used.
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 a 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 light shield to perform pattern exposure. In other words, the exposure step of pattern-exposing the photosensitive composition layer by bringing the exposed surface of the laminate from which the temporary support has been peeled away into contact with the photomask is preferable. When the transfer film described later has a 3-layer structure of a temporary support, an intermediate layer, and a photosensitive composition layer, the exposed surface corresponds to the surface of the intermediate layer.
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 case where a temporary support peeling step described later is performed between the exposure step and the development step, the exposure step is preferably an exposure step in which the surface of the transfer film on the side opposite to the side having the substrate in the laminate of the substrate and the transfer film obtained in the bonding step is brought into contact with a photomask to perform pattern exposure.
In the exposure step of performing pattern exposure, a curing reaction of the components contained in the photosensitive composition layer can be generated in an exposed region (region corresponding to the opening of the photomask) of the photosensitive composition layer. By performing a developing process after exposure, the non-exposed region of the photosensitive composition layer is removed to form a resist pattern.
The method of the present invention preferably includes a photomask removing step of removing the photomask used in the exposure step between the exposure step and the development step.
Examples of the photomask peeling step include a known peeling step.
The light source for pattern exposure may be selected and used as appropriate as long as it can irradiate light (for example, 365nm or 405 nm) in a wavelength region in which at least the photosensitive composition layer can be cured. Among them, the dominant wavelength of exposure light for pattern exposure is preferably 365nm. The dominant wavelength is a wavelength having the maximum intensity.
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 。
Preferable examples of the light source, exposure amount, and exposure method used for exposure are described in, for example, paragraphs [0146] to [0147] of International publication No. 2018/155193, which are incorporated herein by reference.
[ procedure for peeling off temporary support ]
The temporary support peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer between the bonding step and the exposure step or between the exposure step and a developing step described later.
The peeling method is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs [0161] to [0162] of japanese patent application laid-open No. 2010-072589 can be used.
[ developing Process ]
The developing step is a step of forming a resist pattern by performing a developing treatment on the exposed photosensitive composition layer.
The photosensitive composition layer can be developed using a developer.
As the developer, an aqueous alkali solution is preferable. Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-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, with respect to the total mass of the developer.
The content of the alkaline compound 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 development method include spin immersion development, shower development, spin development, and immersion development.
The developer preferably used in this specification includes, for example, the developer described in paragraph [0194] of international publication No. 2015/093271, and the developing method preferably used includes, for example, the developing 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 metal 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 metal layer are not particularly limited, but preferably include a fine line shape.
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.
[ plating Process ]
The plating step is a step of plating the metal layer located in the region where the resist pattern is not arranged.
More specifically, the plating step is a step of forming a plating layer by plating on a metal layer (a metal layer exposed on the surface in the developing step) located in a region where no resist pattern is arranged.
Examples of the plating method include an electrolytic plating method and an electroless plating method, and the electrolytic plating method is preferable 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 metal 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, the plating layer preferably contains copper as a main component from the viewpoint of more excellent conductivity of the conductive pattern.
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.
[ peeling Process ]
The stripping step is a step of stripping the residual resist pattern.
The method of removing the residual resist pattern is not particularly limited, and a method of removing by chemical treatment, preferably a method of removing using a stripping solution, may be mentioned.
The removal may be performed by a known method such as spray coating, shower coating, spin coating, or the like using a stripping liquid.
Examples of the stripping solution include a solution obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic base component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound. As the basic organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferable.
The stripping liquid also preferably does not dissolve the conductive layer.
As a method for removing the resist pattern, a method of immersing the substrate having the residual resist pattern in a stripping liquid while stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes can be mentioned.
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 when the stripping treatment is performed is preferably higher than the liquid temperature of the developing liquid when the developing treatment is performed. 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 with 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 Process ]
The removing step is a step of removing the metal layer exposed in the peeling step and forming a conductor pattern on the substrate.
In the removal process, etching treatment of the metal 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 by the plating process as an etching resist.
The method for removing a part of the metal 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 metal layer exposed on the surface is removed from the substrate, and the plating layer (conductor pattern) having the pattern shape remains, whereby a laminate having the conductor pattern can be obtained.
The upper limit of 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 not particularly limited, but is often 1 μm or more.
[ other Processes ]
The method for producing the laminate having the conductor pattern may include any process (other process) other than the above-described process.
Examples of the step include, but are not limited to, the step of reducing the visible light reflectance described in paragraph [0172] of international publication No. 2019/022089, and the step of forming a new metal layer on the insulating film described in paragraph [0172] of international publication No. 2019/022089.
(step of reducing reflectance of visible ray)
The method for manufacturing a laminate having a conductor pattern may include a step of performing a treatment for reducing the visible light reflectance of part or all of the plurality of metal layers included in the substrate.
As the treatment for reducing the reflectance of visible rays, oxidation treatment may be mentioned. When the substrate has a metal layer containing copper, the visible light reflectance of the metal layer can be reduced by oxidizing copper to form copper oxide and blackening the metal layer.
The treatment for reducing the reflectance of visible light is described in paragraphs [0017] to [0025] of Japanese patent application laid-open No. 2014-150118 and paragraphs [0041], [0042], [0048] and [0058] of Japanese patent application laid-open No. 2013-206315, and the contents of these publications are incorporated in the present specification.
(step of Forming insulating film, step of Forming New conductive layer on surface of insulating film)
The method of manufacturing a laminate having a conductor pattern preferably includes a step of forming an insulating film on a surface of the circuit wiring and a step of forming a new conductive layer on a surface of the insulating film.
Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film may be used. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive layer on the insulating film is not particularly limited, and a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.
In the method of manufacturing a laminate having a conductor pattern, it is also preferable to use a substrate having a plurality of metal layers on both surfaces of the substrate, and to form a circuit successively or simultaneously with respect to the metal layers formed on both surfaces of the substrate. With this configuration, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface. Further, it is also preferable that the circuit wiring for a touch panel having such a configuration is formed from both surfaces of the substrate in a roll-to-roll manner.
< use of laminate having conductor Pattern >
The method for manufacturing a laminate having a conductor pattern can be applied to the manufacture of conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic wave shielding materials, and light adjusting films; manufacturing a printed circuit board and a semiconductor package; manufacturing a column and a pin for interconnection between semiconductor chips or packages; manufacturing a metal mask; and manufacturing Tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding).
The touch panel may be a capacitance type touch panel. The method for manufacturing a laminate according to the present invention can be used for forming a conductive film or a peripheral circuit wiring in a touch panel. The touch panel can be applied to display devices such as an organic EL (electro-luminescence) display device and a liquid crystal display device.
< transfer film >
The transfer film used in the method for producing a laminate having a conductor pattern of the present invention comprises a temporary support and a photosensitive composition layer, wherein the photosensitive composition layer contains a resin having a crosslinkable group, the weight average molecular weight of the resin is 5000 or more, and the mass ratio of a polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.
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 other members (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, 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 of the maximum width of the corrugations is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.
The maximum width of the moire of the transfer film is a value measured by the following procedure.
First, a transfer film was cut in a direction perpendicular to a main surface into a size of 20cm long × 20cm wide to prepare a test sample. In addition, when the transfer film has a protective film, the protective film is peeled off. 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 was opposed to the table. After standing, the surface of the test sample is scanned with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) over a range of 10cm square from the center of the test sample to obtain a three-dimensional surface image, 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 defined as "maximum width of moire of 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.
[ temporary support ]
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.
As the temporary support, a film is preferable, and a resin film is more preferable. 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, and the transmittance at 365nm is preferably 60% or more, more preferably 70% or more.
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 value of the haze of the temporary support is preferably 2% or less, more preferably 1.0% or less, and further preferably 0.1% or less. The lower limit is not particularly limited, and may be 0.01% or more.
From the viewpoint of pattern formability during pattern exposure via the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of particles, foreign matters and defects having a diameter of 1 μm or more in the temporary support is preferably 50/10 mm 2 Hereinafter, more preferably 10/10 mm 2 Hereinafter, 3/10 mm is more preferable 2 Hereinafter, particularly preferably 0 piece/10 mm 2 。
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 ease of handling and versatility.
The thickness of the temporary support was calculated as an average value of arbitrary 5 points measured by cross-sectional observation using 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 trade marks of 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 contains a resin a described later. The photosensitive composition layer may further contain a polymerizable compound and a polymerization initiator.
Such a photosensitive composition layer preferably contains, based on the total mass of the photosensitive composition layer, a resin a:10 to 95 mass percent; a polymerizable compound: 0 to 70 mass%; polymerization initiator: 0.01 to 20 mass%. The mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer to the resin a described later is 0.85 or less.
Hereinafter, each component that the photosensitive composition layer may contain will be described.
(resin)
The photosensitive composition layer contains a resin having a crosslinkable group (hereinafter, also referred to as resin a).
The resin A has a crosslinkable group, and the weight-average molecular weight of the resin A is 3000 or more.
The mode of the crosslinkable group of the resin a is not particularly limited, but the resin a preferably contains a structural unit having a crosslinkable group. The structural unit having a crosslinkable group is described in detail later.
The resin a is preferably an alkali-soluble polymer.
The acid value of the resin a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and even more preferably less than 190mgKOH/g, from the viewpoint of suppressing swelling of the negative photosensitive composition layer by the developer to further improve the resolution.
The lower limit of the acid value of the resin A is not particularly limited, but from the viewpoint of further improving the developability, it is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, and particularly preferably 170mgKOH/g or more.
The acid value (mgKOH/g) was defined as the mass [ mg ] of potassium hydroxide required for neutralizing 1g of the sample. The acid value can be calculated from the average content of acid groups in the compound, for example. The acid value of the resin a may be adjusted by the kind of the structural unit constituting the resin a and the content of the structural unit containing an acid group described later.
Hereinafter, the structural unit that the resin a may contain will be described in detail.
Structural units having crosslinkable groups-
The resin a preferably contains a structural unit having a crosslinkable group.
The crosslinkable group can link the polymer chains constituting the resin a to each other by a covalent bond. Examples of the crosslinkable group include polymerizable groups, and polymerizable groups are preferred. That is, the resin a preferably contains a structural unit having a polymerizable group.
The polymerizable group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. Also, when the resin a has an ethylenically unsaturated group, the resin a preferably contains a structural unit having an ethylenically unsaturated group in a side chain.
In the present specification, "main chain" represents a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" represents a group of atoms branched from the main chain.
As the ethylenically unsaturated group, allyl or (meth) acryloyloxy is more preferable.
The structural unit having a polymerizable group is preferably a structural unit represented by the formula (P).
[ chemical formula 1]
Figure BDA0003790819850000191
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 crosslinkable 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 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 alkylene group may have a heteroatom, and a methylene group in the alkylene group may be substituted with a heteroatom. 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, phenylene group is preferable.
The cycloalkylene group and the arylene group may have a hetero atom as a ring member atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.
The above 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 An alkylene group which may have a hetero atom is preferable.
P represents a crosslinkable group.
The crosslinkable group is preferably a polymerizable group, as described above.
Examples of the structural unit having a polymerizable group include the structural units described below, but are not limited thereto.
[ chemical formula 2]
Figure BDA0003790819850000201
In the above structural units, rx represents a hydrogen atom or a methyl group. In the above structural units, ry represents a hydrogen atom or a methyl group.
The resin a may contain one kind of structural unit having a crosslinkable group alone, or may contain two or more kinds.
The content of the structural unit having a polymerizable group in the resin a is preferably 2 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 20 to 55% by mass, based on all the structural units of the resin a, from the viewpoint of more excellent conductor pattern formability.
From the viewpoint of further improving the effect of the present invention, the content of the structural unit having a polymerizable group in the resin a is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the resin a.
Examples of the method for introducing a polymerizable group into the resin a include the following methods: compounds such as epoxy compounds, blocked isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds and carboxylic anhydride compounds are reacted with functional groups such as hydroxyl group, carboxyl group, primary amino group, secondary amino group, acetoacetyl group (acetoacetyl group) and sulfo group.
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 polymerization reaction, (meth) acryloyloxy group is introduced into the polymer by reacting a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate with a part of the carboxyl group of the obtained polymer by a high molecular reaction. Another method includes the following steps: after a polymer having a hydroxyl group is synthesized by a polymerization reaction, (meth) acryloyloxy group is introduced into the polymer by reacting a (meth) acrylate having an isocyanate group with a part of the hydroxyl group of the obtained polymer by a high molecular reaction.
By this method, a resin a having a (meth) acryloyloxy group in a side chain can be obtained.
The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃ and more preferably at a temperature of 80 to 90 ℃. As the polymerization initiator used for the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. The polymerization reaction is preferably carried out at a temperature of 80 to 110 ℃. In the above-mentioned polymer reaction, a catalyst such as ammonium salt is preferably used.
Structural units having acid groups
The resin a preferably contains a structural unit having an acid group from the viewpoint of more excellent conductor pattern formability.
Examples of the acid group include a carboxyl group, a sulfo group, a phosphonic acid group and a phosphoric acid group, and a carboxyl group is preferable.
As the structural unit having the acid group, a structural unit derived from (meth) acrylic acid is preferable, and a structural unit derived from methacrylic acid is more preferable.
The resin a may contain one kind of structural unit having an acid group alone, or may contain two or more kinds.
When the resin a contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 30% by mass, relative to the mass of all the structural units of the resin a.
In addition, from the viewpoint of further improving the effect of the present invention, the content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on all the structural units of the binder polymer.
Structural units having an alicyclic or polycyclic structure
The resin A preferably contains a structural unit having an alicyclic structure or polycyclic structure.
The ring constituting the polycyclic structure is preferably an alicyclic ring.
By using a monomer containing a group having an alicyclic structure or a monomer containing a group having a polycyclic structure, an alicyclic structure or a polycyclic structure can be introduced into the side chain of the resin a.
Examples of the monomer containing a group having an alicyclic structure include monomers having an alicyclic aliphatic hydrocarbon group, and (meth) acrylates having an alicyclic hydrocarbon group are preferable.
Examples of the monomer containing a group having a polycyclic structure include a monomer having a polycyclic aliphatic hydrocarbon group, and a (meth) acrylate having a polycyclic aliphatic hydrocarbon group is preferable.
Specific examples of the (meth) acrylate having an alicyclic hydrocarbon group include 1-menthyl (meth) acrylate, 2,2,5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Among them, cyclohexyl (meth) acrylate and 1-menthyl (meth) acrylate are preferable as the (meth) acrylate having an alicyclic hydrocarbon group.
Specific examples of the (meth) acrylate having a polycyclic aliphatic hydrocarbon group include bicyclo [2.2.1] heptyl-2 ] acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 62 zxft 3562-triethyl-1-adamantyl (meth) acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7-transmethylaindeno (meth) acrylate, and 3732-methylhydro-1-adamantyl (meth) acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, (norbornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and fenchyl (meth) acrylate.
Among them, as the (meth) acrylate having a polycyclic aliphatic hydrocarbon group, norbornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, or tricyclodecane (meth) acrylate is preferable.
When the resin a contains a structural unit having an alicyclic or polycyclic structure, the content of the structural unit having an alicyclic or polycyclic structure is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 20% by mass, based on the mass of all the structural units of the resin a.
The content of the alicyclic or polycyclic structural unit in the resin a is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and still more preferably 10 to 30 mol% based on all the structural units of the binder polymer.
Structural units derived from (meth) acrylate monomers having a hydrocarbon group having 9 or more carbon atoms-
From the viewpoint of excellent conductor pattern formability, the resin a preferably contains a structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms.
The (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms is preferably a (meth) acrylate monomer having an alicyclic hydrocarbon group having 9 or more carbon atoms, and more preferably a (meth) acrylate monomer having a polycyclic aliphatic hydrocarbon group having 9 or more carbon atoms.
Examples of the hydrocarbon group in the (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms include isobornyl, adamantyl, dicyclopentyl, dicyclopentenyl, phenethyl, and menthyl groups, and groups obtained by substituting a hydrogen atom of these groups with an alkyl group having 1 to 3 carbon atoms or a hydroxyl group.
The hydrocarbon group in the (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms preferably has a branched chain. Examples of the group having a branched chain include an isobornyl group, a dicyclopentenyl group, a phenethyl group and a menthyl group.
When the resin a contains a structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms, the content of the structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass, based on the mass of all the structural units of the resin a.
The content of the structural unit derived from the (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms in the resin a is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and still more preferably 10 to 30 mol% based on all the structural units of the binder polymer.
Structural units derived from monomers having aromatic hydrocarbon groups
In addition, the resin a preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing deterioration in the line width or resolution when the focus position shifts during exposure. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
The content of the structural unit derived from a monomer having an aromatic hydrocarbon group in the resin a is preferably 20 mass% or more, more preferably 30 mass% or more, with respect to all the structural units of the resin a. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less. In addition, when a plurality of resins a are contained, it is preferable that the average value of the contents of the structural units derived from the monomer having an aromatic hydrocarbon group is 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, styrene dimer, styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable.
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 15 to 65% by mass, and still more preferably 15 to 55% by mass, based on all the structural units of the resin a. When the photosensitive composition layer contains a plurality of types of the resin a, the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.
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 and the like.
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 70% by mass, more preferably 15 to 65% by mass, further preferably 20 to 60% by mass, and particularly preferably 25 to 55% by mass, based on all the structural units of the resin a.
-non-acidic structural units-
The resin a may contain a non-acidic structural unit derived from a monomer which is non-acidic and has at least 1 polymerizable unsaturated group in the molecule.
Examples of the monomer (non-acidic monomer) include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, sec-butyl (meth) acrylate, isoamyl (meth) acrylate, t-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, t-octyl (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, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable.
The content of the structural unit derived from a non-acidic monomer in the resin a is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and still more preferably 1 to 30% by mass, based on all the structural units of the resin a.
One kind of the resin A may be used alone, or two or more kinds may be used.
When two or more kinds are used, it is preferable to use two kinds of the resin a containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixed manner or to use the resin a containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixed manner and the resin a not containing a structural unit derived from a monomer having an aromatic hydrocarbon group in a mixed manner. In the latter case, the proportion of the resin a containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the resin a.
The resin a can be synthesized by polymerizing the above-mentioned single or plural monomers using a radical polymerization initiator such as a peroxide polymerization initiator (e.g., benzoyl peroxide) and 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, and 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 the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
Property of the resin-
The glass transition temperature (Tg) of the resin A is preferably 50 ℃ or higher. That is, the Tg of the film formed only of the resin A is preferably 50 ℃ or higher. The upper limit of the Tg of the film formed only of the resin a is not particularly limited, and 135 ℃.
From the viewpoint of improving the edge melting resistance, it is preferable to use the resin a having a Tg of 50 ℃ or more. From this viewpoint, the Tg of the resin A is preferably 60 ℃ or higher, more preferably 70 ℃ or higher.
Further, by using the resin a having a Tg of 135 ℃ or less, it is possible to suppress deterioration in the line width and resolution when the focus position is shifted during exposure. 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.
The Tg of the resin a refers to a value measured by a differential scanning calorimeter.
The weight average molecular weight of the resin A is 3000 or more, preferably 5000 to 500000. When the weight average molecular weight is 500000 or less, it is preferable from the viewpoint of improving the resolution and the developability. The weight average molecular weight is more preferably 100000 or less, still more preferably 60000 or less, particularly preferably 30000 or less, and most preferably 18000 or less. On the other hand, when the weight average molecular weight is 5000 or more, it is preferable from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as the edge meltability and the chipping property in the case of using the photosensitive resin laminate. The weight average molecular weight is more preferably 8000 or more, still more preferably 10000 or more, and particularly preferably 15000 or more.
The edge meltability means how easily the photosensitive composition layer overflows from the end face of the roll when the transfer film is wound into a roll as a photosensitive resin laminate. 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 photosensitive resin laminate, they are transferred to a mask in a subsequent exposure step or the like, resulting in a defective product.
The degree of dispersion of the resin A 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. In the present invention, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight). In the present invention, the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography.
The photosensitive composition layer may contain other resins than the resin a described above.
Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.
The content of the resin a is preferably 10 to 95% 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. From the viewpoint of controlling the development time, the content of the resin a is preferably 95% by mass or less. On the other hand, from the viewpoint of improving the edge melting resistance, the content of the resin a is preferably 10% by mass or more.
(polymerizable Compound)
The photosensitive composition layer may contain a polymerizable compound having a polymerizable group. As the polymerizable compound, an ethylenically unsaturated compound is preferable.
In the present specification, the term "polymerizable compound" refers to a compound different from the resin a and polymerizable by the action of 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.
Examples of the ethylenically unsaturated group of the ethylenically unsaturated compound include a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group. As the ethylenically unsaturated group, an acryloyl group or a methacryloyl group is preferable.
The polymerizable group of the polymerizable compound other than the ethylenically unsaturated compound is not particularly limited as long as it is a group participating in a polymerization reaction, and examples thereof include groups having a cationically polymerizable group such as an epoxy group and an oxetanyl group.
The ethylenically unsaturated compound will be described below.
The ethylenically unsaturated compound is preferably a compound having 2 or more ethylenically unsaturated groups in one molecule (polyfunctional ethylenically unsaturated compound) from the viewpoint of more excellent photosensitivity.
In addition, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and further preferably 2 or less, from the viewpoint of further excellent resolution and peelability.
From the viewpoint of more excellent balance between the photosensitivity, the resolution, and the releasability of the photosensitive composition layer, the 2-or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in one molecule is preferably contained, and the 2-functional ethylenically unsaturated compound having 2 ethylenically unsaturated groups in one molecule is more preferably contained.
From the viewpoint of excellent peelability, the content of the 2-functional ethylenically unsaturated compound with respect to the total mass of the polymerizable compounds is preferably 20 mass% or more, more preferably more than 40 mass%, and further preferably 55 mass% or more. The upper limit is not particularly limited and may be 100 mass%. That is, the polymerizable compounds may be all 2-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 photosensitive composition layer also preferably contains, as a polymerizable compound, a polymerizable compound B1 having an aromatic ring and 2 ethylenically unsaturated groups.
In the photosensitive composition layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compounds is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of more excellent resolution. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.
Examples of the aromatic ring included in the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring, and condensed rings thereof, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. The aromatic ring may have a substituent.
The polymerizable compound B1 may have only 1 aromatic ring, or may have 2 or more aromatic rings.
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 preferable.
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 2 polymerizable groups, or may be bonded through 1 or more alkyleneoxy groups, preferably 1 or more alkyleneoxy groups. That is, the polymerizable compound B1 preferably has an alkylene oxide-modified bisphenol structure.
The alkyleneoxy group 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 to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule.
The polymerizable compound B1 having a bisphenol structure is described in paragraphs [0072] to [0080] of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated 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) acryloyloxyalkyl) phenyl) propane.
Examples of 2,2-bis (4- ((meth) acryloyloxyalkylpolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324m, manufactured by hitachi Chemical Co., ltd., product), 2,2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (BPE-500, shift-Nakamura Chemical Co., manufactured by ltd., product), 2,2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200 my, hitachi Chemical Co., ltd., product), 2,2-bis (4- (methacryloyloxypentadecyloxy) phenyl) propane (BPE-1300, n-3924-bis (4- (methacryloyloxydiethoxy) phenyl) propane (BPE-3534, manufactured by shin-200, bisphenol a-120, n-propylene glycol acrylate (naph-propylene glycol).
As the polymerizable compound B1, a compound represented by the following general formula (B1) is also preferable.
[ chemical formula 3]
Figure BDA0003790819850000291
In the general formula (B1), R 1 And R 2 Each independently represents a hydrogen atom or a methyl group. A represents C 2 H 4 . B represents C 3 H 6 . n1 and n3 are each independently an integer of 1 to 39, and n1+ n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2+ n4 is an integer of 0 to 30. The arrangement of the structural units- (A-O) -and- (B-O) -may be random, it may be a block. Also, in the case of a block, either one of- (A-O) -and- (B-O) -may be on the biphenyl (bisphenyl) side.
In one aspect, 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.
The polymerizable compound B1 may be used alone or in combination of two or more.
From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 is preferably 10 mass% or more, and more preferably 20 mass% or more, with respect to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive resin bleeds out from the end of the transfer member).
The photosensitive composition layer may contain a polymerizable compound other than the polymerizable compound B1.
The polymerizable compound other than the polymerizable compound B1 is not particularly limited, and can be appropriately selected from known compounds. For example, there may be mentioned a compound having 1 ethylenically unsaturated group in one 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.), ltd.,), polyethylene glycol dimethacrylate (4G, 9G, 14G, 23G, etc., shin-Nakamura Chemical co., ltd., ltd.), ARONIX (registered trademark) M-220 (TOAGOSEI co., ltd.), ARONIX (registered trademark) M-240 (TOAGOSEI co., ltd., ltd, manufactured), aroni (registered trademark) M-270 (TOAGOSEI co., ltd, manufactured), ethylene glycol dimethacrylate, 1, 10-decanedioldiacrylate, 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. Examples of commercially available products 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.
In the above description, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
In one aspect, the photosensitive composition layer preferably contains the polymerizable compound B1 and an ethylenically unsaturated compound having 3 or more functions, and more preferably contains the polymerizable compound B1 and two or more ethylenically unsaturated compounds having 3 or more functions. In this case, the mass ratio of the polymerizable compound B1 to the 3-or more-functional ethylenically unsaturated compound is preferably (total mass of the polymerizable compound B1 (total mass of the 3-or more-functional ethylenically unsaturated compounds) = 1: 1 to 5:1, more preferably 1.2: 1 to 4: 1, and further preferably 1.5: 1 to 3: 1.
In one embodiment, the photosensitive composition layer preferably contains the polymerizable compound B1 and two or more 3-functional ethylenically unsaturated compounds.
Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20 manufactured by Ltd., shin-Nakamura Chemical Co., A-9300-1CL manufactured by Ltd.), ethoxylated trimethylolpropane trimethacrylate (e.g., TOMOE Engineering Co., SR454, SR499, and SR502 manufactured by Ltd.), alkylene oxide-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD RP-1040 manufactured by ltd., shin-Nakamura Chemical co., ATM-35E manufactured by ltd., and a-9300, EBECRYL (registered trademark) 135 manufactured by DAICEL-allex ltd., etc.), ethoxylated glycerol trimethacrylate (Shin-Nakamura Chemical co., a-GLY-9E manufactured by ltd., etc.), ARONIX (registered trademark) TO-2349 (TOAGOSEI co., ltd., etc.), ARONIX M-520 (TOAGOSEI co., ltd., manufactured), and ARONIX M-510 (TOAGOSEI co., ltd., manufactured).
As the polymerizable compound, a polymerizable compound having an acid group (e.g., a carboxyl group) can be used. The acid groups may form anhydride groups. 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 (weight average molecular weight when having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3000, more preferably 280 to 2200, and still more preferably 300 to 2200.
The polymerizable compound may be used alone or in combination of two or more.
The content of the polymerizable compound is preferably 0 to 70% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on the total mass of the photosensitive composition layer.
As described above, the mass ratio of the polymerizable compound other than the resin a contained in the photosensitive composition layer to the resin a is 0.85 or less. The lower limit of the mass ratio is 0.00.
The mass ratio is preferably 0.00 to 0.80, more preferably 0.00 to 0.70, and further preferably 0.30 to 0.65, from the viewpoint of more excellent conductor pattern formability.
(polymerization initiator)
The photosensitive composition layer may contain 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. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, 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.
In addition, from the viewpoint of photosensitivity, visibility of exposed portions and unexposed portions, and resolution, the photosensitive composition layer preferably contains at least one selected from 2,4,5-triarylimidazole dimer and a derivative thereof as a photo radical polymerization initiator. In addition, 2,4,5-triarylimidazole dimer and its derivatives, 22,4,5-triarylimidazole structures may be the same or different.
Examples of 2,4,5-triarylimidazole dimer derivatives 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 the polymerization initiators described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-95716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-14783.
Examples of the photo-radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p '-dimethoxybenzyl) anise ester, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, 4,4' -bis (diethylamino) benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (BASF Co., ltd.), omnirad651 and 369 (trade name: IGM Resins B.V., ltd.), and 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1,2' -biimidazole (Tokyo Co., ltd.).
Examples of commercially available products of the photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), IRGACURE OXE-04 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omnirad 37EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropan-1-one (trade name: omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl ] phenyl } -2-methylpropan-1-one (trade name: omnirad) phenyl } -2-methylpropan-1-one (trade name: IGM Resins B.V.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropan-2-methylpropan-1-one (trade name: IGM-1.V): omnirad 369, igm Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173, manufactured by igm Resins b.v.), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184, igm Resins b.v.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: omnirad651, igm Resins b.v., manufactured), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad TPO H, manufactured by IGM Resins b.v.), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819, igm Resins b.v.), oxime ester type photopolymerization initiators (trade name: lunar 6, manufactured by dksh Japan k.k.), 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by hamford corporation), 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd., manufactured), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PB6-305, changzhou Tronly New Electronic Materials CO., ltd., manufactured), 1,2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (trade name: TR-PBG-326, changzzhou Tronly New Electronic Materials CO, ltd. Manufactured) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1,2-dione-2- (O-benzoyl oxime) (trade name: 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. The photo cation polymerization initiator is preferably a compound which generates an acid by being irradiated with an activating light having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure is not limited. 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 cationic polymerization initiator, a photo cationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photo cationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photo cationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly limited, but is preferably at least-10.0.
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.
As the ionic photo-cationic polymerization initiator, the ionic photo-cationic polymerization initiators described in paragraphs [0114] to [0133] of Japanese patent application laid-open No. 2014-085643 can be used.
Examples of the nonionic photo cation polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds and imide sulfonate compounds, the compounds described in paragraphs [0083] to [0088] of Japanese patent application laid-open No. 2011-221494 can be used. Furthermore, as the oxime sulfonate compound, the compounds described in paragraphs [0084] to [0088] of International publication No. 2018/179640 can be used.
The photosensitive composition layer preferably contains a photo radical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof.
One kind of the polymerization initiator may be used alone, or two or more kinds may be used.
The content of the polymerization initiator (preferably, photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, relative to the total mass of the photosensitive composition layer.
(sensitizer)
The photosensitive composition layer preferably contains a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthenone (xanthone) compounds, thioxanthone (thioxanthone) compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, distyrylbenzene (distyrylbenzene), styrylbenzene (styrylbenzene), triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. In addition, the above-mentioned compounds include derivatives of the above-mentioned compounds.
Among them, as the sensitizer, a dialkylaminobenzophenone compound, an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is preferable, an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is more preferable, and an anthracene derivative, a distyrylbenzene derivative, or a styrylpyridine derivative is further preferable.
One or more kinds of the sensitizer may be used alone.
When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing rate by the balance of the polymerization rate and the chain transfer, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, relative to the total mass of the photosensitive composition layer.
(pigments)
From the viewpoint of visibility of exposed portions and non-exposed portions, pattern visibility after development, and resolution, the photosensitive composition layer preferably contains a dye (also referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 to 780nm during color development is 450nm or more and whose maximum absorption wavelength is changed by an acid, an alkali, or a radical. When the pigment N is contained, although the detailed mechanism is not clear, the adhesion with an adjacent layer (for example, a water-soluble resin layer) is improved and the resolution is further excellent.
In the present specification, the "change in the maximum absorption wavelength of the dye by an acid, an alkali, or a radical" may refer to any one of a method in which the dye in a colored state is decolored by an acid, an alkali, or a radical, a method in which the dye in a decolored state is colored by an acid, an alkali, or a radical, and a method in which the dye in a colored state is changed to a colored state of another color.
Specifically, the dye N may be a compound that develops color by changing from a decolored state by exposure, or may be a compound that develops color by changing from a colored state by exposure. In this 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 color development or the decolored state, or may be one in which the state (for example, pH) in the photosensitive composition layer is changed by an acid, a base, or a radical to change the color development or the decolored state. Further, the dye may be a dye that changes its color or decolored state by being directly stimulated by an acid, a base, or a radical without exposure.
Among them, the pigment N is preferably a pigment whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a pigment 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.
When the photosensitive composition layer is a negative photosensitive composition layer, the negative 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, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.
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 method 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, and then by a radical, an acid, or a base 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 color development of the dye N is preferably 550nm or more, more preferably 550 to 700nm, and still more preferably 550 to 650nm.
The dye N may have only the maximum absorption wavelength in the wavelength range of 400 to 780nm in 1 color development, or may have 2 or more. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm when developing color, 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 is determined by using a spectrophotometer under an atmospheric environment: UV3100 (manufactured by Shimadzu Corporation) is obtained by measuring the transmission spectrum of a solution containing a dye N (liquid temperature 25 ℃) in a wavelength range of 400nm to 780nm and detecting a 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 dye decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
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 colorant), a colorless compound having a spiropyran skeleton (spiropyran-based colorant), a colorless compound having a fluoran skeleton (fluoran-based colorant), a colorless compound having a diarylmethane skeleton (diarylmethane-based colorant), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based colorant), a colorless compound having an indolylphthalein skeleton (indolylphthalein-based colorant), and a colorless compound having a leuco auramine skeleton (leuco auramine-based colorant).
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.
The colorless compound preferably has a lactone ring, a sulfinyl lactone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sulfinyl lactone ring or sultone ring of the colorless compound can be reacted with a radical generated by the photo radical polymerization initiator or an acid generated by the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolor the colorless compound, or the colorless compound can be changed into an open ring state and develop 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 dye N include the following dyes and leuco compounds.
<xnotran> N , , (brilliant green), , , , (basic fuchsine), 2B, (quinaldine red), (rose bengal), (metanil yellow), (thymol sulfonphthalein), (xylenol) , , , , (benzopurpurine) 4B, α - , (nile blue) 2B, A, , (malachite green), (parafuchsin), (victoria pure blue) - , BOH (Hodogaya Chemical Co., ltd. ), #603 (Orient Chemical Industries Co., ltd. ), #312 (Orient Chemical Industries Co., ltd. ), 5B (Orient Chemical Industries Co., ltd. ), (oil scarlet) #308 (Orient Chemical Industries Co., ltd. ), OG (Orient Chemical Industries Co., ltd. ), RR (Orient Chemical Industries Co., ltd. ), #502 (Orient Chemical Industries Co., ltd. ), 8978 zxft 8978 (spi lon red) BEH (Hodogaya Chemical Co., ltd. ), , , B, 6G, B, ,4- ,2- -4- , </xnotran> 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.
<xnotran> N , , p, p', p "- ( ), pergascript Blue SRB (Ciba-Geigy ), , , ,2- (N- -N- ) -6- (N- -N- ) ,2- -3- -6- (N- - ) , 5363 zxft 5363- ,3- (N, N- ) -5- -7- (N, N- ) ,3- (N- -N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -6- -7- ,3- (N, N- ) -7- (4- ) , </xnotran> 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3-piperidinyl-6-methyl-7-anilinofluorane, 3-pyrrolidinyl-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide (phthalide), 3,3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophenyl-6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-3 ' -diphenylamino) -3-ethyl-3 ' -diphenylindol-3-yl) phthalide, and 3- (4-ethyl-2-methyl-3 ' -diphenylindol-3-yl) 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 which develops color by a radical, from the viewpoints of 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 kind of the pigment N may be used alone, or two or more kinds thereof may be used.
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 viewpoints of visibility of exposed portions and non-exposed portions, pattern visibility after development, and resolution.
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 was prepared by dissolving 0.001g and 0.01g of a coloring matter in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photo radical polymerization initiator (trade name, 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 into a colored state. Then, the absorbance of each solution at 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 pigments were developed was measured by the same method as described above except that 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer based on the calibration curve.
The photosensitive composition layer 3g was the same as the photosensitive composition layer 3g in terms of total solid content.
(thermally crosslinkable Compound)
When the photosensitive composition layer is a negative photosensitive composition layer, a thermally crosslinkable compound may be contained from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound but as a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among them, blocked isocyanate compounds are preferable 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 a resin, a polymerizable compound, or the like has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function tends to be enhanced when a film obtained by curing the negative photosensitive composition layer is used as a protective film.
The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".
The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃, more preferably 130 to 150 ℃.
The dissociation temperature of the blocked isocyanate means "a temperature of an endothermic peak accompanying deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter".
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC 6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited thereto.
Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound [ malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ], an oxime compound (a compound having a structure represented by-C (= N-OH) -in a molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).
Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably at least one selected from oxime compounds, for example, from the viewpoint of storage stability.
For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving the brittleness of the film, improving the adhesion to the transfer target, and the like.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanurating hexamethylene diisocyanate to protect it.
Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferable from the viewpoint that the dissociation temperature is more easily set in a preferable range and the development residue is easily reduced than those of compounds having no oxime structure.
The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferred.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group.
Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and still more preferably an acryloyloxy group.
As the blocked isocyanate compound, commercially available products can be used.
Examples of commercially available products of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, and the like (manufactured by SHOWA DENKO K., supra), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, manufactured by Asahi Kasei Chemicals Corporation).
Further, as the blocked isocyanate compound, a compound having the following structure can be used.
[ chemical formula 4]
Figure BDA0003790819850000421
The thermally crosslinkable compound may be used alone or in combination of two or more.
When the photosensitive composition layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.
(pigment)
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 of 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 in the case of forming a black pattern, a black pigment is preferable.
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, a 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, light calcium carbonate, white carbon, aluminum oxide, 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 a silica treatment, an alumina treatment, a titania treatment, a zirconia treatment, or an organic 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 BO (Color Index) (hereinafter, also referred to as "c.i.") 42595), auramine (c.i.41000), fat black (fatbreak) HB (c.i.26150), morronite yellow (monolithic 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), husktaba red (hostaperm red) ESB (c.i. pigment violet 19), permanent ruby red (permanent ruby) FBH (c.i. pigment red 11), french red (peruvi) B (superpura) (c.i. pigment red 149), black pigment red (c.i. pigment red) 168, 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 168, c.i. pigment red 168, c.e. pigment red, 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, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a 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 known additives as needed, in addition to the above components.
Examples of the additives include radical polymerization inhibitors, antioxidants (e.g., phenidone), rust inhibitors (e.g., benzotriazoles and carboxybenzotriazoles), sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazole), pyridines (e.g., isonicotinamide), and purine bases (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.
Each additive may be used alone or in combination of two or more.
The photosensitive composition layer may contain a radical polymerization inhibitor.
Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph [0018] of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other radical polymerization inhibitors include naphthylamine, cuprous chloride, aluminum N-nitrosophenylhydroxylamine salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition layer, an N-nitrosophenylhydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor.
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.
Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
Examples of 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. As the carboxybenzotriazole, for example, a commercially available product such as CBT-1 (johakuchemica co., ltd., trade name) can be used.
The total content of the benzotriazole and carboxybenzotriazole 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 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 content is 3% by mass or less, the maintenance of sensitivity and the inhibition of discoloration of the dye are more excellent.
Examples of the surfactant include surfactants described in paragraphs [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application No. 2009-237362.
The surfactant is preferably a nonionic surfactant, a fluorine surfactant, or a silicone surfactant.
<xnotran> , 5754 zxft 5754-171, 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-551-3252 zxft 3252-552, F-554, F-555-3532 zxft 3532-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS- -628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-3425 zxft 3425-21 ( DIC Corporation ), fluorad FC430, FC431, FC171 ( Sumitomo 3M Limited ), surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 ( AGC Inc. ), polyFox PF636, PF656, PF6320, PF6520, PF7002 ( OMNOVA Solutions Inc. ), ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 ( Neos Corporation ), </xnotran> U-120E (UNICHEM CO., LTD. Manufactured), and the like.
Further, the fluorine-based surfactant can also preferably use an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, and the functional group containing a fluorine atom is partially cleaved when heat is applied, thereby volatilizing the fluorine atom. Examples of such fluorine-based surfactants include MEGAFACE DS series (chemical industry journal (2016, 22/2 and 23/2016) and sunrise industry news (2016, 2/23) manufactured by DIC Corporation), for example MEGAFACE DS-21.
Further, as the fluorine-based surfactant, a polymer 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.
Further, as the fluorine-based surfactant, a terminal-capped polymer can also be used.
Further, as the fluorine-based surfactant, 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) can also be preferably used.
Further, as the fluorine-based surfactant, a fluorine-containing polymer having a group having an ethylenically unsaturated bond in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation).
From the viewpoint of improving environmental compatibility, preferred as the fluorine-based surfactant 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, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, 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. Specific examples thereof include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2, HYDROPALAT WE 3323 (manufactured by BASF Corporation, supra), tetronic (registered trademark) 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation, supra), solsperse 20000 (manufactured by Lubrizol Japan Limited, supra), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation, supra), PIONIN D-1105, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., ltd., supra), olfine E1010, surfynol 104, 400, 440 (manufactured by Nissin Co., ltd., etc.).
Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals thereof.
Specific examples of Silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (see above, DIC Corporation), DOW 8032ADDITIVE, 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 (see above, dow Corning Toray Co., ltd., ltd. Manufacture) and X-22-4952, X-22-4272, X-22-6266, KF-351-A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Silicone Co., ltd., above), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc., above), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BY378K 348, BYK349, BYK370, BYK377, miK 370 (manufactured by Mie, above), and the like.
One kind of surfactant may be used alone, or two or more kinds may be used in combination.
When the photosensitive composition layer contains a surfactant, 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 0.80% by mass, based on the total mass of the photosensitive composition layer.
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%, based on the total mass of the photosensitive composition layer.
The layer thickness (film thickness) of the photosensitive composition layer is generally 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 15 μm, particularly preferably 0.5 to 10 μm, most preferably 0.5 to 8 μm. This improves the developability of the photosensitive composition layer, and can improve the resolution.
In one embodiment, the thickness is preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm, and still more preferably 0.5 to 3 μm.
(impurities, etc.)
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.
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 contamination, 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.
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 mass ppb or more, more preferably 100 mass ppb 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 transfer film production method described later can be given. The content of the residual organic solvent can be quantified by a known method such as gas chromatography.
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%, based on the total mass of the photosensitive composition layer.
(Properties of photosensitive composition layer)
Hereinafter, the properties of the photosensitive composition layer will be described.
Total double bond content-
From the viewpoint of excellent conductor pattern formability, the total double bond content in the photosensitive composition layer is preferably more than 1.00mmol/g with respect to the total mass of the photosensitive composition layer. The total double bond content is more preferably more than 1.20mmol/g, still more preferably more than 2.00mmol/g. The upper limit is not particularly limited, but is 4.00mmol/g or less.
The total double bond content can be calculated as the sum of the double bond content derived from the resin and the double bond content derived from the polymerizable compound.
The double bond content derived from the polymerizable compound can be calculated from the following formula.
(formula) (content ratio of polymerizable compound to total mass of photosensitive composition layer) × (number of double bonds contained in polymerizable compound)/(molecular weight of polymerizable compound)
When the photosensitive composition layer contains a plurality of polymerizable compounds, the content of double bonds derived from the polymerizable compounds may be calculated for each polymerizable compound by the above formula and the calculated content may be added together.
The method of calculating the double bond content derived from the resin is as follows.
The total double bond content can be adjusted by the type of resin, the type of polymerizable compound, the content and ratio thereof, and the like.
Double bond content from the resin
The content of the double bond derived from the resin a is preferably more than 0.20mmol/g with respect to the total mass of the photosensitive composition layer from the viewpoint of excellent conductor pattern formability. The above-mentioned double bond content is more preferably more than 0.55mmol/g, still more preferably more than 0.70mmol/g, particularly preferably more than 1.00mmol/g, most preferably more than 1.10mmol/g. The upper limit is not particularly limited, but may be 2.00mmol/g or less.
The double bond content can be calculated from the following formula, for example. In the following formula, "MD" represents a structural unit having a double bond.
(formula) (content ratio of resin to total mass of photosensitive composition layer) × (content ratio of MD to total mass of resin) × (number of double bonds contained in MD)/(molecular weight of MD)
When the photosensitive composition layer contains a plurality of resins, the double bond content derived from the resin may be calculated from the above formula for each resin, and the calculated double bond content may be added together.
The double bond content can be adjusted by the content of the resin and/or the content of the structural unit having a crosslinkable group in the resin.
In addition, from the viewpoint of excellent conductor pattern formability, it is also preferable that the resin (resin a) contains a structural unit having an alicyclic structure or polycyclic structure and satisfies the requirement of the double bond content (for example, more than 0.55mmol/g or more than 1.00 mmol/g).
Further, it is also preferable that the resin (resin a) contains a structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms and satisfies the requirement of the double bond content (for example, more than 0.55mmol/g or more than 1.00 mmol/g).
Glass transition temperature-
The glass transition temperature of the photosensitive composition layer after exposure to i-ray with an exposure amount of 20mJ/cm2 is preferably 30 ℃ or higher. The upper limit of the glass transition temperature is not particularly limited, and may be 100 ℃.
When the glass transition temperature is 30 ℃ or higher, swelling due to the plating solution during plating treatment is less likely to occur, and the conductive pattern formability is further improved.
The glass transition temperature is 20mJ/cm by i-ray 2 The glass transition temperature of the photosensitive composition layer of 3.0 μm after exposure was measured by a differential scanning calorimeter.
-thickness-
The thickness of the photosensitive composition layer is not particularly limited and can be appropriately selected according to the application, but is preferably 0.5 to 20 μm.
[ intermediate layer ]
The transfer film preferably has 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 alkali 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 water-soluble resin layer (intermediate layer) can contain will be described.
The water-soluble resin layer (intermediate layer) contains a resin.
The resin preferably contains a water-soluble resin as a part or all thereof.
Examples of the resin that can be used as the water-soluble resin include resins such as polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.
Further, as the water-soluble resin, a copolymer of (meth) acrylic acid/vinyl compound, or the like can also be used. As the copolymer of (meth) acrylic acid/vinyl compound, a copolymer of (meth) acrylic acid/(meth) allyl acrylate is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable.
When the water-soluble resin is a copolymer of (meth) acrylic acid/vinyl compound, the composition ratio (% by mole) is, for example, preferably 90/10 to 20/80, more preferably 80/20 to 30/70.
The lower limit of the weight average molecular weight of the water-soluble resin is preferably 5000 or more, more preferably 7000 or more, and still more preferably 10000 or more. The upper limit value is preferably 200000 or less, more preferably 100000 or less, and still more preferably 50000 or less.
The dispersity (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
One kind of the water-soluble resin may be used alone, or two or more kinds thereof may be used.
The content of the water-soluble resin is not particularly limited, but 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 water-soluble resin layer (intermediate layer), from the viewpoint of further improving the oxygen barrier property and the interlayer mixing suppression ability. The upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less.
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 polyol include compounds obtained by adding an ethyleneoxy group, a propyleneoxy group, or the like to the above polyol.
The average addition number of alkyleneoxy groups is preferably 1 to 100, more preferably 2 to 50, and further 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 5000, more preferably 4000 or less, still more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. The lower limit is preferably 60 or more.
One or more of the other components may be used alone.
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.
The intermediate layer may contain impurities.
Examples of the impurities include impurities contained in the photosensitive composition layer.
The thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the interlayer mixing suppression capability is excellent without lowering the oxygen barrier property. In addition, the increase in the time for removing the water-soluble resin layer (intermediate layer) during development can be further suppressed.
[ protective film ]
The transfer film may have a protective film on the photosensitive composition layer.
As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include 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 can be used.
Among these, as the protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polypropylene film is further 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 relative low cost.
In the protective film, the number of fish eyes (fisherye) having a diameter of 80 μm or more contained in the protective film is preferably 5/m 2 The following.
The term "fish eye" refers to a phenomenon in which foreign matter, undissolved matter, oxidized and degraded matter, etc. of a material are taken into a film when the material is melted, kneaded, extruded, and the film is produced by a method such as biaxial stretching or casting.
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, more preferably 5 pieces/mm 2 The following.
This can suppress defects caused by transfer of the unevenness caused by the particles contained in the protective film to the photosensitive composition layer or the metal layer.
From the viewpoint of imparting windability, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the side in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, further preferably 0.03 μm or more, and particularly preferably more than 0.05 μm. On the other hand, it is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.
From the viewpoint of suppressing defects at the time of transfer, the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. On the other hand, it is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.
[ 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 on 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 produced by forming the composition layer 17 on the protective film 19.
(Water-soluble resin composition and method for Forming intermediate layer (Water-soluble resin layer))
The water-soluble resin composition preferably contains various components and solvents for forming the 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 2500 parts by mass, more preferably 50 to 1900 parts by mass, and still more preferably 100 to 900 parts by mass, per 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 (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 layer by using a photosensitive composition containing a component (for example, the resin a, the polymerizable compound, the polymerization initiator, and the like) constituting the photosensitive composition layer and a solvent by a coating method.
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 preferably contains various components for forming the photosensitive composition layer and a solvent. In the photosensitive 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 photosensitive composition layer.
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, 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, 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.
As the solvent, a solvent described in paragraphs [0092] to [0094] of international publication nos. 2018/179640 and a solvent described in paragraph [0014] of japanese patent application laid-open No. 2018-177889 can be used, and these contents are incorporated in the present specification.
One solvent may be used alone, or two or more solvents may be used.
The content of the solvent is preferably 50 to 1900 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.
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).
As a method for drying the coating film of the photosensitive composition, heating drying and drying under reduced pressure are preferable.
The drying temperature is preferably 90 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 110 ℃ or higher. The upper limit is not particularly limited, but 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 value is not particularly limited, but is preferably 450 seconds or less, and more preferably 300 seconds or less. The drying temperature is preferably 80 ℃ or higher, more preferably 90 ℃ or higher. The upper limit thereof is preferably 130 ℃ or lower, more preferably 120 ℃ or lower. Drying can also be performed by continuously changing the temperature.
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 value is not particularly limited, but is preferably 600 seconds or less, and more preferably 300 seconds or less.
Further, the transfer film can be manufactured by bonding a protective film to the photosensitive composition layer.
The method for bonding the protective film to the photosensitive composition layer is not particularly limited, and known methods can be exemplified.
Examples of the device for bonding the protective film to the photosensitive composition layer include known laminating machines such as a vacuum laminating machine and an automatic cutting laminating machine.
The laminator is preferably provided with an optional heatable roller such as a rubber roller and can be pressurized and heated.
[ 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 treatment, the steps of the treatment, and the like shown 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.
In the following examples, the weight average molecular weight of the resin was determined by polystyrene conversion based on Gel Permeation Chromatography (GPC). The acid value of the resin is a theoretical acid value derived from the ratio of the structural units of the resin.
< transfer film >
Transfer films were produced using the compositions shown in tables 2 and 3 of the subsequent stage.
First, each component used for manufacturing a transfer film will be described.
[ photosensitive composition ]
The photosensitive composition layer of the transfer film is formed using the photosensitive composition.
The materials shown in tables 2 and 3 in the latter stage were mixed according to the formulations shown in tables 2 and 3 to obtain photosensitive compositions used for the production of transfer films of examples and comparative examples.
Hereinafter, each component used for producing the photosensitive composition will be described.
(resin)
Synthesis of resin A1
67g of propylene glycol monomethyl ether was charged into a flask and heated to 90 ℃ under a nitrogen stream. To this liquid, a solution prepared by dissolving 47.7g of styrene, 1.3g of methyl methacrylate, 19g of methacrylic acid and 4g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) in 33g of propylene glycol monomethyl ether was added dropwise over 3 hours. After completion of the dropwise addition, 1g of V-601 was added 3 times per 1 hour. Then, it was further reacted for 3 hours. After the reaction, the reaction mixture was diluted with 33g of propylene glycol monomethyl ether acetate and 100g of propylene glycol monomethyl ether.
The diluted reaction solution was heated to 100 ℃ under an air stream, and 0.53g of tetraethylammonium bromide and 0.26g of p-methoxyphenol were added. To the liquid, 32G of glycidyl methacrylate (BLEMMER G manufactured by NOF CORPORATION) was added dropwise over a period of 20 minutes. After the reaction of the liquid at 100 ℃ for 7 hours, the reaction mixture was diluted with propylene glycol monomethyl ether acetate to obtain a solution of resin A1 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 to A9 shown in table 1 were synthesized by the same method. The amount of residual monomer in each resin as determined by gas chromatography was less than 0.1% by mass relative to the polymer solids in either monomer.
The amount of structural units, weight average molecular weight, double bond content, and glass transition temperature (Tg) of each resin synthesized are shown in table 1.
In table 1, the respective abbreviation names are as follows.
St: styrene (meth) acrylic acid ester
MMA: methacrylic acid methyl ester
MAA: methacrylic acid
GMA-MAA: structural unit obtained by adding glycidyl methacrylate to structural unit derived from methacrylic acid
DCPMA: methacrylic acid dicyclopentyl ester
IBMA: isobornyl methacrylate
BzMA: methacrylic acid benzyl ester
GMA-MAA represents a structural unit represented by the following chemical formula.
[ chemical formula 5]
Figure BDA0003790819850000581
[ Table 1]
Figure BDA0003790819850000582
(polymerizable Compound)
BPE-100: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd. (double bond content: 4.30 mmol/g)
M-270: ARONIX M-270, polypropylene glycol diacrylate (n. Apprxeq.12), TOAGOSEI CO., LTD. (double bond content: 2.50 mmol/g)
SR494: ethoxylated (4) pentaerythritol tetraacrylate, TOMOE Engineering Co., ltd. (double bond content: 7.58 mmol/g)
BPE-500: ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., ltd. (double bond content: 2.49 mmol/g)
(photopolymerization initiator)
B-IMD:2- (o-chlorophenyl) -4,5-diphenylimidazole dimer
(sensitizer)
EAB-F:4,4' -bis (diethylamino) benzophenone
DBA:9,10-dibutoxyanthracene
DSP:2,5-distyrylpyridine
DSB: trans, trans-1,4-distyrylbenzene
(polymerization inhibitor)
Phenothiazine
Phenidone: 1% of phenidone MEK solution
(chain transfer agent)
Compound a: N-Phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation)
(color-developing agent)
LCV: colorless crystal violet: manufactured by Tokyo Chemical Industry Co., ltd
(Rust preventive)
CBT-1: carboxy benzotriazole, joohoku CHEMICAL co
(surfactant)
F-552: MEGAFACE F-552 manufactured by DIC Corporation
(solvent)
MMPGAc: 1-methoxy-2-propyl acetate
MEK: methyl ethyl ketone
MFG: propylene glycol monomethyl ether
[ composition for Forming intermediate layer ]
The intermediate layer of the transfer film is formed using the intermediate layer-forming composition.
The materials shown in tables 2 and 3 in the latter stage were mixed according to the formulations shown in tables 2 and 3 to obtain intermediate layer-forming compositions used for production of transfer films of examples and comparative examples.
(resin)
PVA: polyvinyl alcohol, product name "KURARAAY POVAL PVA-205", manufactured by Kuraray Co., ltd
PVP: polyvinylpyrrolidone, product name "polyvinylpyrrolidone K-30", NIPPON shokubali co
(surfactant)
F444: MEGAFACE F444, fluorosurfactant, DIC Corporation
(solvent)
Pure water
MeOH: methanol
[ production of transfer film ]
Each transfer film used in each example was produced, which was composed of a temporary support, an intermediate layer, and a photosensitive composition layer. The transfer film used in the comparative example was produced in the same manner as the transfer films of the examples, except that the intermediate layer was not formed. The details are as follows.
First, an intermediate layer-forming composition was applied to the surface of a temporary support (a 16 μm thick polyethylene terephthalate film (lumiror (registered trademark) 169440, manufactured by toray industries, inc.) using a bar coater so that the thickness after drying became 1.1 μm. The coating film was dried at 90 ℃ using an oven to form an intermediate layer.
Next, a photosensitive composition was applied onto the surface of the formed intermediate layer using a bar coater so that the thickness after drying became 3.0 μm. The coating film was dried at 80 ℃ using an oven to form a photosensitive composition layer (negative photosensitive composition layer).
A transfer film used in each example or comparative example was prepared by pressure-bonding polyethylene terephthalate (169440, manufactured by TORAY INDUSTRIES, INC.) having a thickness of 16 μm as a protective film onto the obtained photosensitive composition layer.
< evaluation >
[ formation of resist Pattern ]
As the substrate having a metal layer, a PET substrate with a copper layer was used in which a copper layer having a thickness of 500nm was formed on a PET film (polyethylene terephthalate film) having a thickness of 188 μm by a sputtering method.
The transfer film produced in the above procedure was cut into a 50cm square, and the protective film was peeled off, and the transfer film was laminated on the PET substrate with 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.
At this point, the laminate had a structure of "PET film-copper layer-photosensitive composition layer-intermediate layer-temporary support".
Next, the temporary support was peeled from the obtained laminate, and the intermediate layer (photosensitive composition layer in comparative example 1) was exposed on the surface of the laminate. A photomask having a pattern with a line width of 0.5 to 1.0 [ mu ] m (increasing in units of 0.1 [ mu ] m), 1.2 to 1.8 [ mu ] m (increasing in units of 0.3 [ mu ] m), and 2.0 to 10.0 [ mu ] m (increasing in units of 1.0 [ mu ] m) at a ratio of line ([ mu ] m)/space ([ mu ] m) of 1/1 is brought into close contact with the exposed intermediate layer of the laminate.
The photosensitive composition layer was exposed by irradiating the laminate with light using a high-pressure mercury lamp exposure machine (MAP-1200L, japan Science Engineering Co., ltd., dominant wavelength: 365 nm). The exposure amount was set to an exposure amount in which a resist pattern of a portion corresponding to a line and space shape of 5 μm of the photomask was reproduced after development in a line and space shape of 5 μm.
Then, development was performed using a 1.0% sodium carbonate aqueous solution (pH = 11.4) at 30 ℃ as a developer. Specifically, the developer was removed by spraying with a developer for 30 seconds and air knife (AirKnife) treatment, and then the developer was sprayed with pure water for 30 seconds and further air knife treatment was performed.
Thus, a laminate having a resist pattern with a line-and-space shape having a line width/space width = 1: 1 was obtained.
At this point, the laminate had a structure of "PET film-copper layer-resist pattern".
[ formation of conductor Pattern ]
The laminate obtained through the above-described steps was immersed in an acidic degreasing agent (OKUNO CHEMICAL additives C0., ATS PURE CLEAN N3 manufactured by ltd.) at a liquid temperature of 45 ℃ for 5 minutes to be subjected to an acid degreasing treatment. Further, the acid activation treatment was performed by immersing the substrate in 10% sulfuric acid at room temperature for 3 minutes.
Placing in copper sulfate plating solution (Top Lucina SF manufactured by Okuno CHEMICAL Industroes CO., LTD.) at a concentration of 1A/dm 2 Copper plating treatment was performed under the conditions of (1).
After the copper plating-treated laminate was washed with water and dried, the laminate was immersed in a1 mass% potassium hydroxide aqueous solution (pH = 13.5) at 50 ℃, whereby the resist pattern was peeled off.
The copper layer (seed layer) of the laminate after the resist pattern stripping step was removed with an aqueous solution containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide to obtain a conductor pattern (copper wiring pattern).
[ evaluation of conductor Pattern formability ]
When the conductor pattern was observed with a field emission scanning electron microscope (FE-SEM, manufactured by JEOL ltd., JSM-7200F), it was confirmed that the minimum pattern line width corresponding to the photomask, which enables formation of the conductor pattern without defects such as disconnection, short circuit, or collapse of the conductor pattern, was possible. The minimum pattern line widths are shown in tables 2 and 3.
From the minimum pattern line width, the conductor pattern formability was evaluated by the following evaluation criteria. The evaluation results of the conductor pattern formability are shown in tables 2 and 3.
When the minimum pattern line width is small, the conductor pattern formability is good, and in practice, the evaluation of C or more is preferable.
(evaluation criteria for conductor Pattern formability)
A: minimum pattern line width of 1.0 μm or less
B: minimum pattern line width of more than 1.0 μm and 1.5 μm or less
C: minimum pattern line width of more than 1.5 μm and 2.0 μm or less
D: minimum pattern line width exceeding 2.0 μm
< results >
Table 2 and table 3 show the composition formulations of the intermediate layer and the transfer film and the evaluation results of the conductive pattern formability in each example and each comparative example.
In tables 2 and 3, the components of the photosensitive composition and the composition for forming an intermediate layer were as described above.
In tables 2 and 3, the contents of the respective components are parts by mass.
In tables 2 and 3, the symbol "polymerizable compound/resin" indicates the ratio of the content of the polymerizable compound to the solid content of the resin.
[ Table 2]
Figure BDA0003790819850000631
[ Table 3]
Figure BDA0003790819850000641
From the results in tables 2 and 3, it was confirmed that the method for producing a laminate having a conductor pattern according to the present invention exhibited the desired effects.
From the comparison between example 4 and other examples, it was confirmed that when the content of the double bond derived from the resin is more than 0.20mmol/g based on the total mass of the photosensitive composition layer, the conductor pattern formability is more excellent.
From the comparison of examples 2, 7 and 10 to 12 with other examples, it was confirmed that when the content of the double bond derived from the resin is more than 1.00mmol/g based on the total mass of the photosensitive composition layer, the conductor pattern formability is more excellent.
As confirmed by comparison of example 3 with other examples, when the exposure amount is 20mJ/cm using i-ray 2 When the glass transition temperature of the photosensitive composition layer after exposure is 30 ℃ or higher, the conductive pattern formability is further excellent.
From comparison of example 4 with other examples, it was confirmed that when the resin contains a structural unit containing a group having a double bond and the content of the structural unit is 10 mass% or more with respect to the total mass of the resin, the conductor pattern formability is more excellent.
It was confirmed from comparison of example 9 with other examples that when the weight average molecular weight of the resin was 3000 to 18000, the conductor pattern formability was more excellent.
[ examples 13 to 18]
Transfer films for examples 13 to 18 were produced in the same manner as in examples 1 to 6 except that in examples 1 to 6, the photosensitive composition was applied such that the thickness of the photosensitive composition layer after drying became 19.0 μm.
Using the transfer films used in examples 13 to 18, resist patterns were formed in the same manner as in examples 1 to 6, and conductor patterns were formed. However, in the formation of the resist pattern, a photomask having a pattern in which a line (μm)/space (μm) ratio is 1/1 and line widths of the lines are 0.5 to 1.0 μm (increasing in units of 0.1 μm), 1.2 to 1.8 μm (increasing in units of 0.3 μm), and 2.0 to 20.0 μm (increasing in units of 1.0 μm) was used as a photomask. The exposure amount was set so that the resist pattern at the portion corresponding to the 10.0 μm line-and-space shape of the photomask reproduced the exposure amount at the 10.0 μm line-and-space shape after development.
Similarly to the above, the formed conductor pattern was observed with a field emission scanning electron microscope, and the minimum pattern line width was confirmed. In examples 13 to 18, the conductor pattern formability was evaluated based on the minimum pattern line width in the following evaluation criteria. The evaluation results of the minimum pattern line width and the conductor pattern formability are shown in table 4.
When the minimum pattern line width is small, the conductor pattern formability is good, and in practice, the evaluation of C or more is preferable.
(evaluation criteria for conductor Pattern formability)
A: minimum pattern line width of 5.0 μm or less
B: minimum pattern line width exceeding 5.0 μm and 6.0 μm or less
C: minimum pattern line width of more than 6.0 μm and 8.0 μm or less
D: minimum pattern line width exceeding 8.0 μm
[ Table 4]
Figure BDA0003790819850000661
From the results in table 4, it was confirmed that the method for producing a laminate having a conductor pattern according to the present invention exhibited the desired effects.
From the comparison between example 16 and other examples, it was confirmed that when the content of the double bond derived from the resin is more than 0.20mmol/g based on the total mass of the photosensitive composition layer, the conductor pattern formability is more excellent.
From the comparison between example 14 and other examples, it was confirmed that when the content of the double bond derived from the resin is more than 1.00mmol/g based on the total mass of the photosensitive composition layer, the conductor pattern formability is more excellent.
From example 15 to other examplesThe comparison confirmed that when the i-ray is used, the exposure amount is 20mJ/cm 2 When the glass transition temperature of the photosensitive composition layer after exposure is 30 ℃ or higher, the conductive pattern formability is further excellent.
From comparison of example 16 with other examples, it was confirmed that when the resin contains a structural unit containing a group having a double bond and the content of the structural unit is 10 mass% or more with respect to the total mass of the resin, the conductor pattern formability is more excellent.
[ examples 19 to 25]
In example 2, transfer films for examples 19 to 25 were produced in the same manner as in example 2, except that the types of the surfactant for the intermediate layer and the surfactant for the photosensitive composition layer were changed as shown in table 5 in the subsequent stage.
Using the transfer films used in examples 19 to 25, a resist pattern was formed in the same manner as in example 2, and formation of a conductor pattern was performed.
Similarly to the above, the formed conductor pattern was observed with a field emission scanning electron microscope, and the minimum pattern line width was confirmed. In examples 19 to 25, the conductor pattern formability was evaluated based on the minimum pattern line width by the same evaluation criteria as in example 2. The evaluation results of the minimum pattern line width and the conductor pattern formability are shown in table 5.
In table 5, the abbreviated names of the surfactants used for the intermediate layer and the surfactant used for the photosensitive composition layer are as follows.
(surfactant)
F-552: MEGAFACE F-552 manufactured by DIC Corporation
EXP.S-315: silicone based surfactants, DIC manufacture
EXP.S-503-2: silicone based surfactant, manufactured by DIC Corporation
KP-124: silicone surfactant, shin-Etsu Chemical Co., ltd
F444: MEGAFACE F444, fluorosurfactant, DIC Corporation
BYK-345: silicone based surfactant, BYK Japan K.K
BYK-348: silicone based surfactant, BYK Japan K.K. manufacture
EXP.S-506: silicone based surfactant, manufactured by DIC Corporation
[ Table 5]
Figure BDA0003790819850000681
From the results in table 5, it was confirmed that the method for producing a laminate having a conductor pattern according to the present invention exhibited the desired effects, and examples 19 to 25 exhibited the same evaluation results as example 2.
[ examples 101 to 107]
Transfer films for examples 101 to 107 were produced in the same manner as in example 2, except that the protective film was changed to the protective film shown in table 6 shown in the subsequent stage in example 2. In table 6, "P2" in the column of the type of the photosensitive composition layer indicates that the same photosensitive composition layer as used in example 2 was used.
The transfer films used in examples 101 to 107 were evaluated for the conductor pattern formability in the same manner as in example 2, and the results thereof were the same as in example 2.
Further, the transfer films used in examples 101 to 107 were taken out under a condition of 4 m/min and transported, and as a result, the transportability was good and no blocking was caused. Specifically, when the transfer film was transported in a roll-to-roll manner, it was visually confirmed that wrinkles, twists, and the like did not occur in the transfer film. In particular, the transfer films used in examples 101 to 106 were rolled out under a condition of 4 m/min and transported, and as a result, transportability was more excellent.
[ examples 108 to 114]
Transfer films for examples 108 to 114 were produced in the same manner as in example 14, except that in example 14, the protective film was changed to the protective film of table 6 in the subsequent stage. In table 6, "P14" in the column of the type of the photosensitive composition layer indicates that the same photosensitive composition layer as used in example 14 was used.
The transfer films used in examples 108 to 114 were evaluated for the conductor pattern formability in the same manner as in example 14, and the results thereof were the same as those in example 14, respectively.
Further, the transfer films used in examples 108 to 114 were taken out and conveyed under conditions of 4 m/min, and as a result, the conveyance performance was good and no blocking was caused. Specifically, when the transfer film is transported in a roll-to-roll manner, it is visually confirmed that wrinkles, twists, and the like do not occur in the transfer film. In particular, the transfer films used in examples 108 to 113 were rolled out under a condition of 4 m/min and transported, and as a result, transportability was more excellent.
[ examples 115 to 121]
Transfer films used in examples 115 to 121 were produced in the same manner as in examples 19 to 25, except that the protective film was changed to the protective film of table 7 in the subsequent stage in examples 19 to 25. In table 7, "P19" in the column of the type of the photosensitive composition layer indicates that the same photosensitive composition layer as that used in example 19 was used, and the same applies to P20 to P25.
The transfer films used in examples 115 to 121 were evaluated for conductor pattern formability in the same manner as in examples 19 to 25, and the results thereof were the same as in examples 19 to 25, respectively.
Further, the transfer films used in examples 115 to 121 were rolled out under a condition of 4 m/min and transported, and as a result, the transportability was good and no blocking was caused. Specifically, when the transfer film was transported in a roll-to-roll manner, it was visually confirmed that wrinkles, twists, and the like did not occur in the transfer film.
[ Table 6]
Figure BDA0003790819850000701
[ Table 7]
Figure BDA0003790819850000702
Description of the symbols
10-transfer film, 11-temporary support, 13-intermediate layer, 15-photosensitive composition layer, 17-composition layer, 19-protective film.

Claims (26)

1. A method for manufacturing a laminate having a conductor pattern, comprising:
a bonding step of bonding a transfer film having a temporary support and a photosensitive composition layer to a substrate having a metal layer on a surface thereof so that the surface of the transfer film opposite to the temporary support is in contact with the metal layer of the substrate;
an exposure step of pattern-exposing the photosensitive composition layer;
a developing step of performing a developing treatment on the exposed photosensitive composition layer to form a resist pattern;
a plating step of performing plating treatment on the metal layer located in a region where the resist pattern is not arranged;
a stripping step of stripping the resist pattern; and
a removing step of removing the metal layer exposed in the peeling step to form a conductor pattern on the substrate,
a temporary support peeling step of peeling the temporary support between the bonding step and the exposure step or between the exposure step and the development step,
the photosensitive composition layer contains a resin having a crosslinkable group,
the weight average molecular weight of the resin is more than 3000,
the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less.
2. The method for producing a laminate having a conductor pattern according to claim 1,
the total double bond content in the photosensitive composition layer is greater than 1.00mmol/g relative to the total mass of the photosensitive composition layer.
3. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the double bond content derived from the resin is more than 0.20mmol/g relative to the total mass of the photosensitive composition layer.
4. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the double bond content derived from the resin is more than 1.00mmol/g relative to the total mass of the photosensitive composition layer.
5. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
exposure at 20mJ/cm using i-ray 2 The glass transition temperature of the photosensitive composition layer after exposure is 30 ℃ or higher.
6. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the glass transition temperature of a film formed solely of the resin is 50 ℃ or higher.
7. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the resin comprises a structural unit containing a group having a double bond,
the content of the structural unit is 10 mass% or more with respect to the total mass of the resin.
8. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the resin includes a structural unit derived from a monomer having an alicyclic structure or a polycyclic structure.
9. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the resin contains a structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms.
10. The method for manufacturing a laminate having a conductor pattern according to claim 9,
the hydrocarbon group has a branch.
11. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer.
12. The method for producing a laminate having a conductor pattern according to claim 1 or 2,
the exposure step is a step of performing pattern exposure through a photomask.
13. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using an activating light beam on which an image of a photomask is projected.
14. The method for manufacturing a laminate having a conductor pattern according to claim 1 or 2,
a temporary support stripping step is provided between the bonding step and the exposure step,
the exposure step is a step of exposing a pattern by bringing the surface exposed by peeling off the temporary support into contact with a photomask.
15. A transfer film having a temporary support and a photosensitive composition layer,
the photosensitive composition layer contains a resin having a crosslinkable group,
the weight average molecular weight of the resin is more than 3000,
the mass ratio of the polymerizable compound other than the resin contained in the photosensitive composition layer to the resin is 0.85 or less,
the temporary support has a haze of 1.0% or less.
16. The transfer film according to claim 15,
the double bond content derived from the resin is more than 0.55mmol/g relative to the total mass of the photosensitive composition layer,
the resin includes a structural unit derived from a monomer having an alicyclic structure or a polycyclic structure.
17. The transfer film according to claim 15 or 16,
the double bond content derived from the resin is more than 0.55mmol/g relative to the total mass of the photosensitive composition layer,
the resin contains a structural unit derived from a (meth) acrylate monomer having a hydrocarbon group having 9 or more carbon atoms.
18. The transfer film according to claim 17,
the hydrocarbon group has a branch.
19. The transfer film according to claim 15 or 16,
the weight average molecular weight of the resin is 3000-18000.
20. The transfer film according to claim 15 or 16,
the thickness of the temporary support is 50 [ mu ] m or less.
21. The transfer film according to claim 15 or 16,
the photosensitive composition layer further comprises a sensitizer,
the sensitizer is selected from distyrylbenzene derivatives, styrylpyridine derivatives and anthracene derivatives.
22. The transfer film according to claim 15 or 16,
the photosensitive composition layer further contains a polymerizable compound,
the polymerizable compound includes an alkylene oxide-modified bisphenol structure.
23. The transfer film according to claim 15 or 16, which has an intermediate layer between the temporary support and the photosensitive composition layer.
24. The transfer film according to claim 23,
the middle layer is a water-soluble resin layer.
25. The transfer film according to claim 15 or 16, which is a transfer film comprising the temporary support, the photosensitive composition layer, and a protective film in this order,
the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the side in contact with the photosensitive composition layer exceeds 0.05 [ mu ] m.
26. The transfer film according to claim 15 or 16, which is a transfer film comprising the temporary support, the photosensitive composition layer, and a protective film in this order,
the protective film is a polypropylene film.
CN202210958155.0A 2021-08-31 2022-08-10 Method for manufacturing laminate having conductor pattern, and transfer film Pending CN115729044A (en)

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