CN116762040A - Method for producing laminate, method for producing circuit wiring, and transfer film - Google Patents

Method for producing laminate, method for producing circuit wiring, and transfer film Download PDF

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Publication number
CN116762040A
CN116762040A CN202180085898.5A CN202180085898A CN116762040A CN 116762040 A CN116762040 A CN 116762040A CN 202180085898 A CN202180085898 A CN 202180085898A CN 116762040 A CN116762040 A CN 116762040A
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CN
China
Prior art keywords
photosensitive composition
composition layer
transfer film
layer
mass
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CN202180085898.5A
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Chinese (zh)
Inventor
石坂壮二
松田知树
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN116762040A publication Critical patent/CN116762040A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a method for manufacturing a laminate including a pattern having excellent pattern shape and excellent pattern adhesion, a method for manufacturing a circuit wiring, and a transfer film. The method for producing a laminate of the present invention comprises: a bonding step of bringing a surface of a photosensitive composition layer of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, which surface is opposite to the intermediate layer side, into contact with a substrate, and bonding the transfer film and the substrate; a peeling step of peeling the temporary support between the temporary support and the intermediate layer; an exposure step of exposing the photosensitive composition layer to a pattern; and a developing step of developing the exposed photosensitive composition layer with a developing solution to form a pattern, wherein the elastic modulus X obtained in the measurement X is 1.0-10.0 GPa.

Description

Method for producing laminate, method for producing circuit wiring, and transfer film
Technical Field
The invention relates to a method for manufacturing a laminate, a method for manufacturing a circuit wiring, and a transfer film.
Background
Since the number of steps for obtaining a predetermined pattern is small, a method of disposing a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing the exposed photosensitive composition layer is widely used.
For example, patent document 1 discloses a photosensitive resin laminate in which an intermediate layer and a photosensitive resin layer are laminated in this order on a support film.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2008-175957
Disclosure of Invention
Technical problem to be solved by the invention
As a result of studies on a method for producing a laminate using a conventional transfer film or the like as described in patent document 1, the inventors have found that the shape of the obtained pattern is likely to be defective. It has also been found that the above-described problems are likely to occur particularly when the temporary support is peeled off for exposure in order to obtain a higher definition pattern. Specifically, the transfer film is attached to the transfer body, and after the temporary support is peeled off, pattern exposure is performed, and then development is performed to obtain a desired pattern. When the cross-sectional shape of the obtained pattern was observed, it was found that the pattern shape was likely to be a skirt spread shape in which the pattern width was widened as it was approached from the side opposite to the substrate side. That is, the skirt expansion shape is a pattern shape in which the length of the lower bottom surface (substrate side) is longer than the length of the upper bottom surface (substrate opposite side) among the obtained pattern shapes. More specifically, as shown in fig. 1, in the pattern 2 arranged on the substrate 1, there is a problem that the skirt extension 3 as shown in the broken line portion occurs.
Hereinafter, the obtained pattern is also referred to as excellent pattern shape when it is less likely to have a skirt expansion shape.
On the other hand, there is also a demand for a pattern obtained by transferring a photosensitive composition layer in a transfer film to a transfer body and exposing and developing the photosensitive composition layer to light, which is less likely to be peeled off from the transfer body, and which has excellent pattern adhesion. In particular, higher definition patterns are required to have excellent adhesion.
Accordingly, an object of the present invention is to provide a method for producing a laminate including a pattern having an excellent pattern shape and also having excellent pattern adhesion.
The present invention also provides a method for producing a circuit wiring and a transfer film.
Means for solving the technical problems
As a result of intensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following constitution.
[ 1 ] A method for producing a laminate, comprising:
a bonding step of bringing a surface of a photosensitive composition layer of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, which surface is opposite to the intermediate layer side, into contact with a substrate, and bonding the transfer film and the substrate;
a peeling step of peeling the temporary support between the temporary support and the intermediate layer;
An exposure step of performing pattern exposure on the photosensitive composition layer; a kind of electronic device with high-pressure air-conditioning system
A developing step of developing the photosensitive composition layer after exposure with a developing solution to form a pattern,
the elastic modulus X obtained in the measurement X described later is 1.0 to 10.0GPa.
The method for producing a laminate according to [ 1 ], wherein,
the elastic modulus Y obtained in the measurement Y described later is 3.5MPa or less.
The method for producing a laminate according to [ 2 ], wherein,
the ratio of the elastic modulus X to the elastic modulus Y is 1500 to 10000.
The method for producing a laminate according to any one of [ 1 ] to [ 3 ], wherein,
the content of double bonds in the photosensitive composition layer is 1.0 to 3.0mmol/g.
The method for producing a laminate according to any one of [ 1 ] to [ 4 ], wherein,
the photosensitive composition layer contains a resin,
the glass transition temperature Tg of the resin is 90-150 ℃.
The method for producing a laminate according to any one of [ 1 ] to [ 5 ], wherein,
the acid value of the photosensitive composition layer is 50-100 mgKOH/g.
The method for producing a laminate according to any one of [ 1 ] to [ 6 ], wherein,
The photosensitive composition layer contains a polymerizable compound having 2 or more functions and a resin,
the mass ratio of the content of the 2-functional or higher polymerizable compound to the content of the resin is 0.60 to 1.00.
The method for producing a laminate according to any one of [ 1 ] to [ 7 ], wherein,
the intermediate layer contains at least 1 selected from the group consisting of polyols, oxide adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.
The method for producing a laminate according to any one of [ 1 ] to [ 8 ], wherein,
the thickness of the photosensitive composition layer is 1-20 μm.
The method for producing a laminate according to any one of [ 1 ] to [ 9 ], wherein,
the thickness of the intermediate layer is 3.0 μm or less.
The method for producing a laminate according to any one of [ 1 ] to [ 10 ], wherein,
the exposure step is an exposure step of exposing the pattern by bringing the exposed intermediate layer into contact with a mask.
[ 12 ] A method for manufacturing a circuit wiring, comprising:
a bonding step of bringing a surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, the surface being on the opposite side of the photosensitive composition layer from the intermediate layer side, into contact with a substrate having a conductive layer, and bonding the transfer film and the substrate;
A peeling step of peeling the temporary support between the temporary support and the intermediate layer;
an exposure step of performing pattern exposure on the photosensitive composition layer;
a developing step of developing the photosensitive composition layer after exposure with a developing solution to form a pattern; a kind of electronic device with high-pressure air-conditioning system
An etching step of etching the conductive layer in a region where the pattern is not arranged,
the elastic modulus X obtained in the measurement X described later is 1.0 to 10.0GPa.
[ 13 ] A transfer film comprising, in order, a temporary support, an intermediate layer and a photosensitive composition layer,
and an exposure step of performing pattern exposure on the photosensitive composition layer,
the elastic modulus X obtained in the measurement X described later is 1.0 to 10.0GPa.
The transfer film according to [ 13 ], wherein,
the elastic modulus Y obtained in the measurement Y described later is 3.5MPa or less.
The transfer film according to [ 15 ], wherein,
the ratio of the elastic modulus X to the elastic modulus Y is 1500 to 10000.
The transfer film according to any one of [ 13 ] to [ 15 ], wherein,
the content of double bonds in the photosensitive composition layer is 1.0 to 3.0mmol/g.
The transfer film according to any one of [ 13 ] to [ 16 ], wherein,
the photosensitive composition layer contains a resin,
the glass transition temperature Tg of the resin is 90-150 ℃.
The transfer film according to any one of [ 13 ] to [ 17 ], wherein,
the acid value of the photosensitive composition layer is 50-100 mgKOH/g.
The transfer film according to any one of [ 13 ] to [ 18 ], wherein,
the photosensitive composition layer contains a polymerizable compound having 2 or more functions and a resin,
the mass ratio of the content of the 2-functional or higher polymerizable compound to the content of the resin is 0.60 to 1.00.
The transfer film according to any one of [ 13 ] to [ 19 ], wherein,
the intermediate layer contains at least 1 selected from the group consisting of polyols, oxide adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.
The transfer film according to any one of [ 13 ] to [ 20 ], wherein,
the thickness of the photosensitive composition layer is 1-20 μm.
The transfer film according to any one of [ 13 ] to [ 21 ], wherein,
The thickness of the intermediate layer is 3.0 μm or less.
Effects of the invention
According to the present invention, a method for manufacturing a laminate including a pattern having an excellent pattern shape and also having an excellent pattern adhesion can be provided.
Further, according to the present invention, a method for manufacturing a circuit wiring and a transfer film can be provided.
Drawings
Fig. 1 is a schematic diagram showing an example of a skirt expansion shape.
Fig. 2 is a schematic diagram showing an example of the structure of the transfer film.
Detailed Description
The present invention will be described in detail below.
In the present specification, a numerical range indicated by "to" means a range including numerical values described before and after "to" as a lower limit and an upper limit.
In the numerical ranges described in stages in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. 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 value shown in the examples.
In the present specification, the term "process" includes not only an independent process but also the term if the process cannot be clearly distinguished from other processes, as long as the intended function of the process is exhibited.
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 specification, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, 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 converted from polystyrene using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (each of product names manufactured by TOSOH CORPORATION) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, polystyrene as a standard, and polystyrene as a standard measured by a Gel Permeation Chromatography (GPC) analyzer.
In the present specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight (Mw).
In the present specification, unless otherwise specified, the content of the metal element is a value measured using an inductively coupled plasma (ICP: inductively Coupled Plasma) spectroscopic analysis device.
In the present specification, unless otherwise specified, the refractive index is a value measured at a wavelength of 550nm using an ellipsometer.
In the present specification, unless otherwise specified, hue is a value measured using a color difference meter (CR-221, minolta Co., ltd.).
In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth) acryloyloxy" is a concept including both acryloyloxy and methacryloyloxy.
In the present specification, "alkali-soluble" means that the solubility of sodium carbonate in 100g of a 1 mass% aqueous solution is 0.1g or more at 22 ℃.
In the present specification, "water-soluble" means that the solubility in 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more. For example, the water-soluble resin means a resin satisfying the above solubility condition.
In the present specification, the "solid component" of the composition means a component forming a composition layer (photosensitive composition layer, intermediate layer, and thermoplastic resin layer) formed using the composition, and when the composition contains a solvent (organic solvent, water, or the like), all the components excluding the solvent are represented. Further, as long as the composition layer is formed, the liquid component is also regarded as a solid component.
[ method for producing laminate ]
The method for producing a laminate of the present invention comprises:
a bonding step of bringing a surface of a photosensitive composition layer of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, which surface is opposite to the intermediate layer side, into contact with a substrate, and bonding the transfer film and the substrate;
a peeling step of peeling the temporary support between the temporary support and the intermediate layer;
an exposure step of exposing the photosensitive composition layer to a pattern; a kind of electronic device with high-pressure air-conditioning system
A developing step of developing the exposed photosensitive composition layer with a developing solution to form a pattern,
the elastic modulus X obtained in the measurement X is 1.0 to 10.0GPa.
As 1 preferred embodiment of the method for producing a laminate, there is a laminate having the above-described lamination step, peeling step, exposure step, and development step in this order.
The characteristic point of the method for producing a laminate of the present invention is that the elastic modulus X obtained in measurement X described later is 1.0 to 10.0GPa.
Although the details of the mechanism of action by which the method for producing a laminate of the present invention exhibits the desired effect are not clear, the present inventors have speculated that the following is possible.
The present inventors found the following phenomena: in the case where the elastic modulus X is less than 1.0GPa, since the strength of the pattern (cured layer) obtained by exposing the photosensitive composition layer is too low, the pattern becomes a lower hem expansion shape by swelling and dissolution of the pattern when developing with a developer; and, in the case where the elastic modulus X is more than 10.0GPa, since the strength of the pattern (cured layer) obtained by exposing the photosensitive composition layer is too high, the adhesion between the cured layer and the transfer body is poor.
In view of the above, in the method for producing a laminate of the present invention, by adjusting the elastic modulus X to a predetermined range, it is possible to make the pattern shape excellent and the pattern adhesion excellent.
Hereinafter, the effect of the present invention is also referred to as being more excellent when at least one of more excellent pattern shape and more excellent pattern adhesion is obtained.
Hereinafter, the method for producing the laminate of the present invention and the respective steps will be described in detail. The following description of the constituent elements is based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
[ elastic modulus ]
< elastic modulus X >)
In the method for producing a laminate of the present invention, the elastic modulus X obtained in measurement X is preferably 1.0 to 10.0GPa, more preferably 2.0 to 8.0GPa, still more preferably 3.0 to 6.0GPa, and particularly preferably 4.0 to 6.0GPa, from the viewpoint of further excellent effects of the present invention.
The elastic modulus X is a value obtained in the following measurement X.
The measurement X is as follows: the surface of the photosensitive composition layer opposite to the intermediate layer side of the transfer film is brought into contact with the substrate, the transfer film and the substrate are bonded, the temporary support is peeled from the obtained laminate and between the temporary support and the intermediate layer, the photosensitive composition layer is subjected to full-face exposure from the exposed intermediate layer side, the exposed intermediate layer is peeled, and then the elastic modulus of the exposed cured layer is measured as the elastic modulus X.
The exposure conditions (type of light source, exposure amount, etc.) for performing the above-described full-face exposure are the same as those for the exposure process described later. That is, the entire exposure performed in the measurement X corresponds to changing the exposure range of the pattern exposure performed in the exposure step described later to the exposure of the entire surface of the photosensitive composition layer.
As a method for measuring the elastic modulus, for example, a rheometer DFR-2 manufactured by TA Instruments, inc. can be used, and the measurement can be performed under conditions of a set temperature of 20 to 125 ℃, a heating rate of 5 ℃ per minute, a frequency of 1Hz, and a distortion of 0.5%.
As a method for peeling the exposed intermediate layer, for example, a known peeling method is mentioned, and tape peeling is preferable.
In the case where the transfer film has a protective film, measurement X is performed after the protective film is peeled from the transfer film.
The substrate used in measurement X is a substrate used in the method for manufacturing a laminate, and will be described in detail later.
< elastic modulus Y >)
From the viewpoint of excellent inhibition of development residues, the elastic modulus Y obtained in measurement Y is preferably 10.0MPa or less, more preferably 5.0MPa or less, still more preferably 3.5MPa or less, particularly preferably 1.0MPa or less, and most preferably 0.8MPa or less. The lower limit is preferably 0.1MPa or more.
The modulus of elasticity Y is determined as follows: the elastic modulus of the photosensitive composition layer of the transfer film was measured as the elastic modulus Y. That is, the elastic modulus Y corresponds to the elastic modulus of the unexposed portion of the photosensitive composition layer that has not been subjected to the exposure treatment.
Examples of the method for measuring the elastic modulus include the method for measuring the elastic modulus used in the elastic modulus X described above.
The measurement of Y may be performed after the intermediate layer is peeled from the transfer film. As a method for peeling the intermediate layer, for example, a known peeling method is mentioned, and tape peeling is preferable.
In the case where the transfer film has a protective film, measurement Y is performed after the protective film is peeled from the transfer film.
From the viewpoint of excellent inhibition of development residues, the ratio of the elastic modulus X to the elastic modulus Y (elastic modulus X/elastic modulus Y) is preferably 100 or more, more preferably 200 to 10000, still more preferably 1000 to 10000, particularly preferably 1500 to 10000, and most preferably 3000 to 8000.
Examples of the method for adjusting the elastic modulus X and the elastic modulus Y include changing the type and the content of the resin contained in the photosensitive composition layer.
Specifically, the following method is given as examples of the resin: a method of using a resin having a weight average molecular weight, an acid value, and Tg (glass transition temperature) adjusted to preferred embodiments described below, a method of using a resin synthesized by using a monomer having 3 or more functions and/or an aromatic hydrocarbon monomer in the preferred embodiments, and a method of combining these.
[ laminating step ]
The bonding step is a bonding step of bonding the transfer film and the substrate by bringing the surface of the photosensitive composition layer of the transfer film having the temporary support, the intermediate layer, and the photosensitive composition layer in this order into contact with the substrate on the side opposite to the intermediate layer side.
In the case where the transfer film has a protective film, the bonding step may be performed after the protective film is peeled off.
In the bonding step, the surface of the photosensitive composition layer of the transfer film opposite to the intermediate layer side is brought into contact with and pressure-bonded to the surface.
Examples of the pressure bonding method include a known transfer method and a lamination method.
Among them, as the pressure bonding method, it is preferable to superimpose the surface of the photosensitive composition layer of the transfer film on the side opposite to the intermediate layer side on the substrate, and to apply pressure and heat by a roller or the like.
As the bonding method, a known bonding method using a vacuum laminator, an automatic cutting laminator, or the like can be used.
The lamination temperature is preferably 70 to 130 ℃.
As the substrate, a substrate having a conductive layer is preferable.
Any layer other than the above-described conductive layer may be formed on the substrate of the substrate having the conductive layer as required. That is, the substrate is preferably a conductive substrate having at least a conductive layer disposed on the substrate.
Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
As the substrate, the substrate described in [0140] of International publication No. 2018/155193 is preferable, and these are incorporated herein by reference.
As a material of the resin substrate, cycloolefin polymer or polyimide is preferable.
The thickness of the resin substrate is preferably 5 to 200. Mu.m, more preferably 10 to 100. Mu.m.
The conductive layer is preferably at least 1 conductive layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoints of conductivity and fine line formation.
Only 1 conductive layer may be provided on the substrate, or 2 or more conductive layers may be provided. In the case of disposing 2 or more conductive layers, it is preferable to dispose 2 or more conductive layers of different materials from each other.
The conductive layer is preferably the conductive layer described in [0141] of International publication No. 2018/155193, and these are incorporated herein by reference.
[ stripping step ]
The peeling step is a step of peeling the temporary support between the temporary support and the intermediate layer.
As a method for peeling off the temporary support, for example, a known peeling method is given. Specifically, the cover film peeling mechanism described in paragraphs [0161] to [0162] of JP 2010-072589 can be cited.
[ Exposure procedure ]
The exposure step is a step of exposing the photosensitive composition layer to a pattern.
The "pattern exposure" refers to exposure in a pattern form, that is, exposure indicating the presence of an exposed portion and a non-exposed portion.
The positional relationship between the exposed region and the unexposed region in the pattern exposure is not particularly limited, and can be appropriately adjusted.
The direction of exposure is not particularly limited, and exposure may be performed from the intermediate layer side of the photosensitive composition layer, or may be performed from the side (substrate side) of the photosensitive composition layer opposite to the intermediate layer side.
The exposure step is preferably performed by bringing the intermediate layer exposed in the peeling step into contact with a mask to perform pattern exposure. The mask is contacted with the mask to perform pattern exposure, thereby obtaining a high-definition pattern.
Specifically, it is preferable that the intermediate layer exposed by peeling off the temporary support is arranged so as to be in close contact with a mask having a predetermined opening, and pattern exposure is performed.
By performing the exposure step of bringing the intermediate layer into contact with the mask, a curing reaction of the components contained in the photosensitive composition layer can be generated in the exposed region (corresponding to the position of the opening of the mask) of the photosensitive composition layer. The non-exposed areas of the photosensitive composition layer are removed by performing an alkali development treatment after exposure, thereby forming a pattern.
The method for producing a laminate preferably includes a peeling step of peeling off a mask used in the exposure step between the exposure step and the development step.
The light source for pattern exposure may be appropriately selected and used as long as it is a light source capable of irradiating light in at least a wavelength region (e.g., 365nm and 405 nm) capable of curing the photosensitive composition layer.
Among them, 365nm is preferable as the dominant wavelength of the exposure light for pattern exposure. The dominant wavelength is the wavelength with the highest intensity.
Examples of the light source include various lasers, light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps.
The exposure is preferably 5 to 200mJ/cm 2 More preferably 10 to 200mJ/cm 2 。
Examples of the light source, the exposure amount, and the exposure method include those described in paragraphs [0146] to [0147] of International publication No. 2018/155193, which are incorporated herein by reference.
[ developing Process ]
The developing step is a step of developing the exposed photosensitive composition layer with a developing solution to form a pattern.
The non-exposed region of the photosensitive composition layer is removed by development using an alkaline developer (alkaline aqueous solution), and a pattern having an opening of the mask as a convex portion is formed.
As the developer, an alkaline aqueous solution is preferable.
Examples of the basic compound (a compound which dissolves in water and exhibits basicity) contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyl trimethylammonium hydroxide).
As the developing method, for example, a known developing method is given. Specifically, water pit development, shower development, spin development, and dip development are examples.
As the developing method, the developing method described in paragraph [0195] of International publication No. 2015/093271 is preferred.
[ post-exposure Process and post-baking Process ]
The method for producing a laminate of the present invention may further include a step of exposing the pattern obtained by the development step (hereinafter, also referred to as "post-exposure step") and/or a step of heating (hereinafter, also referred to as "post-baking step").
In the case where the method for producing a laminate includes both the post-exposure step and the post-baking step, the post-baking step is preferably performed after the post-exposure step.
The exposure amount in the post-exposure step is preferably 100 to 5000mJ/cm 2 More preferably 200 to 3000mJ/cm 2 。
In the post-drying step, the post-drying temperature is preferably 80 to 250 ℃, more preferably 90 to 160 ℃.
In the post-drying step, the post-drying time is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
The position and size of the pattern formed on the substrate obtained by the method of manufacturing the laminate are not particularly limited.
Among them, a fine line shape is preferable as the pattern. Specifically, the width of the pattern is preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more, more preferably 3 μm or more.
[ use of laminate ]
The laminate produced by the method for producing a laminate of the present invention can be applied to various devices. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to a display device such as an organic EL (electro luminescence) display device or a liquid crystal display device.
[ method for manufacturing Circuit Wiring ]
The method for manufacturing a circuit wiring according to the present invention includes an etching step of etching a conductive layer in a region where no pattern is arranged in a laminate having a pattern manufactured by the method for manufacturing a laminate, when a conductive substrate is used as a substrate.
Hereinafter, each step of the method for manufacturing a circuit wiring of the present invention will be described in detail. The following description of the constituent elements is based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
[ etching step ]
The etching step is a step of etching the conductive layer in the region where the pattern is not arranged.
Specifically, in the etching step, the conductive layer is etched using the pattern obtained from the photosensitive composition layer by the developing step in the method for producing a laminate as a resist.
The substrate is synonymous with the substrate in the above-described method for producing a laminate, and the same is preferable.
As a method of etching treatment, for example, a known etching method is given.
Specifically, examples of the method include the method described in paragraphs [0209] to [0210] of JP-A2017-120435, the method described in paragraphs [0048] to [0054] of JP-A2010-152155, and dry etching such as wet etching and plasma etching in an etching liquid.
The etching liquid used in the wet etching can be appropriately selected from an acidic etching liquid and an alkaline etching liquid according to the etching target.
Examples of the acidic etching solution include an acidic aqueous solution containing 1 or 2 or more acidic compounds and an acidic mixed aqueous solution of an acidic compound and at least 1 salt selected from the group consisting of ferric chloride, ammonium fluoride and potassium permanganate.
The acidic compound (compound which is dissolved in water and exhibits acidity) contained in the acidic aqueous solution is preferably at least 1 acidic compound selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid.
Examples of the alkaline etching liquid include an alkaline aqueous solution containing 1 or 2 or more alkaline compounds and an alkaline mixed aqueous solution of an alkaline compound and a salt (for example, potassium permanganate and the like).
The alkali compound (compound that is dissolved in water and exhibits alkali) contained in the alkali aqueous solution is preferably at least 1 selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (for example, tetramethylammonium hydroxide).
[ removal Process ]
The method for manufacturing a circuit wiring according to the present invention may further include a step of removing the residual pattern.
The removal step is preferably performed after the etching step.
As a method for removing the residual pattern, for example, a method of removing by chemical treatment, preferably a method of removing using a removing liquid, is mentioned.
The liquid temperature of the removing liquid is preferably 30 to 80 ℃, more preferably 50 to 80 ℃.
As a preferred embodiment of the removal method, for example, a method of immersing a substrate having a pattern to be removed in a removal liquid under stirring at a liquid temperature of 50 to 80 ℃ for 1 to 30 minutes is given.
As a method for removing the residual pattern, for example, a method of removing the residual pattern by a known method such as a spray method, a shower method, or a spin-coating immersion method using a removing liquid can be mentioned.
Examples of the removing liquid include a removing liquid obtained by dissolving a basic inorganic compound or a basic organic compound in at least 1 solution selected from the group consisting of water, dimethyl sulfoxide, N-methylpyrrolidone, and a mixed solution thereof.
Examples of the basic inorganic compound include sodium hydroxide and potassium hydroxide.
Examples of the basic organic compound include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium compound.
[ other procedures ]
The method for manufacturing the circuit wiring may have steps other than the steps described above.
Examples of the other steps include a step of reducing the visible light reflectance described in paragraph [0172] of international publication No. 2019/022089 and a step of forming a new conductive layer on the surface of the insulating film described in paragraph [0172] of international publication No. 2019/022089.
< procedure for decreasing visible light reflectivity >
The method for manufacturing the circuit wiring may include a step of performing a process of reducing the visible light reflectance of a part or all of the plurality of conductive layers included in the substrate.
As the treatment for reducing the visible light reflectance, for example, an oxidation treatment is given. In the case where the substrate has a conductive layer containing copper, the conductive layer is blackened by oxidizing copper to form copper oxide, whereby the visible light reflectance of the conductive layer can be reduced.
Examples of the treatment for reducing the visible light reflectance include 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, which are incorporated herein by reference.
< procedure of forming insulating film, procedure of forming new conductive layer on surface of insulating film >)
The method for manufacturing the circuit wiring may include: forming an insulating film on the surface of the circuit wiring; and forming a new conductive layer on the surface of the insulating film.
Through the above steps, the 1 st electrode pattern and the insulating 2 nd electrode pattern can be formed.
Examples of the step of forming the insulating film include a method of forming a known permanent film. Further, an insulating film having a desired pattern can be formed by photolithography using a photosensitive composition having insulating properties.
As a step of forming a new conductive layer on the surface of the insulating film, for example, a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive composition having conductivity.
In the method for manufacturing the circuit wiring, it is preferable that the circuit wiring is formed sequentially or simultaneously with respect to the conductive layers formed on the both surfaces of the base material by using a substrate having a plurality of conductive layers on the both surfaces of the substrate.
According to the above configuration, the circuit wiring for the touch panel in which the 1 st conductive pattern is formed on one substrate surface and the 2 nd conductive pattern is formed on the other substrate surface can be formed. Further, the circuit wiring for a touch panel having the above-described configuration is preferably formed from both surfaces of the substrate by a roll-to-roll method.
[ use of Circuit Wiring ]
The circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices. Examples of the device having the circuit wiring include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to a display device such as an organic EL display device or a liquid crystal display device.
[ transfer film ]
The transfer film of the present invention comprises a temporary support, an intermediate layer, and a photosensitive composition layer in this order, and is subjected to an exposure step of subjecting the photosensitive composition layer to pattern exposure, wherein the elastic modulus X obtained in measurement X is 1.0 to 10.0GPa.
The meaning of the elastic modulus X and the ratio of the elastic modulus X to the elastic modulus Y and the elastic modulus Y in the transfer film are the same as those described in the above-described method for producing the laminate, and the preferable ranges are also the same.
The transfer film may have other layers in addition to the photosensitive composition layer and the intermediate layer.
Examples of the other layer include a thermoplastic resin layer described later. The transfer film may have a protective film described later on the photosensitive composition layer.
The embodiment of the transfer film is not particularly limited, and examples thereof include the following.
(1) "temporary support/intermediate layer/photosensitive composition layer/protective film"
(2) "temporary support/thermoplastic resin layer/intermediate layer/photosensitive composition layer/protective film"
The photosensitive composition layer in each of the above-described configurations is preferably a negative photosensitive composition layer. Further, as the photosensitive composition layer, a colored resin layer is also preferable.
From the viewpoint of suppressing the generation of bubbles in the above-described lamination step, the maximum width of the transfer film waviness is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. The lower limit is preferably 0 μm or more, more preferably 0.1 μm or more, and still more preferably 1 μm or more.
The maximum width of the transfer film waviness is a value measured by the following procedure.
First, a test sample was produced by shearing the transfer film in a direction perpendicular to the main surface to a length of 20cm×20cm wide. In addition, in the case where the transfer film has a protective film, the protective film is peeled from the transfer film. Then, the test sample was allowed to stand on a stage having a smooth and horizontal surface, so that the surface of the temporary support faced the stage. After standing, the surface of the test specimen was scanned with a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) over a range of 10cm square at the center of the test specimen to obtain a three-dimensional surface image, and the lowest concave surface height was subtracted from the maximum convex surface height observed in the obtained three-dimensional surface image. The above operation was performed on 10 test samples, and the arithmetic average value thereof was taken as the maximum width of the transfer film.
From the viewpoint of further excellent adhesion, the transmittance of light having a wavelength of 365nm in the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.
An example of an embodiment of the transfer film will be described.
The transfer film 10 shown in fig. 1 has, in order, a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19.
The transfer film 10 shown in fig. 1 is in the form of a protective film 19, but the protective film 19 may not be provided.
In fig. 1, the layers other than the protective film 19 that can be disposed on the temporary support 11 are also referred to as a composition layer 17.
Further, the transfer film may have a thermoplastic resin layer in addition to the above layers, and the thermoplastic resin layer is preferably disposed between the temporary support 11 and the intermediate layer 13.
Hereinafter, the transfer film of the present invention will be described in detail with respect to each member and each component. The following description of the constituent elements is based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
[ 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 be a single-layer structure or a multi-layer structure.
As the temporary support, a film is preferable, and a resin film is more preferable. The temporary support is preferably a film which is flexible and does not significantly deform, shrink or stretch under pressure or under pressure and heat, and is preferably a film which does not cause deformation such as wrinkles or scratches.
Examples of the film include a polyethylene terephthalate film (for example, a biaxially oriented 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 by the temporary support, the temporary support is preferably high in transparency. Specifically, the transmittance of the temporary support at 365nm is preferably 60% or more, more preferably 70% or more. The upper limit is preferably less than 100%.
From the viewpoints of patterning property at the time of pattern exposure by the temporary support and transparency of the temporary support, it is preferable that the temporary support has a small haze. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less. The lower limit is preferably 0% or more.
From the viewpoints of patterning property at the time of pattern exposure via the temporary support and transparency of the temporary support, the number of particles, foreign matters, and defects in the temporary support is preferably small. Specifically, the number of particles (e.g., particles having a diameter of 1 μm), foreign matters and defects in the temporary support is preferably 50/10 mm 2 Hereinafter, more preferably 10 pieces/10 mm 2 Hereinafter, it is more preferably 3/10 mm 2 Hereinafter, it is particularly preferably 0/10 mm 2 。
The thickness of the temporary support is preferably 5 to 200. Mu.m, more preferably 5 to 150. Mu.m, still more preferably 5 to 50. Mu.m, particularly preferably 5 to 25. Mu.m, from the viewpoint of ease of handling and versatility.
The thickness of the temporary support was calculated as an average value of any 5 points measured by cross-sectional observation based on SEM (scanning electron microscope: scanning Electron Microscope).
From the viewpoint of operability, the temporary support may have a layer (lubricant layer) containing fine particles on one side or both sides of the temporary support.
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.
The surface of the temporary support in contact with the photosensitive composition layer may be subjected to a surface modification treatment from the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer.
Examples of the surface modification treatment include treatment 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 。
When the exposure amount is within the above range, the lamp output and illuminance are not particularly limited.
Examples of the light source for UV irradiation include a mercury-vapor lamp, a high-pressure mercury lamp, a mercury-vapor lamp, a carbon arc lamp, a metal halide lamp, a hernia lamp, a chemical lamp, an electrodeless discharge lamp, and a Light Emitting Diode (LED) which emit light in the wavelength band of 150 to 450 nm.
Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16. Mu.m, a biaxially stretched polyethylene terephthalate film having a thickness of 12. Mu.m, and a biaxially stretched polyethylene terephthalate film having a thickness of 9. Mu.m.
Examples of the temporary support include those described in paragraphs [0017] to [0018] of JP-A2014-085643, paragraphs [0019] to [0026] of JP-A2016-027363, paragraphs [0041] to [0057] of International publication No. 2012/081680, and paragraphs [0029] to [0040] of International publication No. 2018/179370, and these are incorporated herein by reference.
Examples of commercial products of the temporary support include Lumirror16 KS40, lumirror16FB40 (manufactured by TORAY INDUSTRIES, INC, supra), cosmo Shine A4100, cosmo Shine A4300, and Cosmo Shine A8300 (manufactured by TOYOBO CO., LTD, supra).
[ photosensitive composition layer ]
The transfer film of the present invention has a photosensitive composition layer.
In a display device (for example, an organic EL display device, a liquid crystal display device, or the like) including a touch panel such as a capacitive input device, a conductive layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition portion, a peripheral wiring portion, and a wiring of a lead-out wiring portion is provided inside the touch panel. Generally, in order to form a patterned layer, the following method is widely adopted: a negative photosensitive composition layer is provided on a substrate using a transfer film or the like, and the photosensitive layer is exposed to light through a mask having a desired pattern and then developed. Therefore, as the photosensitive composition layer, a negative photosensitive composition layer is preferable. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to a cured layer.
The photosensitive composition layer preferably contains a resin, a polymerizable compound, and a polymerization initiator, which will be described later. As described later, the photosensitive composition layer preferably contains an alkali-soluble resin (such as a resin that is an alkali-soluble resin). That is, the photosensitive composition layer preferably contains a resin of an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.
The photosensitive composition layer preferably contains 10 to 90 mass% of the resin, 5 to 70 mass% of the polymerizable compound, and 0.01 to 20 mass% of the polymerization initiator, based on the total mass of the photosensitive composition layer.
< resin >)
The photosensitive composition layer may include a resin.
As the resin, an alkali-soluble resin is preferable.
As the resin, an alkali-soluble resin in a thermoplastic resin layer described later can be used.
From the viewpoint of suppressing the line width from becoming thicker and the resolution from deteriorating when the focus position is shifted during exposure, the resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon.
Examples of the aromatic hydrocarbon include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
The content of the structural unit derived from the monomer having an aromatic hydrocarbon in the resin is preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% or more, relative to the total mass of the resin. The upper limit is preferably 80 mass% or less, more preferably 60 mass% or less, further preferably 55 mass% or less, and particularly preferably 45 mass% or less, relative to the total mass of the resin. In the case where the photosensitive composition layer contains a plurality of resins, the average value of the content of the structural unit derived from the monomer having an aromatic hydrocarbon is preferably within the above range. The average value is a mass average value.
Examples of the monomer having an aromatic hydrocarbon include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, a styrene dimer, and a styrene trimer), and the monomer having an aralkyl group or styrene is preferable, and styrene is more preferable.
When the monomer having an aromatic hydrocarbon in the resin is styrene, the content of the structural unit derived from styrene is preferably 10 to 80 mass%, more preferably 10 to 60 mass%, even more preferably 20 to 60 mass%, particularly preferably 20 to 55 mass%, and most preferably 30 to 45 mass% relative to the total mass of the resin.
In the case where the photosensitive composition layer contains a plurality of resins, the average value of the content of the structural unit having an aromatic hydrocarbon is preferably within the above range. The average value is a mass average value.
Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (wherein a benzyl group is removed) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.
Examples of the monomer having a phenylalkyl group include phenethyl (meth) acrylate.
Examples of the monomer having a benzyl group include: benzyl group-containing (meth) acrylates such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; and vinyl monomers having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol. Among them, benzyl (meth) acrylate is preferable.
When the monomer component having an aromatic hydrocarbon in the resin is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, relative to the total mass of the resin.
The resin containing a structural unit derived from a monomer having an aromatic hydrocarbon is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon with at least 1 of the 1 st monomers described later and/or at least 1 of the 2 nd monomers described later.
The resin not containing a structural unit derived from a monomer having an aromatic hydrocarbon is preferably obtained by polymerizing at least 1 kind of the 1 st monomer described later, more preferably obtained by copolymerizing at least 1 kind of the 1 st monomer with at least 1 kind of the 2 nd monomer described later.
The 1 st monomer is a monomer having a carboxyl group in the molecule.
Examples of the 1 st monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half-ester, and (meth) acrylic acid is preferable.
The content of the structural unit derived from the 1 st monomer in the resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, relative to the total mass of the resin.
When the content is 5 mass% or more, excellent developability, control of edge meltability, and the like can be achieved. When the content is 50 mass% or less, high resolution of the resist pattern, control of edge shape, and high chemical resistance of the resist pattern can be achieved.
The 2 nd monomer is a monomer which is non-acidic and has at least 1 polymerizable unsaturated group in the molecule.
Examples of the 2 nd 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, tributyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; (meth) acrylonitrile.
Among them, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is preferable, and methyl methacrylate or ethyl (meth) acrylate is more preferable.
The content of the structural unit derived from the 2 nd monomer in the resin is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, further preferably 20 to 60% by mass, particularly preferably 20 to 48% by mass, and most preferably 30 to 48% by mass, relative to the total mass of the resin.
In the case where the resin contains a structural unit derived from a monomer having an aralkyl group and/or a structural unit derived from styrene, it is possible to suppress the line width from becoming thicker and the resolution from deteriorating when the focus position is shifted at the time of exposure.
As the resin, a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate and a structural unit derived from styrene, a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from ethyl methacrylate and a structural unit derived from styrene, or a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate is preferable.
As 1 preferred embodiment of the resin, there is exemplified a resin comprising 30 to 60 mass% of a structural unit derived from a monomer having an aromatic hydrocarbon, 10 to 40 mass% of a structural unit derived from a 1 st monomer, and 20 to 48 mass% of a structural unit derived from a 2 nd monomer.
Another preferable embodiment of the resin includes 70 to 90 mass% of a structural unit derived from a monomer having an aromatic hydrocarbon and 10 to 25 mass% of a structural unit derived from a 1 st monomer.
The resin may have any one of a linear structure, a branched structure, and an alicyclic structure in a side chain.
The branched structure and the alicyclic structure may be introduced into the side chain of the resin by using a monomer containing a group having a branched structure in the side chain or a monomer containing an alicyclic structure in the side chain. The group having an alicyclic structure may be any of a single ring and a multiple ring.
Examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, isopentyl (meth) acrylate, third pentyl (meth) acrylate, second pentyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and third octyl (meth) acrylate.
Among them, isopropyl (meth) acrylate, isobutyl (meth) acrylate or tributyl methacrylate is preferable, and isopropyl methacrylate or tributyl methacrylate is more preferable.
Examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms is exemplified.
Specifically, there may be mentioned (meth) acrylic acid (bicyclo [ 2.2.1 ] heptyl-2), (meth) acrylic acid-1-adamantyl ester, (meth) acrylic acid-2-adamantyl ester, (meth) acrylic acid-3-methyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid-3-ethyladamantanyl ester, (meth) acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid-3, 5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid-2-methyl-2-adamantyl ester, (meth) acrylic acid-2-ethyl-2-adamantyl ester, (meth) acrylic acid-3-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4, 7-menthol indene (menthan) 5-yl ester, (meth) acrylic acid-octahydro-4, 7-indenyl (meth) acrylate, menthyl ester, (meth) acrylic acid-1-menthyl ester 3-hydroxy-2, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Among them, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecane (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is more preferable.
The Tg of the resin is preferably from 30 to 150 ℃, more preferably from 60 to 150 ℃, still more preferably from 90 to 150 ℃, particularly preferably from 100 to 150 ℃, most preferably from 100 to 120 ℃.
From the viewpoint of further excellent effects of the present invention, the acid value of the resin is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, still more preferably less than 190mgKOH/g, and particularly preferably less than 170mgKOH/g. The lower limit is preferably 10mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 70mgKOH/g or more, particularly preferably 90mgKOH/g or more, from the viewpoint of further excellent effects of the present invention.
The acid value (mgKOH/g) is the mass (mg) of potassium hydroxide required to neutralize 1g of the sample. The acid value can be obtained, for example, by the method described in JIS K0070:1992.
The acid value of the resin may be adjusted by the kind of the structural unit of the resin and/or the content of the structural unit containing an acid group.
The weight average molecular weight of the resin is preferably 5,000 ～ 500,000, more preferably 10,000 ～ 100,000, further preferably 20,000 ～ 50,000, and particularly preferably 20,000 ～ 40,000.
When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. When the weight average molecular weight is 5,000 or more, the properties of the developed aggregate, and the properties of the unexposed film such as the edge melting property and dicing property of the transfer film can be controlled. The edge meltability means a degree to which the photosensitive composition layer is easily exposed from the end surface of the roll when the transfer film is wound in a roll shape. Dicing the wafer refers to the degree to which the wafer is easily scattered when the unexposed film is cut by a dicing blade. If the wafer is attached to the upper surface of the transfer film, the wafer is transferred to a mask in a subsequent exposure step or the like, resulting in defective products.
The dispersity of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0.
The photosensitive composition layer may contain other resins in addition to the above-described resins.
Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
The resin may be used alone or in combination of 1 kind or 2 or more kinds.
In the case of using 2 or more kinds of resins, it is preferable to use 2 kinds of resins containing structural units derived from monomers having aromatic hydrocarbons in combination, or to use resins containing structural units derived from monomers having aromatic hydrocarbons in combination and resins not containing structural units derived from monomers having aromatic hydrocarbons in combination. In the latter case, the content of the resin containing the structural unit derived from the monomer having an aromatic hydrocarbon is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the resin. The upper limit is preferably 100 mass% or less.
The content of the resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and particularly preferably 40 to 60% by mass, relative to the total mass of the photosensitive composition layer. When the content of the resin is 90 mass% or less relative to the total mass of the photosensitive composition layer, the development time can be controlled. Further, when the content of the resin is 10 mass% or more relative to the total mass of the photosensitive composition layer, edge melting resistance can be improved.
Examples of the method for synthesizing the resin include a method in which a proper amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the above single or plural monomers with a solvent such as acetone, methyl ethyl ketone, isopropyl alcohol, etc., and the mixture is heated and stirred. The synthesis may be performed while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
In addition, examples of the synthetic method of the resin include bulk polymerization, suspension polymerization, and emulsion polymerization, in addition to the above.
< polymerizable Compound >)
The photosensitive composition layer preferably contains a polymerizable compound having a polymerizable group. In the present specification, the term "polymerizable compound" means a compound that is polymerized by the action of a polymerization initiator described later, and means a compound different from the resin described above.
The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group involved in polymerization reaction, and examples thereof include: a group having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group; and a group having a cationically polymerizable group such as an epoxy group or an oxetanyl group.
Among them, the polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group.
The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups (ethylenically unsaturated compound), more preferably a compound having 2 or more ethylenically unsaturated groups in 1 molecule (polyfunctional ethylenically unsaturated compound), from the viewpoint of more excellent photosensitivity of the photosensitive composition layer.
Further, from the viewpoint of further excellent resolution and releasability, the number of the ethylenically unsaturated groups in 1 molecule of the ethylenically unsaturated compound is preferably 1 to 6, more preferably 1 to 3, still more preferably 2 to 3, and particularly preferably 3.
From the viewpoint of more excellent balance of photosensitivity, resolution and releasability of the photosensitive composition layer, the polymerizable compound preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in 1 molecule, more preferably contains a 3-functional ethylenically unsaturated compound having 3 ethylenically unsaturated groups in 1 molecule.
The elastic modulus X can be adjusted by including the 3-functional ethylenically unsaturated compound.
From the viewpoint of excellent releasability, the content of the 2-functional ethylenically unsaturated compound is preferably 20 mass% or more, more preferably more than 40 mass%, still more preferably 55 mass% or more, and particularly preferably 90 mass% or more, relative to the total mass of the polymerizable compound. The upper limit is not particularly limited, but is preferably 100 mass% or less. That is, all the polymerizable compounds contained in the photosensitive composition layer may be 2-functional ethylenically unsaturated compounds.
From the viewpoint of being able to adjust the elastic modulus X, the content of the 3-functional ethylenically unsaturated compound is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the polymerizable compound. The upper limit is not particularly limited, but is preferably 100 mass% or less, more preferably 80 mass% or less, and still more preferably 50 mass% or less. That is, all the polymerizable compounds contained in the photosensitive composition layer may be 3-functional ethylenically unsaturated compounds.
Further, as the ethylenically unsaturated compound, a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group is preferable.
(polymerizable Compound B1)
The photosensitive composition layer preferably further contains a polymerizable compound B1 having an aromatic ring and 2 ethylenically unsaturated groups. The polymerizable compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in 1 molecule in the polymerizable compound B.
Examples of the aromatic ring of the polymerizable compound B1 include: aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring; aromatic heterocyclic rings such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and condensed rings thereof are preferably aromatic hydrocarbon rings, more preferably benzene rings.
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.
From the viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer due to the developer, the polymerizable compound B1 preferably has a bisphenol structure.
Examples of the bisphenol structure include bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and 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 bisphenol structure may be directly bonded to 2 polymerizable groups at both ends, or may be bonded to 1 or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, ethyleneoxy group or propyleneoxy group is preferable, and ethyleneoxy group is more preferable. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14, per 1 molecule.
Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs [0072] to [0080] of JP-A-2016-224162, and these 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) acryloxypolyalkoxy) phenyl) propane.
Examples of the 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecaethoxy tetrapropoxy) phenyl) propane (manufactured by FA-3200MY,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical co), and manufactured by ltd.10-b.10, and also, the use of the same.
The polymerizable compound B1 is also preferably a compound represented by the general formula (B1).
[ chemical formula 1]
In the formula (B1), R 1 R is 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 each independently represent an integer of 1 to 39. n1+n3 is an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29. n2+n4 is an integer of 0 to 30.
Arrangement of structural units of- (A-O) -and- (B-O) -either random or block. In the case of blocks, - (A-O) -and- (B-O) -may be on the biphenyl side.
The n1+n2+n3+n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. The n2+n4 is preferably 0 to 10, more preferably 0 to 4, still more preferably 0 to 2, and particularly preferably 0.
The polymerizable compound B1 may be used alone or in combination of 1 or 2 or more.
From the viewpoint of further excellent resolution, the content of the polymerizable compound B1 is preferably 10 mass% or more, more preferably 20 mass% or more, and even more preferably 25 mass% or more, relative to the total mass of the photosensitive composition layer. The upper limit is not particularly limited, but is preferably 70 mass% or less, more preferably 60 mass% or less, from the viewpoints of transferability and edge melting (a phenomenon in which a photosensitive resin bleeds out from an end portion of a transfer member).
From the viewpoint of further excellent resolution, the content of the polymerizable compound B1 is preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 55 mass% or more, and particularly preferably 60 mass% or more, relative to the total mass of the polymerizable compounds. The upper limit is not particularly limited, but is preferably 100 mass% or less, more preferably 99 mass% or less, further preferably 95 mass% or less, particularly preferably 90 mass% or less, and most preferably 85 mass% or less from the viewpoint of releasability.
(other polymerizable Compound)
The photosensitive composition layer may contain a polymerizable compound other than the polymerizable compound B1.
The other polymerizable compound is not particularly limited, and may be appropriately selected from known polymerizable compounds. Examples thereof include compounds having 1 ethylenically unsaturated group in 1 molecule (monofunctional ethylenically unsaturated compounds), 2-functional ethylenically unsaturated compounds having no aromatic ring, and ethylenically unsaturated compounds having 3 or more functions.
Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxy ethyl (meth) acrylate.
Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
Examples of alkylene glycol di (meth) acrylates include tricyclodecane dimethanol diacrylate (A-DCP, shin-Nakamura Chemical Co., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 6-hexanediol diacrylate (A-HD-N, shin-Nakamura Chemical Co., manufactured by Ltd.), ethylene glycol dimethacrylate, 1, 10-decane diol diacrylate and neopentyl glycol di (meth) acrylate.
Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
Examples of urethane di (meth) acrylates include propylene oxide modified urethane di (meth) acrylates, and ethylene oxide and propylene oxide modified urethane di (meth) acrylates. Examples of the commercial products include 8UX-015A (TAISEI FINE CHEMICAL CO,. LTD. Times.), UA-32P (Shin-Nakamura Chemical Co., ltd.), and UA-1100H (Shin-Nakamura Chemical Co., ltd.).
Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, neopentyl tetraol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanatotri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof.
Here, "tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
Examples of the alkylene oxide modified product of the 3-functional or higher ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compounds (such as KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical co, a-9300-1CL (manufactured by ltd), alkylene oxide-modified (meth) acrylate compounds (such as KAYARAD RP-1040, shin-Nakamura Chemical co, ATM-35E and a-9300 (manufactured by ltd), DAI-CELL-ALLNEX ltd, EBECRYL (registered trademark) 135 (manufactured by Nippon Kayaku co., ltd), ethoxylated glycerol triacrylate (such as Shin-Nakamura Chemical co., ltd), arofix (registered trademark) TO-2349 (such as toagoi co, ltd), aroix M-520 (manufactured by toagoi co., ltd), and arom-510.
The polymerizable compound may be a polymerizable compound having an acid group (e.g., a carboxyl group). The acid groups may form anhydride groups. Examples of the polymerizable compound having an acid group include arofix (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), arofix (registered trademark) M-520 (manufactured by TOAGOSEI co., ltd.), and arofix (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 JP-A-2004-239942.
The molecular weight (weight average molecular weight in the case of having a molecular weight distribution) of the polymerizable compound (including the polymerizable compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and further preferably 300 to 2,200.
The polymerizable compound may be used alone or in combination of 1 or 2 or more.
The content of the polymerizable compound is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 70% by mass, based on the total mass of the photosensitive composition layer.
From the viewpoint of the more excellent effect of the present invention, the mass ratio of the content of the 2-functional or higher polymerizable compound to the content of the resin (content of the 2-functional or higher polymerizable compound/content of the resin) is preferably 0.10 to 1.00, more preferably 0.50 to 1.00, still more preferably 0.60 to 1.00, and particularly preferably 0.60 to 0.80.
The photosensitive composition layer preferably contains the polymerizable compounds B1 and 3 functional or more ethylenically unsaturated compounds, and more preferably contains the polymerizable compounds B1 and 2 or more ethylenically unsaturated compounds 3 functional or more.
The mass ratio of the polymerizable compound B1 to the mass of the 3-functional or higher ethylenically unsaturated compound is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and even more preferably 1.5 to 3.0.
The photosensitive composition layer preferably contains the polymerizable compounds B1 and 3 and functional ethylenically unsaturated compounds.
< polymerization initiator >)
The photosensitive composition layer also preferably contains a polymerization initiator.
The polymerization initiator may be selected according to the form of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
The polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.
The photosensitive composition layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that starts polymerization of the polymerizable compound upon receiving activation 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 -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.
Further, from the viewpoints of photosensitivity, visibility and resolution of an exposed portion and a non-exposed portion, the photosensitive composition layer preferably contains at least 1 selected from the group consisting of a 2,4, 5-triarylimidazole dimer and a derivative thereof as a photo radical polymerization initiator. In addition, 2,4, 5-triarylimidazole structures in the 2,4, 5-triarylimidazole dimer and the derivative thereof may be the same or different.
Examples of the derivative of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.
Examples of the photo radical polymerization initiator include those described in paragraphs [0031] to [0042] of JP-A-2011-095716 and in paragraphs [0064] to [0081] of JP-A-2015-014783.
Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisole (p, p '-dimethoxybenzyl), TAZ-110 (product name: midori Kagaku Co., ltd.), benzophenone, 4' -bis (diethylamino) benzophenone, TAZ-111 (product name: midori Kagaku Co., ltd.), 1- [4- (phenylthio) ] -1, 2-octadione-2- (O-benzoyl oxime) (product name: IRGACURE (registered trademark) OXE-01, BASF Co., ltd.), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] ethanone-1- (O-acetyl oxime) (product name: IRGACURE-02, BASF Co., ltd.), IRGACUOXE-03 (BASF), IRGAOXE-03 (product name: midori Kagaku Co., ltd.), 1- [4- (phenylthio) ] -1, 2-octadione-2- (registered trademark) OX-01, BASF-9H-carbazole-3-yl ] ethanone-1- (O-acetyl oxime) (product name: IRGACURE-02, BASF Co., IRGACUOXE-03 (product name: IRGACURE) and 3-methyl-2- [ (methyl) 2- [ methyl-ethyl-6- (2-methylbenzoyl) 2- (registered trademark) oxo-2- (registered) methyl-2- (methyl-benzoyl) 2- (methyl) methyl-ethyl-methyl-ketone-3-methyl ether, IGM Resins b.v.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (product name: omnirad 127,IGM Resins B.V. Manufactured), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (product name: omnirad 369,IGM Resins B.V. Manufactured), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: omnirad 1173,IGM Resins B.V. Manufactured), 1-hydroxycyclohexyl phenyl ketone (product name: omnirad 184,IGM Resins B.V, manufactured), 2-dimethoxy-1, 2-diphenylethan-1-one (product name: omnirad 651,IGM Resins B.V. Manufactured), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (product name: omnirad TPO H, IGM Resins b.v.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (product name: omnirad 819,IGM Resins B.V), oxime ester photopolymerization initiator (product name: lunar 6,DKSH Management Ltd, manufactured), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (product name: B-CIM, hampford Research inc.) 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (product name: BCTB, tokyo Chemical Industry co., ltd.) 1- [4- (phenylsulfanyl) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyloxime) (product name: TR-PBG-305,Changzhou Tronly New Electronic Materials CO, ltd.,) 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyloxime) (product name: TR-PBG-326,Changzhou Tronly New Electronic Materials CO, ltd.) (product name: TR-PBG-391,Changzhou Tronly New Electronic Materials CO, ltd.
The photo cation polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving activating light. The photo-cation polymerization initiator is preferably a compound which generates an acid by sensing an activating light having a wavelength of 300nm or more (preferably, a wavelength of 300 to 450 nm). The photo cation polymerization initiator that does not directly induce the activating light having a wavelength of 300nm or more may be preferably used in combination with a sensitizer if it is a compound that generates an acid by inducing the activating light having a wavelength of 300nm or more with a sensitizer.
The photo-cation polymerization initiator is preferably a photo-cation polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, but is preferably-10.0 or more.
Examples of the photo-cationic polymerization initiator include an ionic photo-cationic polymerization initiator and a nonionic photo-cationic polymerization initiator.
Examples of the ionic photo-cation polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
Examples of the ionic photo-cationic polymerization initiator include those described in paragraphs [0114] to [0133] of JP-A-2014-085643.
Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. Examples of the trichloromethyl-s-triazine compound, diazomethane compound and imide sulfonate compound include those described in paragraphs [0083] to [0088] of JP-A2011-221494. Examples of the oxime sulfonate compound include those described in paragraphs [0084] to [0088] of International publication No. 2018/179640.
The polymerization initiator may be used alone or in an amount of 1 kind or 2 or more kinds.
The content of the polymerization initiator (preferably, photopolymerization initiator) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, relative to the total mass of the photosensitive composition layer. The upper limit is preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less, relative to the total mass of the photosensitive composition layer.
Pigment >, pigment
The photosensitive composition layer is also preferably a dye (also referred to as "dye N") containing a dye whose maximum absorption wavelength is 450nm or more in the wavelength range of 400 to 780nm at the time of color development and whose maximum absorption wavelength is changed by an acid, a base or a radical, from the viewpoints of visibility of an exposed portion and a non-exposed portion, and pattern visibility and resolution after development. The detailed mechanism is not clear when pigment N is contained, but the adhesion to an adjacent layer (for example, a water-soluble resin layer) is improved, and the resolution is further excellent.
In the present specification, the "the pigment greatly absorbs the wavelength change by the acid, the base or the radical" may refer to any one of a method in which the pigment in the colored state is decolorized by the acid, the base or the radical, a method in which the pigment in the decolorized state is colored by the acid, the base or the radical, and a method in which the pigment in the colored state is changed to a colored state of another hue.
Specifically, the dye N may be a compound that changes color from a decolored state by exposure, or may be a compound that changes color from a decolored state by exposure. In the above case, the coloring matter may be a coloring matter which changes the state of color development or color removal by generating an acid, an alkali or a radical in the photosensitive composition layer by exposure and allowing the acid, the alkali or the radical to act, or a coloring matter which changes the state of color development or color removal by changing the state (for example, pH) in the photosensitive composition layer by an acid, an alkali or a radical. Further, the coloring matter may be a coloring matter which is not exposed to light but directly receives an acid, an alkali or a radical as a stimulus to change the state of color development or decoloration.
Among them, from the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.
From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, it is preferable that the photosensitive composition layer contains both a dye whose maximum absorption wavelength is changed by radicals as the dye N and a photo radical polymerization initiator.
Further, from the viewpoint of visibility of the exposed portion and the non-exposed portion, the dye N is preferably a dye that develops color by an acid, an alkali, or a radical.
Examples of the coloring means for the coloring matter N include the following: a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator) or a photo base generator is added to the photosensitive composition layer, and a radical reactive dye, an acid reactive dye or a base reactive dye (for example, a leuco dye) develops after exposure due to radicals, acids or bases generated by the photo radical polymerization initiator, the photo cation polymerization initiator or the photo base generator.
The maximum absorption wavelength in the wavelength range of 400 to 780nm at the time of color development of the dye N is preferably 550nm or more, more preferably 550 to 700nm, and still more preferably 550 to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion.
The dye N may have only 1 maximum absorption wavelength in the wavelength range 400 to 780nm at the time of color development, or may have 2 or more. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range 400 to 780nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.
Regarding the maximum absorption wavelength of the pigment N, a spectrophotometer can be used under an atmosphere: UV3100 (manufactured by SHIMADZU CORPORATION), a transmission spectrum of a solution containing pigment N (liquid temperature 25 ℃) was measured in a range of 400 to 780nm, and the intensity of light was measured to a wavelength at which the intensity of light reached a minimum (maximum absorption wavelength).
Examples of the coloring matter which is developed or decolored by exposure to light include colorless compounds.
Examples of the coloring matter to be decolorized by exposure to light include colorless compounds, diarylmethane-based coloring matters, oxazine-based coloring matters, xanthene-based coloring matters, iminonaphthoquinone-based coloring matters, azomethine-based coloring matters, and anthraquinone-based coloring matters.
The coloring matter N is preferably a colorless compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.
Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolyl phthalide skeleton (indolyl phthalide-based dye), and a colorless compound having a colorless gold amine skeleton (colorless gold amine-based dye).
Among them, triarylmethane-based pigments or fluoran-based pigments are preferable, and colorless compounds having a triphenylmethane skeleton (triphenylmethane-based pigments) or fluoran-based pigments are more preferable.
The colorless compound preferably has a lactone ring, a sultone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator to change the colorless compound to a closed-loop state to decolorize or to change the colorless compound to an open-loop state to develop a color. As the colorless compound, a compound having a lactone ring, a sultone ring, or a sultone ring and developing a color by opening the lactone ring, the sultone ring, or the sultone ring by a radical or an acid is preferable, and a compound having a lactone ring and developing a color by opening the lactone ring by a radical or an acid is more preferable.
Examples of the dye N include dyes and colorless compounds.
Examples of dyes include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), mitsunlin yellow (metandil yellow), thymol sulfophthalein (thymol sulfonphthalein), xylenol blue, methyl orange, para-methyl red, congo red, bengal 4B, alpha-naphthyl red, nile blue 2B, nile blue a, methyl violet, malachite green, paramfuchsin, victoria pure blue-naphthalene sulfonate, victoria pure blue BOH (Hodogaya Chemical co., manufactured), oil blue #603 (orint co., manufactured), oil powder #312 (orint Chemical co., manufactured) ltd. Manufactured), oil red 5B (manufactured by Orient Chemical Co., ltd. Manufactured), oil scarlet #308 (manufactured by Orient Chemical Co., ltd. Manufactured), oil red OG (manufactured by Orient Chemical Co., ltd. Manufactured), oil red RR (manufactured by Orient Chemical Co., ltd. Manufactured), oil green #502 (manufactured by Orient Chemical Co., ltd. Manufactured), SPIRON Red BEH SPECIAL (manufactured by Hodogaya Chemical Co., ltd. Manufactured), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonylrhodamine B, gold amine, 4-p-diethylaminophenyl imino naphthoquinone, 2-carboxyphenylamino-4-p-diethylaminophenyl imino naphthoquinone, 2-carboxystearamino-4-p-N, N-bis (hydroxyethyl) amino-phenyl imino naphthoquinone, methyl phenol red, rhodamine B, gold amine, 4-p-carboxyphenyl imino naphthoquinone, 2-carboxystearamino-4-p-N, N-bis (hydroxyethyl) amino-phenyl imino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenyl imino-5-pyrazolone and 1-beta-naphthalene-4-p-diethylaminophenyl imino-5-pyrazolone.
Examples of the colorless compound include p, p', p "-hexamethyltriphenylmethane (colorless crystal violet), pergascript Blue SRB (Ciba Geigy corporation), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran, 2-phenylamino-3-methyl-6- (N-ethyl-p-tolyl) fluoran, 3, 6-dimethoxy fluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamin) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylamino fluoran, 3- (N, N-diethylamino) -6-methyl-7-amino fluoran, 3- (N, N-diethylamino) -6-methyl-7-chloro fluoran, 3- (N, N-diethylamino) -6-methoxy fluoran, 3- (N-dimethylamino) -fluoran, 3- (N-diethylamino) -6-methyl-7-chloro fluoran, n-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-phenylaminofluoran, 3- (N, N-dibutylamino) -6-methyl-7-stubble aminofluoran, 3-piperidinyl-6-methyl-7-phenylaminofluoran, 3-pyrrolidinyl-6-methyl-7-phenylaminofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (3-ethyl-3-methyl-4-acetylamino-4-azaphthalide, 3- (1-ethyl-2-ethoxyphenyl) -3-methyl-4-methylbenzofuran-3' -bis (1-3-methyl-4-methylbenzofuran), 9' - [9H ] xanthen-3-one.
From the viewpoint of excellent visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution, the dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and more preferably a dye which develops color by radicals.
As pigment N, preference is given to leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate.
The pigment N may be used alone or in combination of 1 or 2 or more.
The content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 to 10 mass%, even more preferably 0.1 to 5 mass%, and particularly preferably 0.1 to 1 mass% relative to the total mass of the photosensitive composition layer, from the viewpoint of excellent visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution.
The content of the dye N represents the content of the dye when all of the dye N included in the total mass of the photosensitive composition layer is in a color development state. Hereinafter, a method for determining the content of the dye N will be described by taking a dye that develops color by a radical as an example.
A solution was prepared by dissolving 0.001g of pigment N and 0.01g in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photo radical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan ltd.) was added, and light having a wavelength of 365nm was irradiated, thereby generating radicals, and all the pigments N were set in a color development state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under an air atmosphere using a spectrophotometer (manufactured by UV3100, SHIMADZU CORPORATION), and a calibration curve was prepared.
Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that 3g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of pigment N. Based on the absorbance of the obtained solution containing the photosensitive composition layer, the content of the pigment N contained in the photosensitive composition layer was calculated from the calibration curve.
The photosensitive composition layer 3g was the same as the total solid content 3g in the photosensitive resin composition.
< thermally crosslinkable Compound >
The photosensitive composition layer may contain a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group described later is not regarded as a polymerizable compound, but is regarded as a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound. Among them, the blocked isocyanate compound is preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
Since the blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group, for example, in the case where the resin and/or the polymerizable compound or the like has at least the hydroxyl group and the carboxyl group,
There is a tendency that the hydrophilicity of the formed film is lowered and the function is enhanced when the photosensitive composition layer is cured and used as a film.
The blocked isocyanate compound means a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".
The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160 ℃, more preferably 130 to 150 ℃.
The dissociation temperature of the blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry: differential scanning calorimetry) analysis using a differential scanning calorimeter".
As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments inc (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited thereto.
Examples of the blocking agent having a dissociation temperature of 100 to 160℃include active methylene compounds (malonic acid diesters (malonic acid dimethyl, malonic acid diethyl, malonic acid di-N-butyl and malonic acid di-2-ethylhexyl), oxime compounds (formaldehyde oxime, aldoxime, acetyl oxime, methyl ethyl ketoxime and cyclohexanone oxime) and other compounds having a structure represented by-C (=N-OH) -in the molecule.
Among them, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably at least 1 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 viewpoint of improving brittleness of the film and improving adhesion to the transfer object.
The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanating hexamethylene diisocyanate to protect it.
Among them, as the blocked isocyanate compound having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferable from the viewpoints that the dissociation temperature is easily set within a preferable range as compared with a compound having no oxime structure and development residues are easily reduced.
The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferable.
Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, (meth) acrylamide group and styryl group, and a group having an epoxy group such as a glycidyl group.
Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and further preferably an acryloyloxy group.
Examples of the blocked isocyanate compound include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP and the like (manufactured by SHOWA DENKO K.K. above), and blocked DURANATE series (for example, manufactured by DURANATE (registered trademark) TPA-B80E, DURANATE (registered trademark) WT32-B75P and the like and Asahi Kasei Chemicals corporation).
Examples of the blocked isocyanate compound include compounds having the following structures.
[ chemical formula 2]
The thermally crosslinkable compound may be used alone or in combination of 1 or 2 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, relative to the total mass of the photosensitive composition layer.
Pigment >, pigment
The photosensitive composition layer may be a colored resin layer containing a pigment.
In recent years, a liquid crystal display window included in an electronic device may be mounted with a cover glass having a black frame-like light shielding layer formed on a rear surface peripheral edge portion of a transparent glass substrate or the like, to protect the liquid crystal display window. In order to form such a light shielding layer, a colored resin layer can be used.
The pigment may be appropriately selected according to a desired hue, and may be selected from a black pigment, a white pigment, and a color pigment other than black and white. Among them, in the case of forming a black-based pattern, a black pigment may be preferably selected as the pigment.
(Black pigment)
As the black pigment, a known black pigment (organic pigment, inorganic pigment, or the like) can be appropriately selected as long as the effect of the present invention is not impaired.
Among them, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, or graphite is preferable as the black pigment from the viewpoint of optical density, and carbon black is more preferable. As the carbon black, carbon black having at least a part of the surface coated with a resin is preferable from the viewpoint of surface resistance.
The particle diameter (number average particle diameter) of the black pigment is preferably 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm from the viewpoint of dispersion stability.
The particle diameter is an average value obtained by obtaining the particle diameter of any 100 particles and averaging the obtained 100 particle diameters, and the diameter of the circle is calculated from a photographic image of the pigment particles taken by an electron microscope and taking into consideration the same area as the area of the pigment particles.
Examples of the white pigment include an inorganic pigment and a white pigment described in paragraph [0015] and [0114] of Japanese patent application laid-open No. 2005-007765.
The inorganic pigment is preferably titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide or barium sulfate, more preferably titanium oxide or zinc oxide, further preferably titanium oxide, particularly preferably rutile or anatase titanium oxide, and most preferably rutile titanium oxide.
Further, the surface of titanium oxide may be subjected to a silica treatment, an alumina treatment, a titania treatment, a zirconia treatment, or an organic treatment, or may be subjected to two or more treatments. Thus, the catalytic activity of titanium oxide is suppressed, and the heat resistance and the gloss reducing property are improved.
From the viewpoint of reducing the thickness of the heated photosensitive composition layer, it is preferable to perform at least one of an alumina treatment and a zirconia treatment, and more preferably to perform both of the alumina treatment and the zirconia treatment, on the surface of titanium oxide.
In the case where 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. When the color pigment is contained, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of further excellent dispersibility. The lower limit is preferably 10nm or more.
Examples of the Color pigments include victoria pure blue BO (Color Index: color Index (hereinafter, c.i.) 42595), gold amine (c.i. 41000), lipo black HB (c.i. 26150), mozzite yellow GT (c.i. pigment yellow 12), permanent yellow GR (c.i. pigment yellow 17), permanent yellow HR (c.i. pigment yellow 83), permanent magenta FBB (c.i. pigment red 146), main yeast red ESB (c.i. pigment violet 19), permanent ruby FBH (c.i. pigment red 11), fastrel powder B Su Pula (c.i. pigment red 81), monazil blue (c.i. pigment blue 15), mozzite black B (c.i. pigment black 1) and carbon, c.i. pigment red 97, c.i. pigment red 122, c.i. pigment red 149, c.i. pigment red 168, c.i. pigment red 177, c.i. pigment red 180, c.i. pigment red 192, c.i. pigment blue 15, c.i. pigment green 15, c.i. pigment blue 15, c.i. pigment red blue: 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.
The pigment may be used alone or in combination of 1 kind or 2 or more kinds.
When the photosensitive composition layer contains a pigment, the content of the pigment is preferably more than 3 mass% and 40 mass% or less, more preferably more than 3 mass% and 35 mass% or less, still more preferably more than 5 mass% and 35 mass% or less, and particularly preferably 10 to 35 mass% or less, relative to the total mass of the photosensitive composition layer.
When the photosensitive composition layer contains a pigment other than a black pigment (white pigment and color pigment), the content of the pigment other than the black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and still more preferably 3 to 15% by mass, based on 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 can also be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or carrier) and dispersing with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. In addition, the vehicle means that, when the vehicle is a pigment dispersion liquid, the vehicle is in a liquid state at a portion of the medium in which the pigment is dispersed, 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, a grinding mill, a super mill, a dissolver, a homomixer, and a sand mixer.
Further, the fine pulverization can be performed by mechanical grinding by friction. Examples of the dispersing machine and the fine grinding include "encyclopedia of pigments" (manufactured by kukukukuku, first edition, asakura Publishing co., ltd.,2000, pages 438 and 310).
< other additives >)
The photosensitive composition layer may contain a known additive (other additive) as required in addition to the above components.
Examples of the other additives include radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (such as triazoles), pyridines (such as isonicotinamide), and purine bases (such as adenine).
Examples of the other additives include metal oxide particles, antioxidants, dispersants, acid-proliferation agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors, and paragraphs [0165] to [0184] of Japanese patent application laid-open No. 2014-085643, and these are incorporated herein.
The other additives may be used alone or in combination of 1 or more than 2.
(free radical polymerization inhibitor)
Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph [0018] of Japanese patent No. 4502784, and phenothiazine, phenoxazine, and 4-methoxyphenol are preferable.
Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenyl hydroxylamine aluminum salt and diphenyl nitrosoamine. Among them, nitrosophenyl hydroxylamine aluminum salt is preferable from the viewpoint of not impairing the sensitivity of the photosensitive composition layer.
The radical polymerization inhibitor may be used alone or in combination of at least 2 kinds.
When the photosensitive composition layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.001 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.02 to 2.0 mass% relative to the total mass of the photosensitive composition layer.
The content of the radical polymerization inhibitor is preferably 0.005 to 5.0 mass%, more preferably 0.01 to 3.0 mass%, and even more preferably 0.01 to 1.0 mass% based on the total mass of the polymerizable compound.
(benzotriazoles)
Examples of benzotriazoles include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.
(carboxybenzotriazoles)
Examples of carboxybenzotriazoles include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.
Specific examples of carboxybenzotriazoles include CBT-1 (JOHOKU CHEMICAL CO., LTD, product name).
The total content of the radical polymerization inhibitor, 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 mass% or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3 mass% or less, the maintenance of sensitivity and the suppression of discoloration of the dye are more excellent.
(sensitizer)
Examples of the sensitizer include known sensitizers, dyes and pigments.
Examples of the sensitizer include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone compound, a thioxanthone compound, an acridone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (e.g., 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.
When the photosensitive composition layer contains a sensitizer, the content of the sensitizer 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, from the viewpoints of improving the sensitivity to a light source and improving the curing speed based on the balance of the polymerization speed and chain transfer.
(surfactant)
Examples of the surfactant include surfactants described in paragraphs [0017] to [0071] of JP-A-2009-237362 in JP-A-4502784.
As the surfactant, nonionic surfactants, fluorine surfactants, or silicone surfactants are preferable.
Commercial products of the fluorine-based surfactant, examples of the materials include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, and R-94 and DS-21 (manufactured above as DIC CORPORATION), fluoro FC430, FC431, FC171 (manufactured above as Sumitomo 3M Limited), surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured above as AGC INC.), polyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured above as OMNOVA Solutions Inc.), FTERGENT 710FL, 710FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730, 650AC, 681, 683 (manufactured above as NEOS CORPORATION), U-120E (UNICHEM CO., LTD.), etc.
The fluorine-based surfactant is preferably an acrylic compound having a molecular structure containing a fluorine atom functional group, and the fluorine atom is volatilized by cutting a portion of the functional group containing a fluorine atom when heated.
Examples of such a fluorine-based surfactant include MEGAFACE DS series (chemical industry journal of the year 2016, 2 and 22 days) and daily industrial news (2016, 2 and 23 days) manufactured by DIC Corporation.
Further, as the fluorine-based surfactant, a polymer of a vinyl ether compound containing a fluorine atom and having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used.
Also, as the fluorine-based surfactant, a block polymer can be used.
The fluorine-containing surfactant is preferably a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
The fluorine-based surfactant may be, for example, a fluorine-containing polymer having a group containing an ethylenic unsaturated bond in a side chain, and examples thereof include MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (manufactured by DIC Corporation).
The fluorine-based surfactant is preferably a surfactant derived from a substitute material of a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), from the viewpoint of improving environmental suitability.
Examples of the nonionic surfactant include: glycerol, trimethylol propane, trimethylol ethane, ethoxylates thereof, propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters; PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (above are manufactured by BASF corporation); TETRONIC 304, 701, 704, 901, 904, and 150R1, hydrostart WE 3323 (manufactured above by BASF corporation); SOLSPERSE 20000 (manufactured above as Lubrizol Japan Ltd.); NCW-101, NCW-1001, and NCW-1002 (manufactured as FUJIFILM Wako Pure Chemical Corporation above); pionin D-1105, D-6112-W, and D-6315 (TAKEMOTO OIL & FAT Co., ltd.); and OLFIN E1010, surfynol 104, 400, 440 (Nissin Chemical Industry co., ltd. Above).
Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains and/or terminal ends.
Specific examples of the silicone surfactant include: EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (manufactured by DIC CORPORATION above), DOWSIL 8032 ADDITITIVE, toray Silicone DC3PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH28PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by BYK-Chemie GmbH above); x-22-4952, X-22-4272, X-22-6266, KF-351A, K L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002, 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 and KP-652 (manufactured by Shi-Ettd Co., above); f-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive Performance Materials Inc. above); and BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 and BYK323 (the above is manufactured by BYK Chemie GmbH).
When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0 mass%, more preferably 0.01 to 1.0 mass%, and even more preferably 0.05 to 0.8 mass% relative to the total mass of the photosensitive composition layer.
Examples of the plasticizer and the heterocyclic compound include those described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of International publication No. 2018/179640.
< impurity >
The photosensitive composition layer may contain impurities.
Examples of the impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.
(Metal impurity and halide ion)
Examples of the metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions thereof, and halide ions. Among them, sodium ions, potassium ions and halide ions are easily mixed, and therefore, the following contents are preferable.
The metal impurities are compounds different from the above-described particles (e.g., metal oxides).
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, relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but is preferably 1 ppb by mass or more, more preferably 0.1 ppm by mass or more, relative to the total mass of the photosensitive composition layer.
Examples of the method for adjusting the impurity content include a method for selecting a material having a small impurity content as a raw material of the photosensitive composition layer, a method for preventing contamination during formation of the photosensitive composition layer, and a method for cleaning and removing the material.
The content of impurities can be determined by a known method such as ICP emission spectrometry, atomic absorption spectrometry, or ion chromatography.
(residual organic solvent)
Examples of the residual organic solvent include benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide and hexane.
The content of the residual organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less, relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but is preferably 10 mass ppb or more, more preferably 100 mass ppb or more.
The content of the residual organic solvent can be prepared by the same method as the impurities of the above-mentioned metals. The content of the residual organic solvent can be determined by a known method such as gas chromatography.
(residual monomer)
The photosensitive composition layer may contain a residual monomer of each structural unit of the above resin.
From the viewpoints of patterning properties and reliability, the content of the residual monomer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and still more preferably 500 mass ppm or less, relative to the total mass of the resin. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, relative to the total mass of the resin.
From the viewpoints of patterning properties and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total mass of the photosensitive composition layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive resin composition layer.
The residual monomer amount of the monomer in synthesizing the alkali-soluble resin by the polymer reaction is also preferably set to the above range. For example, in the case of synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set to the above range.
The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.
The water content in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, from the viewpoint of improving reliability and lamination properties.
[ Properties of photosensitive composition layer ]
The thickness (film thickness) of the photosensitive composition layer is usually 0.1 to 300. Mu.m, preferably 0.2 to 100. Mu.m, more preferably 0.5 to 50. Mu.m, still more preferably 0.5 to 30. Mu.m, particularly preferably 1 to 20. Mu.m. This improves the developability of the photosensitive composition layer, and can improve resolution.
The content of the double bond in the photosensitive composition layer is preferably 0.8 to 3.0mmol/g, more preferably 1.0 to 3.0mmol/g, and even more preferably 1.2 to 2.0mmol/g.
The acid value of the photosensitive composition layer is preferably 10 to 150mgKOH/g, more preferably 40 to 100mgKOH/g, still more preferably 50 to 100mgKOH/g, particularly preferably 50 to 90mgKOH/g, and most preferably 70 to 90mgKOH/g, from the viewpoint of more excellent effect of the present invention.
Examples of the method for measuring the acid value include a method for measuring the acid value in the above-mentioned resin and a method for calculating the acid value from the known resin content.
[ intermediate layer ]
The transfer film of the present invention has an intermediate layer.
Examples of the intermediate layer include a water-soluble resin layer and an oxygen-blocking layer having an oxygen-blocking function described as a "separation layer" in JP-A-5-072724.
The intermediate layer is preferably an oxygen barrier layer from the viewpoints of an improvement in sensitivity at the time of exposure, a reduction in time load of an exposure machine, and an improvement in productivity.
When the transfer film has an oxygen barrier layer, the polymerization reaction can be easily and smoothly performed when the photosensitive composition layer of the transfer film is exposed to light, and the elastic modulus X of the cured layer can be set to a preferable range. As a result, the obtained pattern shape becomes good.
The oxygen barrier layer may be appropriately selected from known layers described in the above publications and the like.
Among them, an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (sodium carbonate 1 mass% aqueous solution at 22 ℃) is preferable.
The components that can be contained in the water-soluble resin layer (intermediate layer) will be described below.
< Water-soluble resin >)
The intermediate layer preferably comprises a water-soluble resin.
Examples of the water-soluble resin include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, polyether resins, gelatin, and polyamide resins.
Examples of the cellulose resin include water-soluble cellulose derivatives.
Examples of the water-soluble cellulose derivative include hydroxyethyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose.
Examples of the polyether resin include polyethylene glycol, polypropylene glycol, alkylene oxide adducts thereof, and vinyl ether resins.
Examples of the polyamide resin include an acrylamide resin, a vinyl amide resin, and an allylamide resin.
Among them, water-soluble cellulose derivatives or polyamide resins are preferable as the water-soluble resin.
Further, as the water-soluble resin, for example, a copolymer of (meth) acrylic acid/vinyl compound can be mentioned. As the copolymer of the (meth) acrylic acid/vinyl ester compound, a copolymer of (meth) acrylic acid/(meth) acrylic acid allyl group is preferable, and a copolymer of methacrylic acid/methacrylic acid allyl group is more preferable. When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the ratio (mol%) of each component is preferably 90/10 to 20/80, more preferably 80/20 to 30/70.
The weight average molecular weight (Mw) of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and further preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 50,000 or less.
The dispersity (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.
The water-soluble resin may be used alone or in combination of 1 kind or 2 or more kinds.
From the viewpoint of more excellent effects of the present invention and/or the viewpoint of more excellent oxygen barrier ability, the content of the water-soluble resin is preferably 50 mass% or more, more preferably 70 mass% or more, relative to the total mass of the intermediate layer. The upper limit is preferably 100 mass% or less, more preferably 99.9 mass% or less, further preferably 99.8 mass% or less, and particularly preferably 99 mass% or less.
< other Components >)
The intermediate layer may contain other components in addition to the above resin.
The molecular weight of the other component is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.
The other component is preferably a polyol, an alkylene oxide adduct of a polyol, a phenol derivative or an amide compound, and more preferably a polyol, a phenol derivative or an amide compound.
Examples of the polyhydric alcohols include glycerol, diglycerol and diethylene glycol.
The number of hydroxyl groups containing the polyhydric alcohol is preferably 2 to 10.
Examples of the alkylene oxide adducts of the polyols include those obtained by adding ethylene oxide, propylene oxide, and the like to the above-mentioned polyols. The average addition number is preferably 1 to 100, more preferably 2 to 50, and still more preferably 2 to 20.
Examples of the phenol derivative include bisphenol a and bisphenol S.
The amide compound may be N-methylpyrrolidone.
The intermediate layer preferably contains at least 1 selected from the group consisting of polyols, oxide adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.
The thickness of the intermediate layer is preferably 3.0 μm or less, more preferably 2.0 μm or less. The lower limit is preferably 1.0 μm or more.
The other components may be used alone or in combination of 1 kind or 2 or more kinds.
The content of the other component is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 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 still more preferably 5% by mass or less.
[ thermoplastic resin layer ]
The transfer film of the present invention may have a thermoplastic resin layer.
The thermoplastic resin layer is typically disposed between the temporary support and the photosensitive composition layer. The transfer film is provided with a thermoplastic resin layer, so that the following property to the substrate in the bonding process of the transfer film and the substrate is improved, and the air bubbles between the substrate and the transfer film can be restrained from mixing. As a result, adhesion to the thermoplastic resin layer adjacent layer (for example, the temporary support) can be ensured.
Examples of the thermoplastic resin layer include paragraphs [0189] to [0193] of JP-A-2014-085643, which are incorporated herein by reference.
From the viewpoint of adhesion to the adjacent layer, the thickness (layer thickness) of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. The upper limit is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less from the viewpoints of developability and resolution.
< thermoplastic resin >)
The thermoplastic resin layer preferably contains a thermoplastic resin.
As the thermoplastic resin, an alkali-soluble resin is preferable.
Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.
As the alkali-soluble resin, an acrylic resin is preferable from the viewpoints of developability and adhesion to an adjacent layer.
Here, the acrylic resin means a resin having at least 1 structural unit selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylamide.
In the acrylic resin, the total content of the structural units derived from (meth) acrylic acid, the structural units derived from (meth) acrylic acid ester, and the structural units derived from (meth) acrylamide is preferably 50 mass% or more with respect to the total mass of the acrylic resin. The upper limit is preferably 100 mass% or less relative to the total mass of the acrylic resin.
Wherein the total content of the structural units derived from (meth) acrylic acid and the structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.
As the alkali-soluble resin, a polymer having an acid group is preferable.
Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonate group, and a carboxyl group is preferable.
From the viewpoint of developability, the acid value of the alkali-soluble resin is preferably 60mgKOH/g or more. The upper limit is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, still more preferably 200mgKOH/g or less, particularly preferably 150mgKOH/g or less.
Among them, the alkali-soluble resin is preferably 60mgKOH/g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more.
The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is not particularly limited, but can be appropriately selected from known resins.
Examples thereof include alkali-soluble resins which are carboxyl-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraph [0025] of JP-A2011-095716, carboxyl-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraphs [0033] to [0052] of JP-A2010-237589, and carboxyl-containing acrylic resins having an acid value of 60mgKOH/g or more in the resins described in paragraphs [0053] to [0068] of JP-A2016-224162.
The copolymerization ratio of the carboxyl group-containing structural units in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, based on the total mass of the acrylic resin.
As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth) acrylic acid is particularly preferable from the viewpoints of developability and adhesion to an adjacent layer.
The alkali-soluble resin may have a reactive group.
The reactive group may be any group capable of addition polymerization, and examples thereof include: an ethylenically unsaturated group; a polycondensate group such as a hydroxyl group or a carboxyl group; and polyaddition reactive groups such as epoxy groups, (block) isocyanate groups, and the like.
The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 ～ 100,000, and further preferably 20,000 ～ 50,000.
The alkali-soluble resin may be used alone in an amount of 1 kind or in an amount of 2 or more kinds.
The content of the alkali-soluble resin is preferably 10 to 99 mass%, more preferably 20 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 50 to 75 mass% with respect to the total mass of the thermoplastic resin layer from the viewpoints of developability and adhesion to the adjacent layer.
Pigment >, pigment
The thermoplastic resin layer preferably contains a dye (hereinafter, also simply referred to as "dye B") having a maximum absorption wavelength of 450nm or more in the wavelength range of 400 to 780nm at the time of color development and having a maximum absorption wavelength changed by an acid, an alkali or a radical.
The preferred embodiment of the dye B is the same as that of the dye N described above, except for the point described below.
The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.
From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains two substances: a dye whose maximum absorption wavelength is changed by an acid as a dye B, and a compound which generates an acid by light, which will be described later.
The pigment B may be used alone or in combination of 1 or 2 or more.
The content of the dye B is preferably 0.2 mass% or more, more preferably 0.2 to 6.0 mass%, even more preferably 0.2 to 5.0 mass%, and particularly preferably 0.25 to 3.0 mass% relative to the total mass of the thermoplastic resin, from the viewpoint of visibility of the exposed portion and the non-exposed portion.
Here, the content of the pigment B means the content of the pigment when all the pigments B contained in the thermoplastic resin layer are in a color development state. Hereinafter, a method for quantifying the content of the dye B will be described by taking a dye that develops color by a radical as an example.
A solution was prepared by dissolving 0.001g of pigment B and 0.01g in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photo radical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan ltd.) was added, and light having a wavelength of 365nm was irradiated, thereby generating radicals, and all the pigments B were set in a colored state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under an air atmosphere using a spectrophotometer (manufactured by UV3100, SHIMADZU CORPORATION), and a calibration curve was prepared.
Next, absorbance of the solution in which the pigment was developed entirely was measured in the same manner as described above except that 0.1g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment B. Based on the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of pigment B contained in the thermoplastic resin layer was calculated from the calibration curve.
The thermoplastic resin layer 3g was the same as the solid content 3g of the composition.
< Compounds which generate acid, base or free radical by light >
The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, also simply referred to as "compound C").
The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving activation light such as ultraviolet light or visible light.
Examples of the compound C include a known photoacid generator, a photobase generator, and a photo radical polymerization initiator (photo radical generator).
(photoacid generator)
From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator.
The photoacid generator may be, for example, a photo-cationic polymerization initiator that can be contained in the photosensitive composition layer, and the same is preferable except for the point described below.
The photoacid generator preferably contains at least 1 compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.
The photoacid generator is preferably one having the following structure.
[ chemical formula 3]
(photo radical polymerization initiator)
The thermoplastic resin layer may contain a photo radical polymerization initiator.
The photo radical polymerization initiator may be, for example, a photo radical polymerization initiator which may be contained in the photosensitive composition layer, and the same preferable embodiment is also adopted.
(photobase generator)
The thermoplastic resin composition may contain a photobase generator.
Examples of the photobase generator include known photobase generators.
Specifically, 2-nitrobenzyl cyclohexyl carbamate, trityl alcohol, O-carbamoyl hydroxyamide, O-carbamoyl oxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane 1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammoniumcobalt (III) tris (tritylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine, and 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine can be mentioned.
The compound C may be used alone or in combination of 1 or 2 or more.
The content of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass% with respect to the total mass of the thermoplastic resin layer from the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion.
Plasticizer >
From the viewpoints of resolution, adhesion to an adjacent layer, and developability, the thermoplastic resin layer preferably contains a plasticizer.
The plasticizer preferably has a molecular weight (weight average molecular weight when it is an oligomer or polymer and has a molecular weight distribution) smaller than that of the alkali-soluble resin. The molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
Further, from the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth) acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to the adjacent layer, it is more preferable that the alkali-soluble resin is an acrylic resin, and the plasticizer contains a (meth) acrylate compound.
Examples of the (meth) acrylate compound used as the plasticizer include (meth) acrylate compounds described as polymerizable compounds that can be contained in the photosensitive composition layer.
In the transfer film, when the thermoplastic resin layer and the photosensitive composition layer are stacked in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth) acrylate compound. This is because the thermoplastic resin layer and the photosensitive composition layer each contain the same (meth) acrylate compound, whereby the diffusion of components between layers can be suppressed and the storage stability can be improved.
In the case where the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize in the exposed portion after exposure from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer.
Further, as the (meth) acrylate compound that can be used as the plasticizer, a polyfunctional (meth) acrylate compound having 2 or more (meth) acryloyl groups in 1 molecule is preferable from the viewpoints of resolution of the thermoplastic resin layer, adhesion to an adjacent layer, and developability.
Further, as the (meth) acrylate compound that can be used as a plasticizer, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.
The plasticizer may be used alone or in combination of 1 kind or 2 or more kinds.
The content of the plasticizer is preferably 1 to 70 mass%, more preferably 10 to 60 mass%, and even more preferably 20 to 50 mass% with respect to the total mass of the thermoplastic resin layer from the viewpoints of resolution of the thermoplastic resin layer, adhesion to an adjacent layer, and developability.
< sensitizer >)
The thermoplastic resin layer may also contain a sensitizer.
The sensitizer is not particularly limited, and examples thereof include those that can be contained in the photosensitive composition layer.
The sensitizer may be used alone or in combination of 1 or 2 or more.
The content of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to the light source and the visibility of the exposed portion and the non-exposed portion.
< other additives >)
In addition to the above components, the thermoplastic resin layer may contain other additives as needed.
Examples of the other additive include other additives that can be contained in the photosensitive composition layer.
< impurity >
The thermoplastic resin layer may contain impurities.
Examples of the impurities include impurities that can be contained in the photosensitive composition layer.
[ other parts ]
The transfer film of the present invention may have other members in addition to the above-described members.
Examples of the other member include a protective film.
(protective film)
As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include a polyolefin film such as a polypropylene film and a polyethylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, and a polystyrene film.
As the protective film, a resin film made of the same material as the temporary support may be used.
Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or a polyethylene film, and further preferably a polyethylene film.
The thickness of the protective film is preferably 1 to 100. Mu.m, more preferably 5 to 50. Mu.m, still more preferably 5 to 40. Mu.m, particularly preferably 15 to 30. Mu.m.
The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and is preferably 100 μm or less from the viewpoint of relatively low cost.
The protective film preferably has a fish eye number of 5/m with a diameter of 80 μm or more 2 The following is given.
"fish eyes" means a substance that is taken into a film by foreign substances, undissolved substances, oxidized degradation substances, or the like of a material when the material is hot-melted and the film is produced by a method such as kneading, extrusion, biaxial stretching, casting, or the like.
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 is given. The lower limit is preferably 0 pieces/mm 2 The above. In the case where the amount is within these ranges, defects caused by transfer of irregularities due to particles contained in the protective film to the photosensitive composition layer or the conductive layer can be suppressed.
From the viewpoint of imparting winding properties, the arithmetic average roughness Ra of the surface of the protective film on the opposite side of the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The upper limit is preferably less than 0.50. Mu.m, more preferably 0.40. Mu.m, still more preferably 0.30. Mu.m.
From the viewpoint of suppressing defects during 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 even more preferably 0.03 μm or more. The upper limit is preferably less than 0.50. Mu.m, more preferably 0.40. Mu.m, still more preferably 0.30. Mu.m.
[ method for producing transfer film ]
The method for producing the transfer film is not particularly limited, and a known method can be used.
Examples of the method for producing the transfer film 10 include: the method comprises the following steps: a step of forming a coating film by applying a water-soluble resin composition to the surface of the temporary support 11, and further forming an intermediate layer 13 by drying the coating film; and a step of forming a coating film by applying a photosensitive composition to the surface of the intermediate layer 13 and further drying the coating film to form a photosensitive composition layer 15.
Further, the method may include a step of forming a thermoplastic resin layer by applying a thermoplastic resin composition to the surface of the temporary support 11 before the step of forming the intermediate layer 13, and then drying the coating film.
The transfer film 10 is manufactured by pressing the protective film 19 against the photosensitive composition layer 15 of the laminate manufactured by the above-described manufacturing method.
As a method for producing the transfer film, 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 the surface of the photosensitive composition layer 15 opposite to the side having the temporary support 11. The transfer film including the temporary support 11, the thermoplastic resin layer, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19 can be manufactured by a process including providing the protective film 19 so as to be in contact with the surface of the photosensitive composition layer 15 on the side opposite to the side having the temporary support 11.
After the transfer film 10 is manufactured by the above manufacturing method, the transfer film 10 may be wound to manufacture and store a transfer film in a roll form. The transfer film in the form of a roll can be supplied as it is to a step of bonding the transfer film to a substrate in a roll-to-roll system described later.
In addition, as a method for producing the transfer film 10, after the photosensitive composition layer 15 and the intermediate layer 13 are formed on the protective film 19, a thermoplastic resin layer is formed on the surface of the intermediate layer 13.
[ photosensitive composition and method for Forming photosensitive composition layer ]
The photosensitive composition containing the components (for example, a resin, a polymerizable compound, a polymerization initiator, and the like) and a solvent constituting the photosensitive composition layer is preferably used and formed by a coating method.
Specifically, a method of forming a photosensitive composition layer by applying a photosensitive composition to an intermediate layer and drying the coating film at a predetermined temperature is preferable as a method of producing a transfer film. The amount of the residual solvent is adjusted by the drying treatment of the coating film.
The photosensitive composition preferably contains various components and solvents for forming the photosensitive composition layer. In the photosensitive composition, the preferable range of the content of each component with respect to the total solid content of the photosensitive 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 each component other than the solvent can be dissolved or dispersed, and known solvents can be used. Specifically, examples thereof include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (N-propyl acetate, etc.), amide solvents, and lactone solvents, and mixed solvents containing 2 or more of them.
The solvent preferably contains at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.
Among them, a mixed solvent containing at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 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 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent is further preferable.
Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (for example, propylene glycol monomethyl ether acetate), 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 solvent include solvents described in paragraphs [0092] to [0094] of Japanese patent application laid-open No. 2018/179640 and solvents described in paragraph [0014] of Japanese patent application laid-open No. 2018-177889, which are incorporated herein by reference.
The solvent may be used alone or in combination of 1 or more than 2.
The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
Examples of the method for applying the photosensitive composition include a printing method, a spraying method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (slit coating method).
As a method for drying the coating film of the photosensitive composition, heat drying and reduced pressure drying 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 preferably 130℃or lower, more preferably 120℃or lower. Further, the temperature may be continuously changed and dried.
The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and still more preferably 300 seconds or less.
Further, the transfer film may be produced by bonding a protective film to the photosensitive composition layer.
As a method for attaching the protective film to the photosensitive composition layer, for example, a known method is given.
Examples of the means for bonding the protective film to the photosensitive composition layer include known laminators such as vacuum laminators and automatic cutting laminators.
The laminator preferably has an arbitrary heatable roll such as a rubber roll, and can perform pressurization and heating.
[ method for Forming Water-soluble resin composition and intermediate layer (Water-soluble resin layer) ]
The water-soluble resin composition preferably contains various components and solvents for forming the 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 1 selected from the group consisting of water and a water-miscible organic solvent, more preferably water or a mixed solvent of water and a water-miscible organic solvent.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.
The solvent may be used alone or in combination of 1 or more than 2.
The content of the solvent is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
The method for forming the water-soluble resin 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, and inkjet coating).
[ composition for Forming thermoplastic resin layer and method for Forming thermoplastic resin layer ]
The method for forming the thermoplastic resin layer on the temporary support is not particularly limited, and a known method can be used. For example, the thermoplastic resin layer-forming composition may be applied to the temporary support and dried as necessary.
The thermoplastic resin layer-forming composition preferably contains various components and solvents for forming the thermoplastic resin layer. In the composition for forming a thermoplastic resin layer, 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 thermoplastic resin layer.
The solvent is not particularly limited as long as each component other than the solvent can be dissolved or dispersed, and known solvents can be used. The solvent may be the same as the solvent contained in the photosensitive composition described later, and the preferable mode is the same.
The solvent content is preferably 50 to 1900 parts by mass, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
The method for forming the thermoplastic 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).
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the embodiments shown below. Unless otherwise specified, "parts" and "%" are based on mass.
In the following examples, the weight average molecular weight of the resin was determined by conversion of polystyrene based on the Gel Permeation Chromatography (GPC) described above. The theoretical acid value was used as the acid value.
[ resin ]
< Synthesis of resin A1 >
Propylene glycol monomethyl ether acetate (PGMEA, 67.0 parts by mass) was added to a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution of MAA (20.0 parts by mass), st (52.0 parts by mass), MMA (28.0 parts by mass), V-601 (4.0 parts by mass) and PGMEA (33.0 parts by mass) was added dropwise to the above flask solution maintained at 90.+ -. 2 ℃ over 2 hours. After the completion of the dropwise addition, the solution in the flask was stirred at 90.+ -. 2 ℃ for 1 hour. A solution of V-601 (1.0 parts by mass) and PGMEA (33.0 parts by mass) was added dropwise to the above flask solution maintained at 90.+ -. 2 ℃ over 30 minutes. After completion of the dropwise addition, the solution in the flask was stirred at 90±2 ℃ for 1 hour, and PGMEA (100.0 parts by mass) was added for dilution to give resin A1 (solid content concentration 30.0 mass%). Further, referring to the method for synthesizing the resin A1, resins A2 to A6 (solid content concentration of any resin is 30.0 mass%) were obtained.
The resins A1 to A6 are shown in table 1 below.
In table 1, the monomers used to form each structural unit (mass%) are abbreviated as "monomers".
The resins A1 to A6 correspond to alkali-soluble resins.
TABLE 1
In table 1, the following description is given.
MAA: methacrylic acid (FUJIFILM Wako Pure Chemical Corporation production)
MMA: methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation manufacture)
EMA: ethyl methacrylate (FUJIFILM Wako Pure Chemical Corporation manufacture)
St: styrene (FUJIFILM Wako Pure Chemical Corporation manufacture)
BzMA: benzyl methacrylate (FUJIFILM Wako Pure Chemical Corporation manufactured)
[ photosensitive composition ]
The following components shown in table 2 and each photosensitive composition blended were prepared.
In table 2, the numerical values described in the component columns indicate the content (parts by mass) of each component. Wherein the amount of each resin in the column of "resin" represents the amount of the resin solution (solid content concentration 30 mass%).
TABLE 2
< polymerizable Compound >)
Ethoxylated bisphenol A dimethacrylate
Ethoxylated (3) trimethylolpropane triacrylate
4-n-octyl phenoxy pentaethylene glycol monopropylene glycol acrylic ester
Ethylene oxide propylene oxide modified urethane dimethacrylate
< photopolymerization initiator >)
2- (o-chlorophenyl) -4, 5-diphenylimidazole
< sensitizer >)
4, 4-bis (diethylamino) benzophenone
< developer >)
Colorless crystal violet
< solvent >
Acetone (acetone)
Toluene (toluene)
Methanol
[ composition for Forming an intermediate layer ]
An intermediate layer-forming composition 1 was prepared using the following components.
4-88LA (67.86 mass%): KURARAY co., ltd. Manufactured, polyvinyl alcohol
PVP K30 (31.06 mass%): FUJIFILM CORPORATION, polyvinylpyrrolidone
Metolose 60SH03 (1.00 mass%): shin-Etsu Chemical co., ltd. Water-soluble cellulose derivative
F444 (0.08 mass%): DIC Corporation, surfactant
[ transfer film ]
As shown in table 3, each transfer film composed of a temporary support, an intermediate layer, and a photosensitive composition layer was produced. Specifically, the following is described.
First, on a temporary support (polyethylene terephthalate film (manufactured by Lumirer16KS40, TORAY INDUSTRIES, INC)) having a thickness of 16 μm, the composition 1 for forming an intermediate layer described above was applied using a bar coater so that the thickness after drying became 1.0 μm, and dried at 90℃using an oven, to form an intermediate layer.
Further, a photosensitive composition for forming a photosensitive composition layer shown in table 3 was applied onto the intermediate layer using a bar coater to a thickness after drying shown in table 3, and dried at 80 ℃ using an oven to form a negative photosensitive composition layer.
On the obtained negative photosensitive composition layer, polyethylene terephthalate (manufactured by 16KS40,TORAY INDUSTRIES,INC) having a thickness of 16 μm was pressure-bonded, and transfer films of examples and comparative examples were produced.
[ measurement and evaluation ]
Elastic modulus >
The elastic modulus X and the elastic modulus Y were measured by the above-described method.
Pattern shape (skirt extended shape) >
The protective film of the transfer film produced in the above was peeled off, and the surface of the exposed photosensitive composition layer was laminated (lamination condition: substrate temperature 80 ℃, rubber roll temperature 110 ℃, wire pressure 3N/cm, transport speed 2 m/min) onto a substrate having a conductive layer plated with Ni (thickness 100 nm) on glass, to obtain a laminate.
Next, the temporary support was peeled off from the obtained laminate, and a photomask having a pattern of 1/1 line (μm)/space (μm) was brought into close contact with the surface of the intermediate layer side of the obtained laminate. Light was irradiated at 100mJ/cm using a high-pressure mercury lamp exposure machine (MAP-1200L,apan Science Engineering Co, manufactured by Ltd., dominant wavelength: 365 nm) 2 For photosensitive composition layerExposure is performed. Then, a pattern was formed by spray development using an aqueous sodium carbonate solution at a liquid temperature of 25 ℃ for 30 seconds. The cross-sectional shape of the obtained pattern was observed by a scanning electron microscope, and the pattern shape was evaluated on the side surface of each pattern based on the following evaluation standard, using the length of the portion (the skirt extension portion in fig. 1) exposed from the upper surface portion (the surface opposite to the substrate side) of the pattern as the skirt length and using the longest skirt length.
A: the length of the lower hem is below 0.3 μm
B: the swing length exceeds 0.3 μm and is less than 0.5 μm
C: the length of the turndown exceeds 0.5 μm
Pattern adhesion >
The protective film of the transfer film produced in the above was peeled off, and the surface of the exposed photosensitive composition layer was laminated (lamination conditions: substrate temperature 80 ℃, rubber roll temperature 110 ℃, wire pressure 3N/cm, transport speed 2 m/min) onto a conductive substrate plated with Ni (thickness 100 nm) on glass to obtain a laminate.
Next, the temporary support was peeled off from the obtained laminate, and a photomask having a pattern of 1/1 line (μm)/space (μm) was brought into close contact with the surface of the intermediate layer side of the obtained laminate. Light was irradiated at 100mJ/cm using a high-pressure mercury lamp exposure machine (MAP-1200L,apan Science Engineering Co, manufactured by Ltd., dominant wavelength: 365 nm) 2 The photosensitive composition layer is exposed to light. Then, a pattern was formed by spray development using an aqueous sodium carbonate solution at a liquid temperature of 25 ℃ for 30 seconds. The obtained pattern was observed with a scanning electron microscope, and the minimum line width without pattern peeling and floating at the end was evaluated as pattern adhesion (μm).
Resolution >, resolution
The protective film of the transfer film produced in the above was peeled off, and the surface of the exposed photosensitive composition layer was laminated (lamination conditions: substrate temperature 80 ℃, rubber roll temperature 110 ℃, wire pressure 3N/cm, transport speed 2 m/min) onto a conductive substrate plated with Ni (thickness 100 nm) on glass to obtain a laminate.
Next, the temporary support was peeled off from the obtained laminate, and a photomask having a pattern of 1/1 line (μm)/space (μm) was brought into close contact with the surface of the intermediate layer side of the obtained laminate. Light was irradiated at 100mJ/cm using a high-pressure mercury lamp exposure machine (MAP-1200L,apan Science Engineering Co, manufactured by Ltd., dominant wavelength: 365 nm) 2 The photosensitive composition layer is exposed to light. Then, a pattern was formed by spray development using an aqueous sodium carbonate solution at a liquid temperature of 25 ℃ for 30 seconds. The minimum line width at which the obtained pattern can be decomposed was set as resolution (μm), and the resolution was evaluated.
< development residue inhibitory Property >)
A pattern was formed in the same manner as in < resolution > described above, and the obtained line/space pattern was subjected to measurement of the thickness of the residue in the space portion observed by a scanning electron microscope and visual observation, and development residue inhibition was evaluated according to the following criteria.
A: the thickness of the residue in the space is 50nm or less, and no residue is observed visually
B: the thickness of the residue at the space is below 50nm, and the residue is visible by eyes
C: the thickness of the residues at the space part exceeds 50nm
The evaluation results are shown in table 3.
Table 3 shows the respective descriptions.
The column "M/B" shows the mass ratio of the content of the polymerizable compound having 2 or more functions to the content of the resin (content of the polymerizable compound having 2 or more functions/content of the resin).
The ratio of the elastic modulus X to the elastic modulus Y (elastic modulus X/elastic modulus Y) is shown in the column "X/Y".
"Tg" means the Tg of the resin contained in the photosensitive composition layer.
"M/B", "content of double bond" and "acid value" represent values of the photosensitive composition layer.
TABLE 3
From the results in table 3, it was confirmed that the method for producing a laminate according to the present invention was excellent in pattern shape and pattern adhesion.
It was also confirmed that the development residue inhibition performance was more excellent when the elastic modulus Y obtained in the above measurement Y was 3.5MPa or less (comparison of example 2 and example 1).
It was also confirmed that the development residue inhibition was more excellent when the ratio of the elastic modulus X to the elastic modulus Y was 1500 to 10000 (comparison of example 2 and example 1).
It was also confirmed that the pattern shape was more excellent when the content of double bonds in the photosensitive composition layer was 1.0 to 3.0mmol/g (comparison of examples 1 to 2 and example 5)
It was also confirmed that the pattern shape was more excellent when the glass transition temperature Tg of the resin was 90 to 150 ℃ (comparison of examples 1 to 2 and example 6).
It was also confirmed that the pattern shape was more excellent when the acid value of the photosensitive composition layer was 50 to 90mgKOH/g (comparison of examples 1 to 2 and example 4).
It was also confirmed that the pattern shape was more excellent when the mass ratio of the content of the polymerizable compound having 2 functions or more to the content of the resin was 0.60 to 1.00 (comparison of examples 1 to 2 and example 3).
Symbol description
1-substrate, 2-pattern (cured layer), 3-skirt extension, 10-transfer film, 11-temporary support, 13-intermediate layer, 15-photosensitive composition layer, 17-composition layer, 19-protective film.

Claims (22)

1. A method for producing a laminate, comprising:
a bonding step of bringing a surface of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order, on the side opposite to the intermediate layer side, into contact with a substrate, and bonding the transfer film and the substrate;
a peeling step of peeling the temporary support between the temporary support and the intermediate layer;
an exposure step of performing pattern exposure on the photosensitive composition layer; a kind of electronic device with high-pressure air-conditioning system
A developing step of developing the photosensitive composition layer after exposure with a developing solution to form a pattern,
in the method for producing the laminate, the elastic modulus X obtained in the measurement X is 1.0GPa to 10.0GPa,
measurement of X: the method comprises the steps of bringing a surface of the photosensitive composition layer of the transfer film on the side opposite to the intermediate layer side into contact with the substrate, bonding the transfer film and the substrate, peeling the temporary support from the obtained laminate and between the temporary support and the intermediate layer, exposing the photosensitive composition layer from the exposed intermediate layer side to the entire surface, peeling the exposed intermediate layer, and measuring the elastic modulus of the exposed cured layer as an elastic modulus X.
2. The method for producing a laminate according to claim 1, wherein,
the elastic modulus Y obtained in the measurement Y is 3.5MPa or less,
measurement of Y: the elastic modulus of the photosensitive composition layer of the transfer film was measured as elastic modulus Y.
3. The method for producing a laminate according to claim 2, wherein,
the ratio of the elastic modulus X to the elastic modulus Y is 1500-10000.
4. The method for producing a laminate according to any one of claim 1 to 3, wherein,
the content of double bonds in the photosensitive composition layer is 1.0 mmol/g-3.0 mmol/g.
5. The method for producing a laminate according to any one of claims 1 to 4, wherein,
the photosensitive composition layer comprises a resin and,
the glass transition temperature Tg of the resin is 90-150 ℃.
6. The method for producing a laminate according to any one of claims 1 to 5, wherein,
the photosensitive composition layer has an acid value of 50mgKOH/g to 100mgKOH/g.
7. The method for producing a laminate according to any one of claims 1 to 6, wherein,
the photosensitive composition layer contains a polymerizable compound having 2 or more functions and a resin,
the mass ratio of the content of the 2-functional or higher polymerizable compound to the content of the resin is 0.60 to 1.00.
8. The method for producing a laminate according to any one of claims 1 to 7, wherein,
the intermediate layer contains at least 1 selected from the group consisting of polyols, oxide adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.
9. The method for producing a laminate according to any one of claims 1 to 8, wherein,
the thickness of the photosensitive composition layer is 1-20 mu m.
10. The method for producing a laminate according to any one of claims 1 to 9, wherein,
the thickness of the intermediate layer is 3.0 μm or less.
11. The method for producing a laminate according to any one of claims 1 to 10, wherein,
the exposure step is an exposure step of exposing the pattern by bringing the exposed intermediate layer into contact with a mask.
12. A method for manufacturing a circuit wiring includes:
a bonding step of bringing a surface of a photosensitive composition layer on the opposite side of a transfer film having a temporary support, an intermediate layer, and a photosensitive composition layer in this order into contact with a substrate having a conductive layer, and bonding the transfer film and the substrate;
A peeling step of peeling the temporary support between the temporary support and the intermediate layer;
an exposure step of performing pattern exposure on the photosensitive composition layer;
a developing step of developing the photosensitive composition layer after exposure with a developing solution to form a pattern; a kind of electronic device with high-pressure air-conditioning system
An etching step of etching the conductive layer in a region where the pattern is not arranged,
in the method for manufacturing the circuit wiring, the elastic modulus X obtained in the measurement X is 1.0GPa to 10.0GPa,
measurement of X: the method comprises the steps of bringing a surface of the photosensitive composition layer of the transfer film on the side opposite to the intermediate layer side into contact with the substrate, bonding the transfer film and the substrate, peeling the temporary support from the obtained laminate and between the temporary support and the intermediate layer, exposing the photosensitive composition layer from the exposed intermediate layer side to the entire surface, peeling the exposed intermediate layer, and measuring the elastic modulus of the exposed cured layer as an elastic modulus X.
13. A transfer film comprising a temporary support, an intermediate layer and a photosensitive composition layer in this order,
and an exposure step of performing pattern exposure on the photosensitive composition layer,
The elastic modulus X of the transfer film obtained in the measurement X is 1.0GPa to 10.0GPa,
measurement of X: the method comprises the steps of bringing a surface of the photosensitive composition layer of the transfer film on the side opposite to the intermediate layer side into contact with a substrate, bonding the transfer film and the substrate, peeling the temporary support from the obtained laminate and between the temporary support and the intermediate layer, performing full-face exposure on the photosensitive composition layer from the exposed intermediate layer side, peeling the exposed intermediate layer, and measuring the elastic modulus of the exposed cured layer as an elastic modulus X.
14. The transfer film according to claim 13, wherein,
the elastic modulus Y obtained in the measurement Y is 3.5MPa or less,
measurement of Y: the elastic modulus of the photosensitive composition layer of the transfer film was measured as elastic modulus Y.
15. The transfer film according to claim 14, wherein,
the ratio of the elastic modulus X to the elastic modulus Y is 1500-10000.
16. The transfer film according to any one of claims 13 to 15, wherein,
the content of double bonds in the photosensitive composition layer is 1.0 mmol/g-3.0 mmol/g.
17. The transfer film according to any one of claims 13 to 16, wherein,
The photosensitive composition layer comprises a resin and,
the glass transition temperature Tg of the resin is 90-150 ℃.
18. The transfer film according to any one of claims 13 to 17, wherein,
the photosensitive composition layer has an acid value of 50mgKOH/g to 100mgKOH/g.
19. The transfer film according to any one of claims 13 to 18, wherein,
the photosensitive composition layer contains a polymerizable compound having 2 or more functions and a resin,
the mass ratio of the content of the 2-functional or higher polymerizable compound to the content of the resin is 0.60 to 1.00.
20. The transfer film according to any one of claims 13 to 19, wherein,
the intermediate layer contains at least 1 selected from the group consisting of polyols, oxide adducts of polyols, phenol derivatives, amide compounds, water-soluble cellulose derivatives, polyether resins, and polyamide resins.
21. The transfer film according to any one of claims 13 to 20, wherein,
the thickness of the photosensitive composition layer is 1-20 mu m.
22. The transfer film according to any one of claims 13 to 21, wherein,
the thickness of the intermediate layer is 3.0 μm or less.
CN202180085898.5A 2020-12-25 2021-12-17 Method for producing laminate, method for producing circuit wiring, and transfer film Pending CN116762040A (en)

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JP2020-217593 2020-12-25
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JP2002296776A (en) * 2001-03-29 2002-10-09 Taiyo Ink Mfg Ltd Photosetting/thermosetting resin composition for printed wiring substrate and printed wiring substrate
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JP6851009B2 (en) * 2016-04-22 2021-03-31 パナソニックＩｐマネジメント株式会社 Resin composition for solder resist, film for solder resist, circuit board and package with solder resist layer
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