CN116917806A - Method for manufacturing laminate with conductor pattern - Google Patents

Method for manufacturing laminate with conductor pattern Download PDF

Info

Publication number
CN116917806A
CN116917806A CN202280016396.1A CN202280016396A CN116917806A CN 116917806 A CN116917806 A CN 116917806A CN 202280016396 A CN202280016396 A CN 202280016396A CN 116917806 A CN116917806 A CN 116917806A
Authority
CN
China
Prior art keywords
photosensitive layer
laminate
conductor pattern
exposure
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280016396.1A
Other languages
Chinese (zh)
Inventor
石坂壮二
鬼塚悠
新田浩二
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority claimed from PCT/JP2022/006927 external-priority patent/WO2022181539A1/en
Publication of CN116917806A publication Critical patent/CN116917806A/en
Pending legal-status Critical Current

Links

Landscapes

  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

The invention provides a method for manufacturing a laminate with a conductor pattern, which can manufacture a laminate with a conductor pattern with excellent linearity. The method for producing a laminate having a conductor pattern according to the present invention includes a predetermined step of using a transfer film or the like having a temporary support and a photosensitive layer, wherein the photosensitive layer has a length X of 1.0 [ mu ] m or less, which is obtained by measuring X as follows. Measurement of X: the cross section of the resist pattern obtained by exposing the photosensitive layer to a line pattern having a line width and a space width of 1:1 and then developing the resist pattern was observed, and the penetration length of the alkali metal into the side surface of the resist pattern was set to be a length X.

Description

Method for manufacturing laminate with conductor pattern
Technical Field
The present invention relates to a method for manufacturing a laminate having a conductor pattern.
Background
Since the number of steps for obtaining a predetermined conductor pattern is small, a resist pattern is arranged on an arbitrary substrate using a transfer film having a photosensitive layer, and a method of forming a conductor pattern using the resist pattern may be used.
Patent document 1 discloses a photosensitive resin laminate in which a predetermined intermediate layer and a predetermined photosensitive resin layer are sequentially laminated 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
However, in the case of a conductor pattern having poor linearity, particularly in the case of thinning the conductor pattern, breakage and/or short-circuiting of the conductor pattern may occur due to a slight difference in linearity, which may adversely affect the energization.
The present inventors have attempted to form a conductor pattern using the photosensitive resin laminate (transfer film) described in patent document 1, and have found that there is room for improvement in the linearity of the conductor pattern formed on the substrate.
Accordingly, an object of the present invention is to provide a method for producing a laminate having a conductor pattern, which can produce a laminate having a conductor pattern with excellent linearity.
Means for solving the technical problems
The present inventors have found that the above problems can be solved by the following configuration.
〔1〕
A method for manufacturing a laminate having a conductor pattern, comprising:
a bonding step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate having a metal layer on a surface thereof, such that the photosensitive layer side is in contact with the metal layer;
An exposure step of performing pattern exposure on the photosensitive layer;
a developing step of developing the exposed photosensitive layer with an aqueous solution containing an alkali metal salt to form a resist pattern;
an etching step of etching the metal layer in a region where the resist pattern is not arranged or a plating step of plating the metal layer;
a resist stripping step of stripping the resist pattern; a kind of electronic device with high-pressure air-conditioning system
A removing step of removing the exposed metal layer by the resist stripping step, and forming a conductor pattern on the substrate,
a temporary support peeling step of peeling off the temporary support between the bonding step and the exposure step or between the exposure step and the developing step,
the length X of the photosensitive layer obtained by the following measurement X is 1.0 μm or less.
Measurement X: the observed pass line width and space width were 1:1, and developing the photosensitive layer with the aqueous solution used in the developing step, and setting the penetration length of the alkali metal into the side surface of the resist pattern to be a length X.
〔2〕
The method for producing a laminate having a conductor pattern according to [ 1 ], wherein,
the crosslinking reaction amount of the photosensitive layer obtained by the formula Y of the photosensitive layer is more than 0.20 mmol/g.
Formula Y:
crosslinking reaction amount= (a×b)/(100)
Wherein the double bond equivalent of the photosensitive layer before exposure is amol/g, the exposure to light of 365nm wavelength by FT-IR using a high-pressure mercury lamp exposure machine was 20mJ/cm 2 The double bond reaction ratio obtained by exposing the photosensitive layer after the exposure was set to B%.
The film thickness of the photosensitive layer exposed by the high-pressure mercury lamp exposure machine was set to 3 μm.
〔3〕
The method for producing a laminate having a conductor pattern according to [ 1 ] or [ 2 ], wherein,
the photosensitive layer contains a polymerization initiator and a polymerizable compound.
〔4〕
The method for producing a laminate having a conductor pattern according to [ 3 ], wherein,
the polymerizable compound contains a polymerizable compound having 2 or more functions.
〔5〕
The method for producing a laminate having a conductor pattern according to [ 3 ] or [ 4 ], wherein,
the polymerizable compound contains a polymerizable compound having 3 or more functions.
〔6〕
The method for producing a laminate having a conductor pattern according to any one of [ 3 ] to [ 5 ], wherein,
the polymerizable compound includes a polymerizable compound having an ethyleneoxy group.
〔7〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 6 ], wherein,
the photosensitive layer contains a resin having an I/O value of less than 0.70.
〔8〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 7 ], wherein,
the photosensitive layer contains a resin having a polymerizable group.
〔9〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 8 ], wherein,
the photosensitive layer contains a resin having a weight average molecular weight of 5,000 to 30,000.
〔10〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 9 ], wherein,
the photosensitive layer contains a resin having an acid value of 80 to 200 mgKOH/g.
〔11〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 10 ], wherein,
the photosensitive layer has a film thickness of 5 μm or less.
〔12〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 11 ], wherein,
The transfer film has an intermediate layer between the temporary support and the photosensitive layer.
〔13〕
The method for producing a laminate having a conductor pattern according to [ 12 ], wherein,
the intermediate layer contains a water-soluble resin.
〔14〕
The method for producing a laminate having a conductor pattern as described in [ 12 ] or [ 13 ], wherein,
the intermediate layer contains at least 1 selected from the group consisting of water-soluble cellulose derivatives, polyols, alkylene oxide adducts of polyols, polyethers, phenol derivatives, and amide compounds.
〔15〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 11 ], wherein,
the temporary support peeling step is provided between the bonding step and the exposing step,
the exposure step is a step of exposing a pattern through a photomask.
〔16〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 11 ], wherein,
the temporary support peeling step is provided between the bonding step and the exposing step,
the exposure step is a step of exposing the exposed surface of the photosensitive layer to a photomask to expose the pattern.
〔17〕
The method for producing a laminate having a conductor pattern according to any one of [ 12 ] to [ 14 ], wherein,
the temporary support peeling step is provided between the bonding step and the exposing step,
the exposure step is a step of exposing the exposed surface of the intermediate layer to a photomask to expose the pattern.
〔18〕
The method for producing a laminate having a conductor pattern according to any one of [ 1 ] to [ 11 ], wherein,
the temporary support peeling step is provided between the exposure step and the development step,
the exposure step is a step of exposing a pattern through a photomask.
〔19〕
The method for producing a laminate having a conductor pattern as defined in any one of [ 15 ] to [ 18 ], wherein,
the photomask includes light shielding portions arranged in a grid.
〔20〕
The method for producing a laminate having a conductor pattern as defined in any one of [ 15 ] to [ 18 ], wherein,
the photomask includes a light shielding portion arranged in a circular dot shape.
〔21〕
The method for producing a laminate having a conductor pattern as defined in any one of [ 15 ] to [ 18 ], wherein,
the photomask includes openings arranged in a circular dot shape.
Effects of the invention
According to the present invention, a method for manufacturing a laminate having a conductor pattern, which can manufacture a laminate having a conductor pattern with excellent linearity, can be provided.
Drawings
Fig. 1 is a partial schematic view of a cross section of a laminate having a linear resist pattern.
Fig. 2 is a schematic diagram showing an example of a transfer film.
Detailed Description
The present invention will be described in detail below.
In the present specification, the numerical range indicated by the term "to" refers to a range including numerical values described before and after the term "to" as a lower limit value and an upper limit value.
In the present specification, the upper limit or the lower limit of a numerical range described in stages may be replaced with the upper limit or the lower limit of a numerical range described in other stages. In the numerical ranges described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be substituted for the values 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 desired purpose of the process is achieved.
In the present specification, unless otherwise specified, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700nm is 80% or more, preferably 90% or more.
In the present specification, the average transmittance of visible light is a value measured by a spectrophotometer, and can be measured by, 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 by using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (each of product names manufactured by TOSOH Corporation) as columns, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, polystyrene as a standard substance, and polystyrene as a standard substance measured by a Gel Permeation Chromatography (GPC) analysis apparatus.
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 P asa) spectroscopic analysis device.
In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, "(meth) acryloyloxy" is a concept including both acryloyloxy and acryloyloxy, "(meth) acrylamido" is a concept including both acrylamido and methacrylamido, and "(meth) acrylate" is a concept including both acrylate and methacrylate.
In the present specification, "alkali-soluble" means that the solubility of 100g of a 1 mass% aqueous sodium carbonate solution at a liquid temperature of 22 ℃ is 0.1g or more. Thus, for example, an alkali-soluble resin refers to a resin that satisfies the solubility conditions described above.
In the present specification, "water-soluble" means that the solubility of 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more. Thus, for example, a water-soluble resin refers to a resin that satisfies the above solubility conditions.
The "solid component" of the composition refers to a component forming a composition layer (for example, a photosensitive layer or an intermediate layer) formed using the composition, and when the composition contains a solvent (for example, an organic solvent, water, or the like), it refers to all components except the solvent. In addition, if the composition layer is formed of a component, the liquid component is also regarded as a solid component.
[ method for producing laminate having conductor pattern ]
The method for producing a laminate having a conductor pattern according to the present invention (hereinafter also simply referred to as the method of the present invention) comprises:
a bonding step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate having a metal layer on a surface thereof, such that the photosensitive layer side is in contact with the metal layer;
an exposure step of pattern-exposing the photosensitive layer;
a developing step of developing the exposed photosensitive layer with an aqueous solution containing an alkali metal salt to form a resist pattern;
an etching step of etching the metal layer in a region where the resist pattern is not arranged or a plating step of plating the metal layer;
a resist stripping step of stripping the resist pattern; a kind of electronic device with high-pressure air-conditioning system
A removing step of removing the exposed metal layer by the resist stripping step, and forming a conductor pattern on the substrate, wherein in the method for manufacturing a laminate having a conductor pattern,
a temporary support peeling step of peeling off the temporary support between the bonding step and the exposure step or between the exposure step and the developing step,
The length X of the photosensitive layer obtained by the following measurement X is 1.0 μm or less.
Measurement X: the cross section of the resist pattern obtained by exposing the photosensitive layer to a line pattern having a line width and a space width of 1:1 and then developing the exposed resist pattern with the aqueous solution used in the developing step was observed, and the penetration length of the alkali metal into the side surface of the resist pattern was set to be a length X.
With the above-described structure, the mechanism of action for solving the problems of the present invention is not clear, but the present inventors consider the following.
First, as a characteristic point of the method of the present invention, there is mentioned a point that the length X of the photosensitive layer used in the method of the present invention, which is obtained by measuring X, becomes 1.0 μm or less. That is, the exposure portion of the photosensitive layer used in the method of the present invention can suppress penetration of the developer used in the developing step.
If the developer penetrates deeply into the exposed portion of the photosensitive layer, the resist pattern formed by the photosensitive layer is likely to have a shape in which the skirt spreads, and the fluctuation in the shape of the skirt is also likely to be large. It is considered that the use of such a resist pattern to form a conductor pattern adversely affects the linearity of the obtained conductor pattern.
On the other hand, if the length X is 1.0 μm or less and penetration of the developer can be suppressed, the extension of the skirt in the resist pattern formed of the photosensitive layer can be suppressed, and the fluctuation of the shape of the skirt can be suppressed even if the shape is formed. Further, it is considered that the straightness of the obtained conductor pattern can be improved as a result of forming the conductor pattern using such a resist pattern.
In addition, a conductor pattern having a small line width in the method of the present invention can be formed.
Hereinafter, the effect of the present invention is also referred to as more excellent, in which the straightness of the conductor pattern of the laminate is more excellent and/or the line width of the conductor pattern of the laminate can be made smaller.
[ measurement of X ]
In the method of the present invention, the length X obtained by measuring X is 1.0 μm or less, preferably 0.6 μm or less, more preferably 0.4 μm or less. The lower limit of the length X is not limited, and is, for example, 0.0 μm or more.
Measurement X was performed as follows.
Measurement of X: the cross section of the resist pattern obtained by exposing the photosensitive layer to a line pattern having a line width and a space width of 1:1 and then developing the exposed resist pattern with an aqueous solution used in a developing step was observed, and the penetration length of alkali metal into the side surface of the resist pattern was set to be a length X.
In measurement X, a photosensitive layer disposed on a substrate having a metal layer on the surface thereof, which is used in the method of the present invention, was subjected to a bonding step and a temporary support peeling step under the same conditions as those of the substrate used in the method of the present invention, using the transfer film used in the method of the present invention.
The transfer film, photosensitive layer, substrate having a metal layer on the surface, bonding step, and temporary support peeling step will be described later.
In addition, in the measurement X, when the exposure is performed by the line pattern having the line width and the space width of 1:1, the same exposure light source as that used for the exposure in the method of the present invention is used as the exposure light source.
The exposure was adjusted to obtain a resist pattern having a line width and a space width of 1:1 after development.
The transfer film has an intermediate layer described later, and when the photosensitive layer disposed on the substrate having the metal layer on the surface has the intermediate layer on the surface, exposure is performed from the intermediate layer side.
The line width of the resist pattern formed for measuring X is sufficiently wide, for example, 10 μm in line width so that an alkali metal infiltrated region starting from both side surfaces of the linear resist pattern (hereinafter, also simply referred to as "line") is not repeated. The pattern of the photomask for exposure is appropriately adjusted in such a manner that a line of an appropriate width is obtained.
In measurement X, development was performed under the same conditions as those of the development step performed in the method of the present invention after exposure. The same developer (aqueous solution) as that used in the developing step performed in the method of the present invention is also used for the developing.
The development step and the developer will be described later.
After development, the laminate having the obtained resist pattern was cut in a direction perpendicular to the longitudinal direction of the line, and the cross section of the resist pattern was observed.
For observation, SEM-EDX (scanning electron microscope-energy dispersive X-ray analysis) mapping analysis was performed using JEOL Ltd. JSM-7200F type FE-SEM (field emission scanning electron microscope) with an acceleration voltage of 5kV and an irradiation current 18. The intensity distribution of the alkali metal in the cross section is plotted from the EDX map of the alkali metal in the cross section, and the half width of the peak is set as a region where infiltration of the alkali metal occurs. Specifically, there is a peak of the detection intensity of the alkali metal at or near the surface of the sidewall of the resist pattern, and the detection intensity of the alkali metal decreases from the peak as it enters the inside of the resist pattern. The region from the outermost surface of the sidewall of the resist pattern to the portion where the detection intensity of the alkali metal on the inner side of the resist pattern is half of the peak is defined as a region where the penetration of the alkali metal occurs.
Next, how long the infiltration region of the alkali metal is generated is determined from the side face of the wire. In addition, regarding the region where the alkali metal infiltration occurs from the upper portion of the wire, the length of the region where the alkali metal infiltration occurs is not determined.
A method for determining the length of a region where alkali metal penetration occurs will be described with reference to fig. 1. Fig. 1 is a partial schematic view of a cross section (a cross section perpendicular to the longitudinal direction of a line) of a laminate having a metal layer on the surface thereof, the laminate having a substrate 101 and a linear resist pattern (line) 107 in this order. The substrate 101 having a metal layer on the surface has a substrate 103 and a metal layer 105 in this order. In the line 107, there are a region 109 where infiltration of alkali metal occurs and a region 111 where infiltration of alkali metal does not occur. In this case, the length x is the length of the region where the infiltration of alkali metal occurs. That is, the length x is a length in the width direction of the line of a region where alkali metal infiltration occurs from the side of the line in a cross-sectional view of the line.
Fig. 1 shows a line in which no drag is generated, and when drag is generated on the line (for example, when the width of the line 107 is widened at a portion near the metal layer 105 in the line 107), the length x is obtained at a position where no increase in line width due to drag is generated.
The length X was obtained from 10 random lines of the cross section of the laminate, and the average value thereof was defined as the length X (alkali metal penetration length) obtained by measuring X.
[ Cross-linking reaction amount, Y ]
In the photosensitive layer used in the method of the present invention, the crosslinking reaction amount obtained by the following formula Y is preferably 0.10mmol/g or more, more preferably 0.20mmol/g or more, and still more preferably 0.30mmol/g or more. The upper limit of the crosslinking reaction amount is preferably 1.20mmol/g or less, more preferably 1.00mmol/g or less, and still more preferably 0.80mmol/g or less.
Formula Y:
crosslinking reaction amount= (a×b)/(100)
In the formula Y, A is the double bond equivalent (unit: mmol/g) of the photosensitive layer before exposure.
The double bond equivalent is the content of polymerizable carbon-carbon double bonds relative to the total mass of the photosensitive layer.
The form of the carbon-carbon double bond is not limited, and may be derived from a resin described later, a polymerizable compound described later, or both.
The double bond equivalent is determined by measuring the photosensitive layer by FT-IR (Fourier Transform Infrared Spectroscopy ).
The Ammol/g is, for example, 0.50 to 3.20mmol/g, preferably 0.60 to 2.60mmol/g, more preferably 1.20 to 2.50mmol/g.
In the formula Y, B means that the exposure amount of light with a wavelength of 365nm is 20mJ/cm by using a high-pressure mercury lamp exposure machine 2 The photosensitive layer was exposed (full-face exposure), and the double bond reaction ratio (unit:%) was determined by observing the photosensitive layer after exposure by FT-IR.
The dominant wavelength of the high-pressure mercury lamp exposure machine is 365nm.
As a high-pressure mercury lamp exposure machine, MAP-1200L, japan Science Engineering Co., ltd. Are generally used.
That is, the amount of carbon-carbon double bonds in the photosensitive layer before exposure was taken as 100%, the amount of carbon-carbon double bonds (Z%) in the photosensitive layer after exposure was obtained, and the value obtained by subtracting Z from 100 was the value of B.
The amount of carbon-carbon double bonds in the photosensitive layer before and after exposure was measured by FT-IR.
The value of B% is preferably 5 to 70%, more preferably 10 to 50%.
The photosensitive layer used for obtaining the value of B is preferably a photosensitive layer prepared by performing a bonding step and a temporary support peeling step under the same conditions as those implemented by the method of the present invention on a substrate having a metal layer on the surface thereof, using a transfer film used in the method of the present invention.
The transfer film has an intermediate layer described later, and when the photosensitive layer disposed on the substrate having the metal layer on the surface has the intermediate layer on the surface, exposure for obtaining the value of B is performed from the intermediate layer side.
In the exposure for obtaining the value of B, the exposure process performed in the method of the present invention is preferably performed in the same manner as the exposure process except for the matters specified as the conditions for obtaining the exposure for obtaining the value of B.
When the value of B was obtained, the film thickness of the photosensitive layer exposed by a high-pressure mercury lamp exposure machine was set to 3. Mu.m.
When the film thickness of the photosensitive layer of the transfer film was not 3 μm, the film thickness of the photosensitive layer was adjusted to 3 μm, and a test was performed.
For example, when the film thickness of the photosensitive layer of the transfer film exceeds 3 μm, the photosensitive layer of the transfer film may be cut to a film thickness of 3 μm in advance to adjust the thickness, and then a step for obtaining the value of B may be performed using the transfer film. When the photosensitive layer of the transfer film is cut, the transfer film can be cooled appropriately.
For example, when the film thickness of the photosensitive layer of the transfer film is smaller than 3 μm, the photosensitive layer having a film thickness of 3 μm can be adjusted by the following steps. That is, first, the photosensitive layer of the transfer film is cut, and a solution in which the cut photosensitive layer is dissolved in a production organic solvent (PGMEA: propylene glycol monomethyl ether acetate, etc.). The above-mentioned solution was applied to a release film and then dried to obtain a coating film (photosensitive layer formed using the solution). At this time, the film thickness of the coating film was adjusted to be 3 μm in total with the film thickness of the photosensitive layer of the transfer film. The transfer film is laminated on the coating film disposed on the surface of the release film so as to overlap the photosensitive layer. Thus, the transfer film had a photosensitive layer having a film thickness of 3 μm in total by the coating film (photosensitive layer formed using the solution) and the photosensitive layer originally possessed by the transfer film. Thereafter, the release film is removed from the transfer film, and a step for obtaining the value of B may be performed using the transfer film having the photosensitive layer (photosensitive layer having a total film thickness of 3 μm).
The transfer film, photosensitive layer, substrate having a metal layer on the surface, bonding step, and temporary support peeling step will be described later.
[ embodiment of the invention ]
In the method of the present invention, there are generally a method of manufacturing a laminate having a conductor pattern through an etching process and a method of manufacturing a laminate having a conductor pattern through a plating process.
Hereinafter, a method of manufacturing a laminate having a conductor pattern through an etching process is also referred to as embodiment 1 in the method of the present invention. The method of manufacturing a laminate having a conductor pattern through a plating treatment step is also referred to as embodiment 2 of the method of the present invention.
First, embodiment 1 will be described, and next, embodiment 2 will be described.
[ embodiment 1 ]
Embodiment 1 of the present invention includes at least the following steps (1-1) to (1-5) in order.
Step (1-1) (bonding step): and a step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate having a metal layer on a surface thereof so that the photosensitive layer side is in contact with the metal layer.
Step (1-2) (exposure step): and exposing the photosensitive layer in a pattern.
Step (1-3) (developing step): and a step of forming a resist pattern by developing the exposed photosensitive layer with an aqueous solution containing an alkali metal salt.
Step (1-4) (etching step): and etching the metal layer in the region where the resist pattern is not arranged.
Step (1-5) (resist stripping step): and stripping the resist pattern.
Embodiment 1 of the present invention includes the following step (1-A) between steps (1-1) and (1-2) or between steps (1-2) and (1-3).
Step (1-A) (temporary support peeling step): and peeling off the temporary support.
The length X of the photosensitive layer used in embodiment 1 of the present invention, which is obtained by the measurement X, is within a predetermined range.
The photosensitive layer used in embodiment 1 of the present invention preferably has a crosslinking reaction amount obtained by the formula Y within a predetermined range.
< step (1-1) and bonding step >
The bonding step is a step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate having a metal layer on a surface thereof so that the photosensitive layer is in contact with the metal layer.
When the transfer film has a protective film to be described later, the laminating step is preferably performed after the protective film is peeled off.
The transfer film preferably further includes an intermediate layer between the temporary support and the photosensitive layer.
The transfer film will be described later.
In the lamination, it is preferable to bring the photosensitive layer side (the surface on the opposite side from the temporary support side) of the transfer film into contact with the metal layer on the substrate and press-contact the same.
As the pressure bonding method, for example, a known transfer method and lamination method are preferable, and a method of pressing and heating by a roller or the like is preferable in which a surface of the transfer film on the side opposite to the temporary support side of the photosensitive layer is overlapped on the substrate.
As the bonding method, for example, a known lamination machine such as a vacuum lamination machine and an automatic cutting lamination machine is used.
The lamination temperature is preferably 70 to 130 ℃.
The substrate having a metal layer on the surface (substrate with a metal layer) includes a substrate and a metal layer disposed on the surface of the substrate.
The substrate with a metal layer may be formed with any layer other than the metal layer described above on the substrate as required. That is, the substrate with a metal layer preferably has at least a substrate and a metal layer disposed on a surface of the substrate.
Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate, and the substrate described in paragraph [0140] of International publication No. 2018/155193 is preferable.
As a material of the resin substrate, polyethylene terephthalate, cyclic olefin 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.
In particular, in the exposure step, when a photomask including light shielding portions arranged in a grid is used, a transparent substrate is preferably used.
The term "transparent" as used herein means that the transmittance at the exposure wavelength is 50% or more. The transmittance of the transparent substrate is preferably 80% or more, more preferably 90%, and even more preferably 95% relative to the total light transmittance.
Examples of the transparent base material include a resin substrate (e.g., a resin film) and a glass substrate. The resin substrate is preferably a resin substrate that transmits visible light. Preferable components of the resin substrate transmitting visible light include, for example, polyamide-based resins, polyethylene terephthalate-based resins, polyethylene naphthalate-based resins, cycloolefin-based resins, polyimide-based resins, and polycarbonate-based resins. More preferable components of the resin substrate transmitting visible light include, for example, polyamide, polyethylene terephthalate (PET), cyclic Olefin Polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate.
Among these transparent substrates, a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer, a polyethylene naphthalate film, a polyimide film, or a polycarbonate film is preferable, and a polyethylene terephthalate film is more preferable.
The thickness of the transparent substrate is not limited. The thickness of the transparent substrate is preferably 10 to 200. Mu.m, more preferably 20 to 120. Mu.m, and still more preferably 20 to 100. Mu.m.
The thickness of the transparent substrate was measured by the following method. A cross section in a direction perpendicular to the main surface of the transparent substrate (i.e., a thickness direction) was observed using a Scanning Electron Microscope (SEM). From the obtained observation image, the thickness of the transparent substrate was measured at 10 points. The average thickness of the transparent substrate was obtained by arithmetically averaging the measured values.
In particular, when a photomask including light shielding portions arranged in a circular dot shape or opening portions arranged in a circular dot shape is used, an organic substrate such as a silicon substrate, a glass substrate, or FR4 (Flame Retardant Type, flame retardant 4) is preferably used as the base material. In this case, the thickness of the base material is not particularly limited, and a wiring pattern may be formed in a part of the base material, or a wiring layer may be laminated. A photomask including light shielding portions arranged in a circular dot shape or opening portions arranged in a circular dot shape will be described in the following section.
The metal layer is a layer containing a metal, and a known metal can be used as the metal without particular limitation. The metal layer is preferably a conductive layer.
Examples of the main component of the metal layer (main metal) include copper, chromium, lead, nickel, gold, silver, tin, and zinc. The main component is a metal having the largest content of metals contained in the metal layer.
The thickness of the metal layer is not particularly limited, but is preferably 50nm or more, and more preferably 100nm or more. The upper limit is not particularly limited, but is preferably 2 μm or less.
The method for forming the metal layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion in which metal fine particles are dispersed to sinter a coating film, a sputtering method, and a vapor deposition method.
The substrate may have 1 or 2 or more metal layers.
In the case of disposing 2 or more metal layers, the metal layers of 2 or more layers may be the same or different from each other, and preferably are metal layers of different materials.
The substrate is preferably a substrate having at least one of a transparent electrode and routing wiring, and the substrate can be used as a substrate for a touch panel.
The transparent electrode can function as an electrode for a touch panel.
The transparent electrode is preferably formed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), and a metal thin wire such as a metal mesh and a metal nanowire.
Examples of the thin metal wire include thin metal wires such as silver and copper, and silver conductive materials such as silver mesh and silver nanowire are preferable.
The material of the wiring is preferably metal.
Examples of the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys of these, and copper, molybdenum, aluminum, or titanium is preferable, and copper is more preferable.
< step (1-2) and Exposure step >
The exposure step is a step of pattern-exposing the photosensitive layer.
The "pattern exposure" refers to exposure in a pattern-like manner, and refers to exposure in a manner in which there are exposed portions and non-exposed portions.
The positional relationship between the exposed portion (exposed region) and the non-exposed portion (non-exposed region) in the pattern exposure can be appropriately adjusted.
The exposure direction may be from the photosensitive layer side or the side opposite to the photosensitive layer side (substrate side).
The exposure process is typically a process of performing pattern exposure through a photomask. In the exposure step, the photomask may or may not be in contact with the laminate as the photosensitive material.
In the case of performing a temporary support peeling step described later between the bonding step and the exposure step, the exposure step is preferably performed by bringing the surface of the laminate from which the temporary support obtained in the temporary support peeling step is peeled on the side opposite to the substrate side into contact with a photomask, and performing pattern exposure. In other words, it is preferable that the exposure step of exposing the photosensitive layer by pattern exposure is performed by bringing the surface (surface of the photosensitive layer, surface of the intermediate layer, or the like) of the laminate from which the temporary support is peeled, which surface is exposed by peeling the temporary support, into contact with the photomask. The exposed surface corresponds to the surface of the photosensitive layer in the case of the transfer film having a 2-layer structure of the temporary support and the photosensitive layer, and corresponds to the surface of the intermediate layer in the case of the transfer film having a 3-layer structure of the temporary support, the intermediate layer, and the photosensitive layer.
By using such an exposure step, a finer resist pattern is obtained, and a finer conductor pattern is finally obtained.
Such an exposure step is particularly preferably used when a temporary support peeling step, which will be described later, is performed between the bonding step and the exposure step.
In the exposure step of performing the pattern exposure, a curing reaction of the components contained in the photosensitive layer can be generated in the exposure region (region corresponding to the opening of the photomask) of the photosensitive layer. After exposure, a developing step is performed to remove the non-exposed region of the photosensitive layer, thereby forming a pattern.
The method of the present invention preferably further includes a photomask peeling step of peeling the photomask used in the exposure step between the exposure step and the development step.
As the photomask peeling step, for example, a known peeling step is given.
The light source for pattern exposure may be any light source capable of irradiating at least a wavelength region (e.g., 365nm and 405 nm) where the photosensitive layer is curable, and is preferably 365nm. "dominant wavelength" refers to 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 amount is preferably 5 to 200mJ/cm 2 More preferably 10 to 200mJ/cm 2 。
Examples of the light source, the exposure amount, and the exposure method include paragraphs [0146] to [0147] of International publication No. 2018/155193, which are incorporated herein by reference.
< step (1-A) and temporary support Release step >
A temporary support peeling step is performed between the bonding step and the exposure step or between the exposure step and the developing step.
Among these, a peeling step is more preferably provided between the bonding step and the exposure step.
The peeling step is a step of peeling the temporary support from the laminate of the transfer film and the substrate with the metal layer.
As a peeling method of 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.
< procedure (1-3) and development procedure >
The developing step is a step of developing the exposed photosensitive layer with an aqueous solution containing an alkali metal salt as a developing solution to form a pattern.
By developing with the developer, the non-exposed region of the photosensitive layer is removed, and a resist pattern is formed with the opening of the photomask as a convex portion.
The developer is preferably an alkaline aqueous solution containing an alkali metal salt.
The alkali metal salt contained in the developer is preferably a compound which is soluble in water and exhibits basicity.
Examples of the alkali metal salt include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate.
The developer may contain a compound which is soluble in water and shows basicity other than alkali metal salts, and examples of these compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyl trimethylammonium hydroxide).
The content of water in the developer is preferably 50 mass% or more and less than 100 mass%, more preferably 90 mass% or more and less than 100 mass%, relative to the total mass of the developer.
The content of the alkali metal salt in the developer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, relative to the total mass of the developer.
As the developing method, for example, a known developing method is given.
Specifically, spin-coating immersion development, spray development, spin development, and immersion development are mentioned.
As the developing method, the developing method described in paragraph [0195] of International publication No. 2015/093271 is preferable.
After development, a rinse treatment for removing the developer remaining on the substrate with the metal layer is preferably performed before the process moves to the next step. Water or the like can be used for the flushing treatment.
After the development and/or rinsing treatment, a drying treatment may be performed to remove the remaining solution from the substrate with the metal layer.
The position and size of the resist pattern formed on the substrate with the metal layer are not particularly limited, and preferably have a thin line shape.
Specifically, the line width of the resist 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, for example, 1.0 μm or more.
< step (1-B) (post-exposure step) and step (1-C) (post-baking step) >
Embodiment 1 may further include a step of exposing a resist pattern obtained on the substrate with a metal layer (hereinafter, also referred to as "step (1-B)" or "post-exposure step") and/or a step of heating (hereinafter, also referred to as "step (1-C)" or "post-baking step") between the development step and the etching step described later.
In the case where embodiment 1 has both the post-exposure step and the post-baking step, it is preferable to perform the post-baking step after performing 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 。
The post-baking temperature in the post-baking step is preferably 80 to 250 ℃, more preferably 90 to 160 ℃.
The post-baking time in the post-baking step is preferably 1 to 180 minutes, more preferably 10 to 60 minutes.
< procedure (1-4) etching procedure >
The etching step is a step of etching the metal layer in a region where the resist pattern is not arranged.
Specifically, in the etching step, the metal layer is etched using the resist pattern obtained up to the above step as an etching resist.
When the etching step is performed, the metal layer is removed from the opening of the resist pattern, and the metal layer has the same pattern shape as the resist pattern.
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 which the substrate is immersed in an etching liquid.
The etching liquid used in the wet etching may be an acidic or alkaline etching liquid appropriately selected according to the object to be etched.
Examples of the acidic etching solution include an acidic aqueous solution containing at least 1 acidic compound and an acidic mixed aqueous solution of an acidic compound and at least 1 selected from the group consisting of ferric trichloride, 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 selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, fluoric acid, oxalic acid and phosphoric acid.
Examples of the alkaline etching solution include an alkaline aqueous solution containing at least 1 alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (for example, potassium permanganate and the like).
As the basic compound (compound which is dissolved in water and exhibits basicity) contained in the basic aqueous solution, for example, at least 1 selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (for example, tetramethylammonium hydroxide, etc.) is preferable.
The etching solution preferably does not dissolve the resist pattern.
The developer used in the developing step may be used as an etching solution used in the etching process. In this case, the development step and the etching step may be performed simultaneously.
After the etching treatment, a rinse treatment for removing the etching liquid remaining on the substrate with the metal layer is preferably performed before the next step. Water or the like can be used for the flushing treatment.
After the etching treatment and/or the rinsing treatment, a drying treatment may be performed to remove the remaining solution from the substrate with the metal layer.
< steps (1-5) and resist stripping step >
The resist stripping step is a step of removing the remaining resist pattern after the etching step.
As a method for removing the remaining resist pattern, for example, a method of removing by chemical treatment, preferably a method of removing using a stripping solution, is mentioned.
As a method for removing the remaining resist pattern, for example, a method of using a stripping solution and removing the resist pattern by a known method such as a spray method, a shower method, or a spin-coating immersion method is mentioned.
Examples of the stripping liquid include a stripping liquid in which an alkaline compound is dissolved in at least 1 selected from water, dimethyl sulfoxide and N-methylpyrrolidone.
Examples of the basic compound (a compound which is dissolved in water and exhibits basicity) include basic inorganic compounds such as sodium hydroxide and potassium hydroxide, and basic organic compounds such as primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium compounds.
The liquid temperature of the stripping liquid is preferably 30 to 80 ℃, more preferably 50 to 80 ℃.
A preferable mode of the removal method is a method in which the substrate to be removed having a pattern is immersed in a stripping liquid under stirring at a liquid temperature of 50 to 80 ℃ for 1 to 30 minutes.
The stripping liquid also preferably does not dissolve the metal layer.
After the resist pattern is stripped by the stripping liquid, a rinse treatment for removing the stripping liquid remaining on the substrate is also preferably performed. Water or the like can be used for the flushing treatment.
After the stripping and/or rinsing treatment of the resist pattern with the stripping liquid, a drying treatment for removing the remaining solution from the substrate may be performed.
When the resist stripping step is performed, the remaining resist pattern is removed from the substrate, and thereby a metal layer (a metal layer having the same pattern shape as the removed resist pattern) existing between the substrate and the resist pattern is exposed on the surface, to obtain a laminate having a conductor pattern.
[ embodiment 2 ]
Embodiment 2 of the present invention includes at least the following steps (2-1) to (2-6) in order.
Step (2-1) (bonding step): and a step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate having a metal layer on a surface thereof so that the photosensitive layer side is in contact with the metal layer.
Step (2-2) (exposure step): and exposing the photosensitive layer in a pattern.
Step (2-3) (developing step): and a step of forming a resist pattern by developing the exposed photosensitive layer with an aqueous solution containing an alkali metal salt.
Step (2-4) (plating treatment step): and a step of plating the metal layer in the region where the resist pattern is not arranged.
Step (2-5) (resist stripping step): and stripping the resist pattern.
Step (2-6) (removal step): and a removing step of removing the metal layer exposed by the resist stripping step and forming a conductor pattern on the substrate.
Embodiment 2 of the present invention includes the following step (2-a) between steps (2-1) and (2-2) or between steps (2-2) and (2-3).
Step (2-A) (temporary support peeling step): and peeling off the temporary support.
Further, the length X of the photosensitive layer used in embodiment 2 of the present invention, which is obtained by the measurement X, is within a predetermined range.
The crosslinking reaction amount of the photosensitive layer preferably used in embodiment 2 of the present invention, which is obtained by the formula Y, is within a predetermined range.
< steps (2-1) to (2-3), (2-A) to (2-C) >)
The steps (2-1) to (2-3) and (2-A) in embodiment 2 are the same as those described for the steps (1-1) to (1-3) and (1-A) in embodiment 1.
In embodiment 2, a step of further exposing a resist pattern obtained on a substrate with a metal layer (hereinafter, also referred to as "step (2-B)" or "post-exposure step") and/or a step of heating (hereinafter, also referred to as "step (2-C)" or "post-baking step") may be provided between the step (2-3) (developing step) and the step (2-4) described later.
The steps (2-B) and (2-C) in embodiment 2 are the same as those described for the steps (1-B) and (1-C) in embodiment 1.
< step (2-4) and plating step >
The plating step is a step of forming a plating layer by plating treatment on the metal layer (the metal layer exposed on the surface by the developing step) located in the region where the resist pattern is not arranged.
Examples of the plating treatment method include an electrolytic plating method and an electroless plating method, and the electrolytic plating method is preferable from the viewpoint of productivity.
When the plating step is performed, a plating layer having the same pattern shape as the region where the resist pattern is not arranged (the opening of the resist pattern) is obtained on the substrate with the metal layer.
Examples of the metal contained in the plating layer include known metals.
Specifically, metals such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals are exemplified.
Among them, the plating layer preferably contains copper or an alloy thereof from the viewpoint of more excellent conductivity of the conductive pattern. Further, from the viewpoint of further excellent conductivity of the conductive pattern, the plating layer preferably contains copper as a main component.
The thickness of the plating layer is preferably 0.1 μm or more, more preferably 1 μm. The upper limit is preferably 20 μm or less.
< step (2-D) and protective layer Forming step >
In embodiment 2, a protective layer forming step is preferably provided between the plating step and a resist stripping step described later.
The protective layer laminating step is a step of forming a protective layer on the plating layer.
As a material of the protective layer, a material having resistance to a stripping liquid and/or an etching liquid in the resist stripping step and/or the removal step is preferable. Examples of the metal include nickel, chromium, tin, zinc, magnesium, gold, silver, and the like, and alloys and resins thereof. Among them, nickel or chromium is preferable as a material of the protective layer.
Examples of the method for forming the protective layer include electroless plating and electroplating, and electroplating is preferred.
The lower limit of the thickness of the protective layer is not particularly limited, but is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The upper limit is not particularly limited, but is preferably 3.0 μm or less, and more preferably 2.0 μm or less.
< step (2-5) and resist stripping step >
The resist stripping step is a step of removing the remaining resist pattern after the plating step or the protective layer forming step.
The steps (2-5) are performed in the same manner as the steps (1-5) described in embodiment 1.
< procedure (2-6) and removal procedure >
The removal step is a step of removing the metal layer exposed by the resist stripping step and obtaining a conductor pattern on the substrate.
In the removal step, the plating layer formed in the plating step is used as an etching resist, and etching treatment of the metal layer is performed in the non-pattern formation region (in other words, the region not protected by the plating layer).
The method for removing a part of the metal layer is not particularly limited, and a known etching solution is preferably used.
Examples of a known etching solution include ferric chloride solution, cupric chloride solution, alkaline ammonia solution, sulfuric acid-hydrogen peroxide mixed solution, phosphoric acid-hydrogen peroxide mixed solution, and the like.
When the removal step is performed, the metal layer exposed on the surface of the substrate is removed, and a plating layer (conductor pattern) having a pattern shape is left, thereby obtaining a laminate having a conductor pattern.
The upper limit value of the line width of the formed conductor pattern is preferably 8 μm or less, more preferably 6 μm or less. The lower limit is not particularly limited, and is usually 2 μm or more.
[ other procedures ]
The method of the present invention (embodiment 1 and/or embodiment 2) may include steps other than the steps described above.
Examples of the other steps include a step of reducing the reflectance of visible light as 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 as described in paragraph [0172] of International publication No. 2019/022089.
< procedure for reducing reflectance of visible ray >
The method of the present invention may include a step of performing a treatment for reducing the reflectance of a part or all of the visible light rays of the conductor pattern included in the laminate.
As the treatment for reducing the reflectance of visible light, for example, an oxidation treatment is given. When the laminate has a conductor pattern containing copper, the visible light reflectance of the laminate can be reduced by oxidizing copper to produce copper oxide and blackening the conductor pattern.
Examples of the treatment for reducing the reflectance of visible light include paragraphs [0017] to [0025] of JP-A-2014-150118 and paragraphs [0041], [0042], [0048] and [0058] of JP-A-2013-206315, which are incorporated herein by reference.
< step of Forming an insulating film, step of Forming a New conductive layer on the surface of an insulating film >
The method of the present invention may include a step of forming an insulating film on the surface of the laminate having the conductor pattern, and a step of forming a new conductive layer (conductor pattern or the like) on the surface of the insulating film.
Through the above steps, the 1 st electrode pattern and the insulated 2 nd electrode pattern can be formed.
As a step of forming the insulating film, for example, a known method of forming a permanent film is given. Further, an insulating film having a desired pattern may 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 photosensitive composition having conductivity can be used, and a new conductive layer having a desired pattern can be formed by photolithography.
The method of the present invention also preferably uses a substrate having a plurality of conductive layers (metal layers, etc.) on both surfaces of the laminate, and uses the conductive layers formed on both surfaces of the substrate to form conductor patterns sequentially or simultaneously.
With the above configuration, it is possible to form 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. Further, it is also preferable to form the circuit wiring for the touch panel having the above-described structure from both surfaces of the substrate in a roll-to-roll manner.
[ use of a method for producing a laminate having a conductor pattern ]
The method for manufacturing a laminate according to the present invention can be applied to manufacturing conductive films such as a touch panel, a transparent heater, a transparent antenna, an electromagnetic wave shielding material, and a light control film; manufacturing a printed wiring board and a semiconductor package; manufacturing a post and a pin for interconnection between semiconductor chips or packages; manufacturing a metal mask; and manufacturing of tape-like substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding) and the like.
The touch panel may be a capacitive touch panel. The method for manufacturing a laminate according to the present invention can be used for forming a conductive film or peripheral circuit wiring in a touch panel. The touch panel can be applied to, for example, a display device such as an organic EL (electro-luminescence) display device or a liquid crystal display device.
As an aspect of the method for producing a laminate having a conductor pattern produced by the method of the present invention, for example, an aspect in which a photomask including light shielding portions arranged in a grid pattern is used in the exposure step in embodiment 2 is given. The above-described manufacturing method is suitable as a manufacturing method of the grid-like metal wiring pattern. The laminate having the conductive pattern obtained by the above-described manufacturing method can be used, for example, as a transparent conductive film. Specifically, the present invention can be used for touch panel electrodes, transparent heaters, transparent antennas, electromagnetic wave shielding materials, light control films, and the like. In this case, the lower the sheet resistance value of the grid pattern region is, the more preferable is 100deg.OMEGA/≡is more preferable, 20Ω/≡is more preferable, and 5Ω/≡is particularly preferable.
As another embodiment of the method for producing a laminate having a conductor pattern produced by the method of the present invention, for example, a method in which a photomask including light shielding portions arranged in a circular dot shape is used in the exposure step in embodiment 2 is mentioned. The above manufacturing method can be preferably used as a manufacturing method of a through hole and a manufacturing method of a post and a pin for interconnection between semiconductor chips or packages. The diameter of the column and the pin is preferably 1 to 20. Mu.m, more preferably 2 to 10. Mu.m, and still more preferably 3 to 8. Mu.m. The length of the column and the pin is preferably 1 to 20. Mu.m, more preferably 3 to 10. Mu.m. As another example, a photomask including openings arranged in a circular dot shape is used in the exposure step in embodiment 2. The above-described manufacturing method is suitable as a manufacturing method of a through hole or the like. The diameter of the through hole is preferably 1 to 20. Mu.m, more preferably 2 to 10. Mu.m, and still more preferably 3 to 8. Mu.m. The depth of the through hole is preferably 1 to 20. Mu.m, more preferably 3 to 10. Mu.m.
As another embodiment of the method for producing a laminate having a conductor pattern produced by the method of the present invention, for example, a method in which a photomask including light shielding portions arranged in a circular dot shape is used in the exposure step in embodiment 1 is mentioned. The above-described manufacturing method is suitable as a manufacturing method of a through hole or the like. The diameter of the through hole is preferably 1 to 20. Mu.m, more preferably 2 to 10. Mu.m, and still more preferably 3 to 8. Mu.m. The depth of the through hole is preferably 1 to 20. Mu.m, more preferably 3 to 10. Mu.m.
The "circle" may be either a perfect circle or a rough circle. The "photomask including the light shielding portions arranged in the circular dots" may be a photomask including 1 circular dot light shielding portion, or may be a photomask including 2 or more circular dot light shielding portions. The "photomask including the openings arranged in the circular dot shape" may be a photomask in which 1 opening is arranged in the circular dot shape, or may be a photomask in which 2 or more openings are arranged in the circular dot shape.
[ transfer film ]
The transfer film used in the method of the present invention has a temporary support and a photosensitive layer.
The length X of the photosensitive layer in the transfer film, which is obtained by the measurement X, is within a predetermined range.
The photosensitive layer used in embodiment 1 of the present invention preferably has a crosslinking reaction amount obtained by the formula Y within a predetermined range.
The transfer film may have a layer other than the photosensitive layer described later.
Examples of the other layer include an intermediate layer described later. The transfer film may have other members (e.g., a protective film) described later.
Examples of the embodiment of the transfer film include the following structures (1) to (2).
Among them, the transfer film preferably has an intermediate layer, and more preferably the following structure (2).
(1) "temporary support/photosensitive layer/protective film"
(2) "temporary support/intermediate layer/photosensitive layer/protective film"
The photosensitive layer in each of the above structures is preferably a negative photosensitive layer described later.
From the viewpoint of suppressing the generation of bubbles in the bonding 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 steps.
The transfer film was cut into a size of 20cm long by 20cm wide in a direction perpendicular to the main surface, and a test sample was produced. In addition, in the case where the transfer film has a protective film, the protective film is peeled from the transfer film. Next, the test sample was allowed to stand on a flat and horizontal stage with the surface of the temporary support facing 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.
In the case where the photosensitive layer of the transfer film further includes another composition layer (for example, the photosensitive layer and/or the intermediate layer) on the side opposite to the temporary support side, the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20% with respect to the thickness of the photosensitive layer.
From the viewpoint of further excellent adhesion, the transmittance of the photosensitive layer for light having a wavelength of 365nm is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.
An example of an embodiment of the transfer film will be described.
The transfer film 10 shown in fig. 2 includes, in order, a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive layer 15, and a protective film 19.
The transfer film 10 shown in fig. 2 has the intermediate layer 13 and the protective film 19, but may not have the intermediate layer 13 and the protective film 19.
In fig. 2, the layers (for example, the photosensitive layer and the intermediate layer) other than the protective film 19 that can be disposed on the temporary support 11 are also referred to as "composition layers".
Hereinafter, each member and each component of the transfer film will be described in detail.
The following description of the constituent elements is made in accordance with the representative embodiment of the present invention, but the present invention is not limited to this embodiment.
[ temporary support ]
The transfer film has a temporary support.
The temporary support is a member for supporting the photosensitive layer, and is finally removed by a temporary support peeling step.
The temporary support may have any one of a single-layer structure and a multi-layer structure.
The temporary support is preferably a film, and more preferably a resin film. The temporary support is preferably a film that is flexible and does not significantly deform, shrink or elongate under pressure or under pressure and heat, and is preferably a film that does not have deformation or scratches such as wrinkles.
Examples of the film include a polyethylene terephthalate film (for example, biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film, and preferably a polyethylene terephthalate film.
From the viewpoint of enabling pattern exposure via 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 pattern formability at the time of pattern exposure via 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 still more preferably 0.1% or less. The lower limit is preferably 0% or more.
From the viewpoints of pattern formability at the time of pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of particles, impurities, and defects in the temporary support be small. The number of particles (e.g., particles having a diameter of 1 μm), impurities 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 less than 1/10 mm 2 . The lower limit is preferably 0/10 mm 2 The above.
The thickness of the temporary support is preferably 5 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 viewpoints 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 using 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 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 layer may be subjected to a surface modification treatment from the viewpoint of improving the adhesion between the temporary support and the photosensitive 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 。
The light output and illuminance are not particularly limited as long as the exposure is within the above range.
Examples of the light source for UV irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and a Light Emitting Diode (LED) which generate light in a wavelength band of 150 to 450 nm.
Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16. 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 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, which are incorporated herein by reference.
Examples of the commercial product of the temporary support include [ umirror 16KS40 and lumiror 16FB40 (manufactured by TORAY INDUSTRIES, INC., supra); cosmosfine a4100, cosmosfine a4300, cosmosfine a8300 (TOYOBO co., ltd. Above).
[ photosensitive layer ]
The transfer film has a photosensitive layer.
The photosensitive layer is preferably a negative photosensitive layer. When the photosensitive layer is a negative photosensitive layer, the pattern formed corresponds to a cured film.
The photosensitive layer preferably contains a resin described later and a polymerizable compound described later or contains a polymerizable compound described later and a polymerizable initiator described later, and more preferably contains a resin described later, a polymerizable compound described later and a polymerizable initiator described later. In addition, the photosensitive layer preferably contains an alkali-soluble resin as well as a resin to be described later. That is, the photosensitive layer preferably contains a resin containing an alkali-soluble resin and a polymerizable compound.
The photosensitive layer preferably contains 10.0 to 90.0 mass% of a resin, 5.0 to 70.0 mass% of a polymerizable compound, and 0.01 to 20.0 mass% of a polymerization initiator, based on the total mass of the photosensitive layer.
Hereinafter, each component that can be contained in the photosensitive layer will be described.
< resin >
The photosensitive layer may contain a resin.
As the resin, an alkali-soluble resin is preferable.
From the viewpoint of suppressing the line width from becoming thicker and the resolution from becoming worse when the focus position is deviated during exposure, the resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group.
Examples of the aromatic hydrocarbon group include a phenyl group which may have a substituent and an aralkyl group which may have a substituent.
The content of the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 10.0 mass% or more, more preferably 20.0 mass% or more, and still more preferably 30.0 mass% or more, based on the total mass of the resin. The upper limit is preferably 80.0 mass% or less, more preferably 60.0 mass% or less, and even more preferably 55.0 mass% or less, based on the total mass of the resin. When the photosensitive layer contains a plurality of resins, the mass average value of the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.
Examples of the aromatic hydrocarbon group-containing monomer include an aralkyl group-containing monomer, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer), and an aralkyl group-containing monomer or styrene is preferable, and styrene is more preferable.
When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 10.0 to 80.0 mass%, more preferably 20.0 to 60.0 mass%, and even more preferably 30.0 to 55.0 mass% based on the total mass of the resin. When the photosensitive layer contains a plurality of resins, the mass average value of the content of the structural unit having an aromatic hydrocarbon group is preferably within the above range.
Examples of the aralkyl group include a phenylalkyl group which may have a substituent (excluding a benzyl group) and a benzyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.
Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.
Examples of the monomer having a benzyl group include benzyl group-containing (meth) acrylates such as benzyl (meth) acrylate and benzyl chloride (meth) acrylate; the vinyl monomer having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol is preferably a (meth) acrylate having a benzyl group, and more preferably benzyl (meth) acrylate.
When the monomer having an aromatic hydrocarbon group is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, and even more preferably 30.0 to 70.0% by mass, based on the total mass of the resin.
The resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group, at least 1 st monomer described later and/or at least 1 nd monomer described later.
The resin not containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least 1 st monomer described later, more preferably obtained by polymerizing at least 1 st monomer and at least 1 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 is preferably 5.0 to 50.0 mass%, more preferably 10.0 to 40.0 mass%, and even more preferably 10.0 to 30.0 mass% relative to the total mass of the resin.
When the content is 5.0 mass% or more, excellent developability, control of edge meltability, and the like can be achieved. When the content is 50.0 mass% or less, high resolution of the resist pattern, control of the skirt shape, and high chemical resistance of the resist pattern can be achieved.
As described later, the structural unit derived from the 1 st monomer in the resin is often reacted with the 3 rd structural unit. In this case, the content of the structural unit derived from the 1 st monomer and not reacting with the 3 rd monomer in the resin is preferably 0 to 50.0% by mass, more preferably 0.0 to 20.0% by mass, and still more preferably 0.0 to 10.0% by mass relative to the total mass of the resin.
The 2 nd monomer is a monomer which is non-acidic and has a polymerizable group in the molecule.
The meaning of the polymerizable group is the same as that of the polymerizable group of the polymerizable compound described later, and the preferable mode is the same.
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, t-butyl (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 (meth) acrylate or ethyl (meth) acrylate is more preferable.
The content of the structural unit derived from the 2 nd monomer is preferably 1.0 to 80.0 mass%, more preferably 1.0 to 60.0 mass%, and even more preferably 1.0 to 50.0 mass% relative to the total mass of the resin.
The resin may have any one of a linear structure, a branched structure, and an alicyclic structure in a side chain.
The branched structure or alicyclic structure is introduced into the side chain of the resin by using a monomer containing a group having a branched structure on the side chain or a monomer containing a group having an alicyclic structure on the side chain. The group having an alicyclic structure may be any of a single ring and a multiple ring.
"side chain" refers to an atomic group branched from a main chain. The "main chain" means a relatively longest bond among molecules of a polymer compound constituting the resin.
Examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate.
Among them, isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.
Examples of the monomer 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) ester, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantanyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) 5-yl (meth) acrylate, octahydro-4, 7-methylindenyl (meth) acrylate, 1-cyclomenthyl (meth) acrylate 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) 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) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is more preferable.
From the viewpoint of more excellent effects of the present invention, the resin preferably has a polymerizable group, more preferably contains a structural unit having a polymerizable group, and further preferably contains a structural unit having an ethylenically unsaturated group in a side chain.
The polymerizable group is preferably an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group, which is included in a polymerizable compound described below.
The polymerizable group is also preferably a polymerizable group capable of undergoing a polymerization reaction with a polymerizable group of a polymerizable compound.
The resin having a polymerizable group also preferably satisfies the appropriate requirements as described above or described later.
The resin containing a structural unit having a polymerizable group is preferably obtained by reacting a resin containing a structural unit derived from the 1 st monomer with the 3 rd monomer.
The 3 rd monomer is a monomer having 2 or more polymerizable groups in the molecule, and preferably a monomer having 2 polymerizable groups in the molecule.
Examples of the polymerizable group include polymerizable groups included in a polymerizable compound described below. Among them, the 3 rd monomer preferably has 2 kinds of polymerizable groups, more preferably has an ethylenically unsaturated group and a cationically polymerizable group, and further preferably has an acryl group or a methacryl group and an epoxy group.
Examples of the 3 rd monomer include glycidyl (meth) acrylate and allyl (meth) acrylate.
The structural unit having a polymerizable group is preferably a structural unit represented by the formula (P).
[ chemical formula 1]
In the formula (P), R P Represents a hydrogen atom or a methyl group. L (L) P Represents a 2-valent linking group. P represents a polymerizable group.
R P Represents a hydrogen atom or a methyl group.
As R P Preferably a hydrogen atom.
L P Represents a 2-valent linking group.
As the above-mentioned 2-valent linking group, examples include-CO-, -O-; -S-, -SO 2 -、-NR N -, a part of hydrocarbyl groups and combinations thereof. R is R N Represents a hydrogen atom or a substituent.
Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.
The alkylene group may be either a straight chain or a branched chain. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 2 to 8, and still more preferably 3 to 5. The alkylene group may have a heteroatom, and the methylene group in the alkylene group may be substituted with a heteroatom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.
The cycloalkylene group may be a single ring or a multiple ring. The number of carbon atoms of the cycloalkylene group is preferably 3 to 20, more preferably 5 to 10, and still more preferably 6 to 8.
The arylene group may be any of a monocyclic ring and a polycyclic ring. The number of carbon atoms of the arylene group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The arylene group is preferably a phenylene group.
The cycloalkylene group and the arylene group may have a heteroatom as a ring member atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.
The above-mentioned hydrocarbon group may have a substituent.
Examples of the substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group, and preferably a hydroxyl group.
As L P Alkylene groups which may have heteroatoms are preferred.
P represents a polymerizable group.
The polymerizable group is as described above.
Examples of the structural unit having a polymerizable group include the following structural units.
[ chemical formula 2]
When the resin contains a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5.0 to 70.0 mass%, more preferably 10.0 to 50.0 mass%, and even more preferably 15.0 to 40.0 mass% relative to the total mass of the resin.
Examples of the method for introducing the polymerizable group into the resin include a method in which an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride are reacted with a group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group of the resin.
As a preferable mode of the method for introducing the polymerizable group into the resin, for example, the following methods are given: after the 1 st monomer is synthesized by polymerization, a 3 rd monomer (preferably, a glycidyl (meth) acrylate) is reacted with a part of the carboxyl group of the structural unit derived from the 1 st monomer of the obtained resin to introduce a polymerizable group (preferably, a (meth) acryloyloxy group) into the resin. The reaction temperature of the polymer reaction is preferably 80 to 110 ℃. The polymer reaction preferably uses a catalyst, and more preferably uses an ammonium salt (tetraethylammonium bromide).
The reaction temperature of the polymerization reaction is preferably 70 to 100 ℃, more preferably 80 to 90 ℃. The polymerization reaction is preferably performed using a polymerization initiator, more preferably an azo-based initiator, and still more preferably V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) or V-65 (manufactured by FUJIFILM Wako Pure Chemical Corporation).
The resin is preferably a resin containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate and a structural unit derived from styrene or a structural unit derived from benzyl methacrylate, or a resin containing a structural unit derived from methacrylic acid and a structural unit derived from styrene, and more preferably a resin further containing a structural unit having a polymerizable group.
Among the above, the content of each structural unit is also preferably set to the above-described preferred embodiment.
The Tg of the resin is preferably 30 to 180 ℃, more preferably 40 to 150 ℃, still more preferably 50 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 200mgKOH/g or less, still more preferably 190mgKOH/g or less, and particularly preferably 170mgKOH/g or less. The lower limit is preferably 10mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 80mgKOH/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)" means the mass (mg) of potassium hydroxide required for neutralization of 1g of the sample. The acid value can be determined, for example, according to JIS K0070: 1992.
The acid value of the resin can 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 resin satisfying the above-mentioned acid value range also preferably satisfies the appropriate requirements as described above or described later.
When the photosensitive layer contains 2 or more resins, the content of the resin satisfying the above-mentioned acid value range is preferably 10 to 100% by mass, more preferably δ0 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total resin.
The I/O value of the resin is preferably 0.90 or less, more preferably less than 0.70.
The I/O value of the resin is preferably 0.10 or more, more preferably 0.30 or more, and still more preferably 0.50 or more.
The I/O value is a parameter indicating the hydrophilic/lipophilic scale of the resin. For the I/O values, reference can be made to "organic conceptual diagrams" (a Tian Shansheng, three co-publications, 1984).
The closer the I/O value of the resin is to 0 (zero), the smaller the polarity of the resin (lipophilicity of the resin), and the larger the I/O value of the resin, the more the polarity of the resin (hydrophilicity of the resin) is.
In the present specification, the I/O value is an I/O value obtained by calculating I (hydrophilicity) and O (lipophilicity) from the chemical structure of the resin, respectively.
The resin satisfying the above-described range of I/O values also preferably satisfies the appropriate requirements as described above or described later.
When the photosensitive layer contains 2 or more resins, the content of the resin satisfying the above-mentioned range of I/O values is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the total resin.
The weight average molecular weight of the resin is preferably 500,000 or less, more preferably 100,000 or less, further preferably 30,000 or less, and particularly preferably 25,000 or less. The weight average molecular weight of the resin is preferably 3,000 or more, more preferably 4,000 or more, further preferably 5,000 or more, and particularly preferably 10,000 or more.
When the weight average molecular weight is 500,000 or less, resolution and developability can be improved. When the weight average molecular weight is 3,000 or more, the properties of the developed aggregate and the properties of the unexposed film such as edge meltability and chipping property of the transfer film can be controlled. The term "edge meltability" refers to the degree to which the photosensitive layer easily overflows from the end surface of the roller when the transfer film is wound into a roll shape. "chipping" refers to the degree to which chips are easily scattered when an unexposed film is cut by a dicing machine. If the chip is attached to the upper surface of the transfer film or the like, the chip is transferred to a mask in a subsequent exposure step or the like, and causes 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 resin satisfying the above range of weight average molecular weight and/or dispersity also preferably satisfies the appropriate requirements as described above or described later.
When the photosensitive layer contains 2 or more resins, the content of the resin satisfying the above range of weight average molecular weight and/or dispersity is preferably 10 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 90 to 100 mass% with respect to the total resin.
The resin may be used alone or in combination of 1 kind or 2 or more kinds.
When 2 or more resins are used, it is preferable to use 2 resins containing structural units derived from a monomer having an aromatic hydrocarbon group in combination or to use resins containing structural units derived from a monomer having an aromatic hydrocarbon group in combination and resins not containing structural units derived from a monomer having an aromatic hydrocarbon group in combination. In the latter case, the content of the resin including the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50.0 mass% or more, more preferably 70.0 mass% or more, still more preferably 80.0 mass% or more, and particularly preferably 90.0 mass% or more, relative to the total mass of the resin. The upper limit is preferably 100.0 mass% or less relative to the total mass of the resin.
The content of the resin is preferably 10.0 to 90.0 mass%, more preferably 20.0 to 80.0 mass%, further preferably 30.0 to 70.0 mass%, and particularly preferably 40.0 to 60.0 mass% relative to the total mass of the photosensitive layer. When the content of the resin is 90.0 mass% or less relative to the total mass of the photosensitive layer, the development time can be controlled. When the resin content is 10.0 mass% or more relative to the total mass of the photosensitive layer, edge melting resistance can be improved.
Examples of the method for synthesizing the resin include a method in which a radical polymerization initiator is appropriately added to a solution obtained by diluting the above-mentioned monomer with a solvent 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.
Examples of the method for synthesizing the resin include bulk polymerization (bulk polymerization), suspension polymerization, and emulsion polymerization, in addition to the above.
The photosensitive layer may contain other resins in addition to the above resins.
Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyethylene formaldehydes, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.
< polymerizable Compound >
The photosensitive layer may contain a polymerizable compound having a polymerizable group.
The "polymerizable compound" is a compound that is polymerized by the action of a polymerization initiator described later and refers to a compound different from the above resin.
Examples of the polymerizable group of the polymerizable compound include groups having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group; 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 (hereinafter, also referred to as "ethylenically unsaturated compound") from the viewpoint of more excellent photosensitivity of the photosensitive layer, and more preferably a compound having 2 or more ethylenically unsaturated groups in the molecule (hereinafter, also referred to as "multifunctional ethylenically unsaturated compound").
In addition, the number of the ethylenically unsaturated groups having an ethylenically unsaturated compound in the molecule is preferably 1 to 6, more preferably 1 to 3, still more preferably 2 to 3, and particularly preferably 3, in terms of more excellent resolution and releasability.
The polymerizable compound may have an alkyleneoxy group.
The alkyleneoxy group is preferably ethyleneoxy or propyleneoxy, and more preferably ethyleneoxy. The number of alkyleneoxy groups added to the polymerizable compound is preferably 2 to 60, more preferably 2 to 30, and still more preferably 2 to 20 per 1 molecule.
The content of the polymerizable compound having an alkyleneoxy group (preferably ethyleneoxy group) is preferably 10 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 90 to 100% by mass relative to the total polymerizable compound in the photosensitive layer.
The polymerizable compound preferably contains a polymerizable compound having 2 or more functions, and more preferably contains a polymerizable compound having 3 or more functions.
In the case where the polymerizable compound exhibits an N function (N is an integer of 1 or more), the value of N refers to the number of polymerizable groups (preferably, ethylenically unsaturated groups) included in the polymerizable compound.
From the viewpoint of more excellent balance of photosensitivity, resolution and releasability of the photosensitive layer, the polymerizable compound preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in the molecule, more preferably contains a 3-functional ethylenically unsaturated compound having 3 ethylenically unsaturated groups in the 1 molecule.
The polymerizable compound preferably contains both a 2-functional polymerizable compound (preferably a 2-functional ethylenically unsaturated compound) and a 3-functional or more polymerizable compound (preferably a 3-functional or more ethylenically unsaturated compound).
The content of the 2-functional polymerizable compound (preferably, the 2-functional ethylenically unsaturated compound) is preferably 20.0 mass% or more, more preferably more than 40.0 mass%, further preferably 55.0 mass% or more, and particularly preferably 90.0 mass% or more, with respect to the total mass of the polymerizable compound, from the viewpoint of excellent releasability. The upper limit is preferably 100.0 mass% or less, more preferably 80.0 mass% or less. That is, all the polymerizable compounds contained in the photosensitive layer may be 2-functional polymerizable compounds.
The content of the polymerizable compound having 3 or more functions (preferably an ethylenically unsaturated compound having 3 or more functions, more preferably an ethylenically unsaturated compound having 3 functions) is preferably 10.0 mass% or more, more preferably 20.0 mass% or more relative to the total mass of the polymerizable compound. The upper limit is preferably 100.0 mass% or less, more preferably 80.0 mass% or less, and still more preferably 50.0 mass% or less. That is, all the polymerizable compounds contained in the photosensitive layer may be 3-functional or more polymerizable compounds.
Further, as the ethylenically unsaturated compound, (meth) acrylate compounds having a (meth) acryloyl group as a polymerizable group are preferable.
(polymerizable Compound B1)
The photosensitive layer preferably also 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 one or more aromatic rings in the molecule among the above polymerizable compounds.
Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an 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; these condensed rings are preferably aromatic hydrocarbon rings, and more preferably benzene rings. The aromatic ring may have a substituent.
The polymerizable compound B1 may have 1 or 2 or more aromatic rings.
From the viewpoint of improving resolution by suppressing swelling of the photosensitive layer by 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 via 1 or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably ethyleneoxy group or propyleneoxy group, and more preferably ethyleneoxy group. The addition amount of the alkyleneoxy group (preferably ethyleneoxy group) added to the bisphenol structure is preferably 2 to 60, more preferably 2 to 30, still more preferably 2 to 20 per 1 molecule.
Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs [0072] to [0080] of JP-A2016-224162, which are incorporated herein by reference.
The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane.
Examples of 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include ethoxylated bisphenol a dimethacrylate (BPE series, shin-Nakamura Chemical co., ltd.) such as 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, hitachi Chemical, co., ltd.,) 2, 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane and 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE series, shin-Nakamura Chemical co., ltd.,) 2, 2-bis (4- (methacryloxydodecaethoxy tetrapropoxy) phenyl) propane (FA-3200 MY, hitachi Chemical co., ltd.,) and ethoxylated (10) bisphenol a diacrylate (NK. A-10, shin-Nakamura Chemical co., ltd.).
The polymerizable compound B1 is also preferably a compound represented by the formula (B1).
[ chemical formula 3]
In the formula (B1), R 1 R is R 2 Each independently represents a hydrogen atom or a methyl group. A represents ethylene. B represents propylene. n1 and n3 each independently represent an integer of 1 to 39. n1+n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29. n2+n4 represents an integer of 0 to 30.
The arrangement of the structural units of- (A-O) -and- (B-O) -may be either random or blocked. In the case of capping, either of- (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.
From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 is preferably 10.0 mass% or more, more preferably 20.0 mass% or more, and even more preferably 25.0 mass% or more, relative to the total mass of the photosensitive layer. The upper limit is preferably 70.0 mass% or less, more preferably 60.0 mass% or less, from the viewpoints of transferability and edge melting (a phenomenon in which the photosensitive composition bleeds out from the end of the transfer member).
From the viewpoint of more excellent resolution, the content of the polymerizable compound B1 is preferably 40.0 mass% or more, more preferably 50.0 mass% or more, still more preferably 55.0 mass% or more, and particularly preferably 60.0 mass% or more, relative to the total mass of the polymerizable compounds. The upper limit is preferably 100.0 mass% or less, more preferably 99.0 mass% or less, and even more preferably 95.0 mass% or less, relative to the total mass of the polymerizable compound, from the viewpoint of releasability.
(other polymerizable Compound)
The photosensitive layer may contain other polymerizable compounds in addition to the above.
Examples of the other polymerizable compound include known polymerizable compounds.
Specifically, examples thereof include a compound having 1 ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.
Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.
Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
Examples of alkylene glycol di (meth) acrylates include tricyclodecane dimethanol diacrylate (A-DCP, shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP, shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, shin-Nakamura Chemical Co., ltd.), 1, 6-hexanediol diacrylate (A-HD-N, shin-Nakamura Chemical Co., ltd.), 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 (NK ESTER 4G and the like, manufactured by Shin-Nakamura Chemical Co., ltd.), dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate (ARONIX M-270 and the like, manufactured by TOAGOSEI CO., LTD.).
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 commercial products of urethane di (meth) acrylate include 8UX-015A (Taisei Fine Chemical co., ltd.), 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, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, and glycerol tri (meth) acrylate, and alkylene oxide modified products thereof.
"(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. Also, "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
Examples of the alkylene oxide-modified products of the ethylenically unsaturated compounds having 3 or more functions include caprolactone-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20 and Shin-Nakamura Chemical Co., ltd., A-9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD RP-1040, shin-Nakamura Chemical Co., ltd., ATM-35E and A-9300, DAICEL-ALLNEX LTD, EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., ltd., A-GLY-9E, etc.), ARONIX (registered trademark) ARTO-2349 (TOOSEI CO., LTD), ARONIX M-520 (AGOSEI CO., LTD), and TOOSEI M454, manufactured by TOOSCo., LTID, and TOCo., LTD. Manufactured by Toba chemical Co., LTD. Co., ltd.).
The polymerizable compound may be a polymerizable compound having an acid group (for example, a carboxyl group or the like). The acid groups may form anhydride groups.
Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., LTD. Manufactured), ARONIX (registered trademark) M-520 (TOAGOSEI CO., LTD. Manufactured), and ARONIX (registered trademark) M-510 (TOAGOSEI CO., LTD. Manufactured).
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 of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.
The polymerizable compound preferably contains a polymerizable compound having a viscosity of 10 to 30000mpa·s, more preferably contains a polymerizable compound having a viscosity of 300 to 5000mpa·s or more, and still more preferably contains a polymerizable compound having a viscosity of 500 to 3000mpa·s or more.
The polymerizable compound satisfying the above viscosity range preferably satisfies the appropriate requirements as described above or described below.
When the photosensitive layer contains 2 or more kinds of polymerizable compounds, the content of the polymerizable compounds having a viscosity satisfying the above range (for example, a range of 300 to 5000mpa·s) is preferably 10 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 90 to 99% by mass, relative to the total polymerizable compounds. The content of the polymerizable compound having a clogP of 500 or more is preferably 10 to 100% by mass, more preferably 20 to 99% by mass, and even more preferably 35 to 65% by mass, based on the total polymerizable compounds.
In the present specification, the viscosity of the polymerizable compound is a viscosity measured at a temperature of 25℃using a Brookfield type viscometer (TOKI SANGYO CO., LTD. TVB-15, etc.).
The content of the polymerizable group in the polymerizable compound is preferably 1.0mmol/g or more, more preferably 2.0mmol/g or more, and further preferably 3.0mmol/g or more from the viewpoint of further excellent effect of the present invention. The upper limit is preferably 10.0mmol/g or less. The solution may be prepared by replacing the polymerizable content with the double bond content.
The "content of the polymerizable group" means an equivalent weight (mol) of the polymerizable group contained in 1g of the polymerizable compound.
The clogP of the polymerizable compound is preferably 1.0 or more, more preferably 3.0 or more, further preferably 5.0 or more, and particularly preferably more than 5.5. The clogP of the polymerizable compound is preferably 10.0 or less, more preferably 7.0 or less.
In the present specification, clogP refers to a value obtained by calculating a normal log P of a partition coefficient P to 1-octanol and water.
The method and software for calculating the clogP can be known, but unless otherwise specified, the clogP program incorporated in ChemBioDraw Ultra 12.0.0 of Cambridge soft corporation is used in the present specification.
The polymerizable compound satisfying the above clogP range also preferably satisfies the appropriate requirements as described above or described below.
When the photosensitive layer contains 2 or more kinds of polymerizable compounds, the content of the polymerizable compounds in which the clogP satisfies the above range (for example, the range of 5.0 or more) is preferably 10 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 90 to 99% by mass, relative to the total polymerizable compounds. The content of the polymerizable compound having a clogP exceeding 5.5 is preferably 10 to 10% by mass, more preferably 20 to 99% by mass, and even more preferably 35 to 65% by mass, based on the total polymerizable compound.
The polymerizable compound may be used alone or in combination of 1 or 2 or more.
Among them, 3 or more polymerizable compounds are also preferable from the viewpoint of further excellent effects of the present invention.
In the case of using 3 kinds of polymerizable compounds, at least 1 of 3 kinds is preferably a polymerizable compound B1, and at least 2 of 3 kinds is more preferably a polymerizable compound B1.
The content of the polymerizable compound is preferably 10.0 to 70.0 mass%, more preferably 15.0 to 70.0 mass%, and even more preferably 20.0 to 70.0 mass% relative to the total mass of the photosensitive layer.
The mass ratio of the content of the polymerizable compound to the content of the resin (content of the polymerizable compound/content of the resin) is preferably 0.10 to 2.00, more preferably 0.50 to 1.50, and even more preferably 0.70 to 1.10 from the viewpoint of further excellent effects of the present invention.
The photosensitive layer preferably contains the polymerizable compounds B1 and 3 or more functional ethylenically unsaturated compounds.
The mass ratio of the content of the polymerizable compound B1 to the content of the ethylenically unsaturated compound of 3 or more (the content of the polymerizable compound B1/the content of the ethylenically unsaturated compound of 3 or more) is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and still more preferably 1.5 to 3.0.
< polymerization initiator >
The photosensitive layer may contain a polymerization initiator.
The polymerization initiator may be, for example, a known polymerization initiator according to the form of polymerization reaction. Specifically, a thermal polymerization initiator and a photopolymerization initiator are exemplified.
The polymerization initiator may be any of a radical polymerization initiator and a cationic polymerization initiator.
The photosensitive layer preferably contains a photopolymerization initiator.
The photopolymerization initiator is a compound that initiates polymerization of the polymerizable compound by exposure to active light such as ultraviolet light, visible light, and X-ray. Examples of the photopolymerization initiator include known photopolymerization initiators.
Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.
Examples of the photo-radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -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.
The photo radical polymerization initiator preferably contains at least 1 selected from the group consisting of 2,4, 5-triarylimidazole dimer and derivatives thereof from the viewpoints of photosensitivity, visibility of exposed portions and non-exposed portions, and resolution. 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 photo radical polymerization initiators described in paragraphs [0031] to [0042] of JP-A2011-095716 and paragraphs [0064] to [0081] of JP-A2015-014783.
Examples of the photo radical polymerization initiator include ethyl Dimethylaminobenzoate (DBE), benzoin methyl ether, anisole (p, p '-dimethoxybenzyl), TAZ-110 (Midori Kagaku Co., ltd.), benzophenone, 4' -bis (diethylamino) benzophenone, TAZ-111 (Midori Kagaku Co., ltd.), 1- [4- (phenylthio) ] -1, 2-octanedione-2- (O-benzoyloxime) (IRGACURE (registered trademark) OXE-01, BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyl oxime) (IRGACURE OXE-02, BASF corporation), IRGACURE OXE-03 (BASF corporation), IRGARE OXE-04 (BASF corporation), 2- (dimethylamino) -2-methylphenyl ] -1- (methylphenyl) -1- (O-benzoyloxime) (IRGACURE) 2- (registered trademark) OXE-01, BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyl oxime) (IRGACURE OXE-02, IRGACURE OXE-04 (BASF corporation), 2- (dimethylamino) -2-methylphenyl ] -1- (2-methylphenyl) methyl-1- (O-acetyl oxime), and (R GACURE-04 (BASF corporation) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (Omnirad 127, manufactured by IGM Resins B.V. Co., ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinyl) butanone-1 (Omnifad 369, manufactured by IGM Resins B.V. Co., ltd.), 2-hydroxy-2-methyl-1-phenylpropane-1-one (Omnifad 1173, manufactured by IGM Resins B.V. Co., ltd.), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins B.V. Co., ltd.), and 2, 2-dimethoxy-1, 2-diphenylethan-1-one (Omnirad 651, manufactured by IGM Resins B.V. Co., ltd.), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V. Co., ltd.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins B.V. Co., ltd.), oxime ester photopolymerization initiator (Lunar 6, manufactured by DKSHJapan Co., ltd.), 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbiimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (B-CIM, manufactured by Hampford Co., ltd.), 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (BCTB, tokyo Chemical Industry Co., ltd.), 1- [4- (phenylsulfanyl) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyloxime) (TR-PBG-305, changzhou Tronly New Flectronic Materials Co., ltd.), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furanylcarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetyl oxime) (TR-PBG-326, changzhou Tronly New Electronic Materials co., ltd.) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) octanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (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 an active light. As the photo cation polymerization initiator, a compound which is sensitive to actinic rays having a wavelength of 300nm or more (preferably 300 to 450 nm) and generates an acid is preferable. The photo-cation polymerization initiator which is not directly sensitive to the actinic rays having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound which is sensitive to the actinic rays having a wavelength of 300nm or more and generates an acid by being used in combination with the 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 still more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit 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, imidosulfonate 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 layer. The upper limit is preferably 20 mass% or less, more preferably 15 mass% or less, and still more preferably 10 mass% or less, relative to the total mass of the photosensitive layer.
< pigment (color former) >
The photosensitive layer may contain a dye (color former) having a maximum absorption wavelength of 450nm or more in a 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, from the viewpoints of visibility of an exposed portion and a non-exposed portion, and pattern visibility and resolution after development. Hereinafter, the coloring matter (color former) is also referred to as "coloring matter N".
In the case of containing the dye N, although the detailed mechanism is not clear, the adhesion to an adjacent layer (for example, an intermediate layer) is improved, and the resolution is further excellent.
The "change in the maximum absorption wavelength of the dye by an acid, an alkali or a radical" may refer to any one of a method in which the dye in a color development state is decolorized by an acid, an alkali or a radical, a method in which the dye in a decolorized state is developed by an acid, an alkali or a radical, and a method in which the dye in a color development state is changed to a color development state of other hues.
Specifically, the dye N may be any one of a compound that changes color from a decolored state by exposure and a compound that changes color from a decolored state by exposure. In the above case, the dye may be a dye that changes state by generating an acid, an alkali or a radical in the photosensitive layer by exposure to light, and thus may be a dye that changes state by generating a color or decoloring by changing the acid, the alkali or the radical in the photosensitive layer (for example, pH). The coloring matter may be a coloring matter which is not exposed to light and is directly subjected to a state change of color development or decoloration by an acid, an alkali or a radical as a stimulus.
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, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength of the dye N is changed by a radical 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 mechanism of the dye N include a system in which a radical, an acid or a base generated from a radical, an acid or a base which is generated from a radical polymerization initiator, a photo cation polymerization initiator (photoacid generator) or a photobase generator after exposure to light is added to a photosensitive layer by a radical polymerization initiator, a photo cation polymerization initiator or a photobase 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 even more preferably 550 to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion.
The dye N may have a maximum absorption wavelength in a wavelength range of 400 to 780nm at the time of color development of 1 or 2 or more. When the dye N has a maximum absorption wavelength in the wavelength range of 400 to 780nm in the case of color development of 2 or more, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.
For the maximum absorption wavelength of pigment N, in the atmospheric environment, a spectrophotometer was used: the UV3100 (manufactured by Shimadzu Corporation) can be measured by measuring the transmission spectrum of a solution containing a dye N (liquid temperature: 25 ℃ C.) in the range of 400 to 780nm, and detecting a wavelength (maximum absorption wavelength) at which the intensity of light is extremely small.
Examples of the coloring matter which is colored or decolored by exposure to light include colorless compounds.
Examples of the dye to be decolorized by exposure include a colorless compound, a diarylmethane dye, a dioxazine dye, a xanthene (xanthene) dye, an iminonaphthoquinone dye, an azomethine dye, and an anthraquinone dye.
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 golden amine skeleton (colorless golden 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 the exposed portion and the non-exposed portion. Thus, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with the radical generated from the photo radical polymerization initiator or the acid generated from the photo cation polymerization initiator to change the colorless compound to a closed state to decolorize the colorless compound, or to change the colorless compound to an open state to color the colorless compound. The colorless compound is preferably a compound having a lactone ring, a sultone ring or a sultone ring, which is colored by free radical or acid ring opening, and more preferably a compound having a lactone ring, which is colored by free radical or acid ring opening.
Examples of the dye N include dyes and colorless compounds.
Examples of the dye include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metamine yellow, thymol sulfophthalein, xylenol blue, methyl orange, para-methyl red, congo red, benzene red violet 4B, α -naphthyl red, nile blue 2B, nile blue a, methyl violet, malachite green, accessory magenta, victoria pure blue-naphthalene sulfonate, victoria pure blue BOH (Hodogaya Chemical co., ltd. System), oil blue #603 (ORIENT CHEMICAL INDUSTRIES co., ltd. System), oil pink #312 (ORIENT CHEMICAL INDUSTRIES co., ltd. System), oil red 5B (ORIENT CHEMICAL INDUSTRIES co., ltd. Manufactured), oil scarlet #308 (ORIENT CHEMICAL INDUSTRIES co., ltd. Manufactured), oil red OG (ORIENT CHEMICAL INDUSTRIES co., ltd. Manufactured), oil red RR (ORIENT CHEMICAL INDUSTRIES co., ltd. Manufactured), oil green #502 (ORIENT CHEMICAL INDUSTRIES co., ltd. Manufactured), shi Bilong red BEH special (Hodogaya Chemical co., ltd. Manufactured), meta-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, golden yellow amine, 4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxystearyl amino-4-p-N, N-bis (hydroxyethyl) amino-phenyl iminonaphthoquinone, m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, golden yellow amine, 4-p-diethylaminophenyl iminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-beta-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.
Examples of the colorless compound include p, p', p "-hexamethyltriphenylamine methane (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-anilino-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-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylaminofluoran, 3- (N, N-diethylamino) -6-methyl-7-chloro-fluoran, 3- (N, N-diethylamino) -6-dimethoxy fluoran, 3- (N-dimethylamino) -fluoran, 3- (N-diethylamino) -6-dimethylamino fluoran, 4-dimethylamino fluoran, 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-dimethylaminofluoran, 3-piperidinyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-aza-phthalide, 3- (4-ethyl-2-methylindol-3-yl) phthalide, 3- (3-ethyl-2-methylindol-3-yl) phthalide and 3-ethyl-3' -4-methylindol-3-yl-phenylphthalide, 6 '-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.
The dye N is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye which develops a color by a radical, from the viewpoints of excellent visibility of an exposed portion and a non-exposed portion, and pattern visibility and resolution after development.
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 layer, from the viewpoint of excellent visibility of the exposed portion and the non-exposed portion, and pattern visibility and resolution after development.
The content of the dye N is the content of the dye when all the dye N included in the total mass of the photosensitive 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 of dissolved pigment N (0.001 g) was prepared 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 365nm light was irradiated, thereby generating radicals to bring all the pigments N into a color-developed 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 colored was measured by the same method as described above, except that the photosensitive layer (3 g) was dissolved in methyl ethyl ketone instead of the pigment N. Based on the absorbance of the obtained solution containing the photosensitive layer, the content of the pigment N contained in the photosensitive layer was calculated from the calibration curve. The meaning of "photosensitive layer (3 g)" is the same as the meaning of 3g of the total solid content in the photosensitive composition.
< thermally crosslinkable Compound >
The photosensitive layer may contain a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.
The heat-crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound but is treated as a heat-crosslinkable compound.
Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound, and blocked isocyanate compounds are 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, when the resin and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the film formed is reduced, and the function of the film obtained by curing the photosensitive layer as a protective film tends to be enhanced.
"blocked isocyanate compound" refers to a compound having a structure in which the isocyanate groups of an isocyanate are protected with a blocking agent.
The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160 ℃, more preferably 130 to 150 ℃.
As a method for measuring the dissociation temperature of the blocked isocyanate compound, for example, a method in which the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound is measured as the dissociation degree by DSC (Differential scanning calorimetry ) analysis using a differential scanning calorimeter (for example, DSC6200, seiko Instruments inc. Product).
Examples of the blocking agent having a dissociation temperature of 100 to 160℃include active methylene compounds such as malonic acid diester and oxime compounds.
Examples of the malonic acid diester include dimethyl malonate, diethyl malonate, di-n-butyl malonate and di-2-ethylhexyl malonate.
Examples of the oxime compound include compounds having a structure represented by-C (=n-OH) -in a molecule, such as aldoxime, ketoxime, methyl ethyl ketoxime, and cyclohexanone oxime.
Among them, the blocking agent having a dissociation temperature of 100 to 160℃is preferably an oxime compound from the viewpoint of storage stability.
The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of improving the brittleness of the film and improving the adhesion of the transferred body.
The blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by isocyanating hexamethylene diisocyanate to protect it.
Among them, from the viewpoint of easier adjustment of the dissociation temperature to a preferable range and reduction of development residues than a compound having no oxime structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferable as the blocked isocyanate compound having an isocyanurate structure.
The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is, for example, the same as the polymerizable group of the polymerizable compound, and preferably the same applies.
Examples of the blocked isocyanate compound include Karenz series (registered trademark) such as AOI-BM, MOI-BM and MOI-BP (manufactured by SHOWA DENKO K.K.); TPA-B80E and WT32-B75P, etc. (registered trademark) (Asahi Kasei Chemicals Co., ltd.).
The blocked isocyanate compound is preferably the following compound.
[ chemical formula 4]
The thermally crosslinkable compound may be used alone or in combination of 1 or 2 or more.
The content of the thermally crosslinkable compound is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, based on the total mass of the photosensitive layer.
< other additives >
The photosensitive layer may contain other additives as required in addition to the above components.
Examples of the other additives include free radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazole, etc.), pyridines (e.g., isonicotinamide, etc.), and purine bases (e.g., adenine, etc.).
Examples of the other additives include metal oxide particles, chain transfer agents, antioxidants, dispersants, acid breeder agents, development accelerators, conductive fibers, ultraviolet absorbers, thickeners, crosslinking agents, organic or inorganic anti-settling agents, and JP-A-2014-085643 [0165] to [0184], which 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 (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 diphenylnitrosoamine, and nitrosophenyl hydroxylamine aluminum salt is preferable from the viewpoint of not impairing the sensitivity of the photosensitive layer.
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 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)
Carboxybenzotriazoles function as, for example, rust inhibitors.
Examples of the carboxybenzotriazoles include carboxybenzotriazoles (4-carboxy-1, 2, 3-benzotriazole and 5-carboxy-1, 2, 3-benzotriazole), N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazoles, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazoles and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazoles.
Specific examples of carboxybenzotriazoles include CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD).
The total content of the radical polymerization inhibitor, benzotriazole and carboxybenzotriazole is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, relative to the total mass of the photosensitive layer. When the content is 0.01 mass% or more, the storage stability of the photosensitive layer is more excellent. On the other hand, when the content is 3 mass% or less, the maintenance of sensitivity and the inhibition of dye discoloration 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 (xanthone) compound, a thioxanthone (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.
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 photosensitive 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 [0060] to [0071] of JP-A-2009-237362 in paragraph [0017] of JP-A-4502784.
The surfactant is preferably a nonionic surfactant, a fluorine-based surfactant or a silicone-based surfactant.
Examples of the fluorine-based surfactant include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-579, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41-LM, R-01, R-40-LM, RS-43, RS-94 and R-94 (DIC-21, DIC, and DIC); fluorad FC430, FC431 and FC171 (supra Sumitomo 3M Limited); SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (the above are manufactured by AGC Co.); polyFox PF636, PF656, PF6320, PF6520, and PF7002 (above OMNOVA SOLUTIONS INC.); futurent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (the above is manufactured by NEOS corporation); U-120E (Uni-chem Co., ltd.).
The fluorine-based surfactant is preferably an acrylic compound having a molecular structure containing a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cleaved to volatilize the fluorine atom.
Examples of such a fluorine-based surfactant include MEGAFACE DS series (chemical industry daily report (2016, 2, 22 days) and daily industrial news (2016, 2, 23 days)) manufactured by DIC CORPORATION.
Further, as the fluorine-based surfactant, a copolymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group is also preferably used.
As the fluorine-based surfactant, a blocked polymer can also be used.
The fluorine-containing surfactant is also preferably a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
The fluorinated surfactant may be, for example, a fluoropolymer having an ethylenically unsaturated group in a side chain, and examples thereof include MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (the above is manufactured by DIC CORPORATION).
From the viewpoint of improving the environmental suitability, 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).
Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, ethoxylates and propoxylates thereof (for example, 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, and sorbitan fatty acid esters; as specific examples, PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (the above are manufactured by BASF corporation); TETRONIC 304, 701, 704, 901, 904, and 150R1, hydrostart WE 3323 (above is manufactured by BASF corporation); SOLSPERSE 20000 (available from Lubrizol Japan Limited, supra); NCW-101, NCW-1001, and NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation, supra); PIONIN D-1105, D-6112-W and D-6315 (Takemoto Oil & Fat Co., ltd.); olfine 1010, SURFYNOL104, 400, and 440 (above Nissin Chemical co., ltd.).
Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers in which an organic group is introduced into a side chain and/or a terminal.
Specific examples of the silicone-based surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (the above is manufactured by DIC CORPORATION); DOWSIL 8032ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC11PA, toray Silicone SH PA, toray Silicone SH28PA, toray Silicone SH29PA, toray Silicone SH30PA, and Toray Silicone SH8400 (made by Dow Corning Toray Silicone Co., ltd.); 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, 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 (above is a Silicone system of Shin-Etsu); f-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive Performance Materials Inc. above); BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (the above are manufactured by BYK Chemie corporation).
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 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 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 these ions and halide ions.
Among them, sodium ions, potassium ions and halide ions are preferably contained in the following amounts from the viewpoint of easy mixing.
The metal impurities are compounds different from the above-mentioned particles (for example, metal oxide particles) that can be contained in the transfer film.
The content of the metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less relative to the total mass of the photosensitive layer. The lower limit 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 layer.
Examples of the method for adjusting the content of the impurity include a method for selecting a material of the photosensitive layer to have a small content of the impurity, a method for preventing the impurity from being mixed when forming the photosensitive layer, and a method for removing the material by cleaning.
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 layer. The lower limit is preferably 10 ppb by mass or more, more preferably 100 ppb by mass or more, relative to the total mass of the photosensitive layer.
As a method for adjusting the content of the residual organic solvent, a method of adjusting the drying treatment conditions in a method for producing a transfer film described later is given. The content of the residual organic solvent can be determined by a known method such as gas chromatography analysis.
(residual monomer)
The photosensitive layer may contain a monomer having each structural unit of the resin.
From the viewpoints of pattern formability 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 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 monomer content of each structural unit of the residual alkali-soluble resin is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, relative to the total mass of the photosensitive layer. The lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, relative to the total mass of the photosensitive layer.
The residual amount of the monomer in synthesizing the alkali-soluble resin by the polymer reaction is also preferably set within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, it is preferable to set the content of glycidyl acrylate within the above range.
As a method for adjusting the content of the residual monomer, for example, a method of adjusting the content of the above-mentioned impurities is mentioned.
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 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.
From the viewpoint of adjusting the length X obtained by measuring X to be within an appropriate range, the photosensitive layer preferably satisfies at least 1 or more (for example, 1 to 4) of the following requirements 1 to 4.
Element 1: the photosensitive layer contains a resin having a weight average molecular weight of 30,000 or less and a polymerizable group.
Element 2: the photosensitive layer contains a resin having a weight average molecular weight of 30,000 or less and a polymerizable compound having a clogP of 5.0 or more (preferably more than 5.5).
Element 3: the photosensitive layer contains a resin having a weight average molecular weight of 30,000 or less and a polymerizable compound having a viscosity of 300 to 5000 mPas.
Element 4: the photosensitive layer contains a resin having a weight average molecular weight of 30,000 or less and a polymerizable compound having 3 functions or more.
In element 1, it is considered that the resin having a weight average molecular weight of 30,000 or less increases the reaction rate in the photosensitive layer, and that the resin has a crosslinkable group, so that a dense crosslinked structure can be formed, and penetration of the developer into the photosensitive layer after exposure can be suppressed.
In element 2, it is considered that the reaction rate in the photosensitive layer is improved by containing a resin having a weight average molecular weight of 30,000 or less, and that the photosensitive layer becomes hydrophobic by containing a polymerizable compound having a clogP of a predetermined value or more, whereby penetration of a developer into the photosensitive layer after exposure can be suppressed.
In element 3, it is considered that the reaction rate in the photosensitive layer is improved by containing a resin having a weight average molecular weight of 30,000 or less, and that the photosensitive layer is less likely to absorb moisture by containing a polymerizable compound having a viscosity of a predetermined value or more, whereby penetration of a developer into the photosensitive layer after exposure can be suppressed.
In element 4, it is considered that the reaction rate in the photosensitive layer is improved by containing a resin having a weight average molecular weight of 30,000 or less, and that a dense crosslinked structure can be formed by containing a polymerizable compound having 3 functions or more, whereby penetration of the developer into the photosensitive layer after exposure can be suppressed.
[ Property of photosensitive layer ]
The thickness (film thickness) of the photosensitive layer is usually 0.1 μm or more, preferably 0.2 μm or more, more preferably 0.5 μm or more, and particularly preferably 1.0 μm or more. The upper limit of the film thickness is 300 μm or less, preferably 100 μm or less, more preferably 50 μm or less, still more preferably 20 μm or less, and particularly preferably 5 μm or less. By setting the film thickness of the photosensitive layer to the above range, the developability of the photosensitive layer can be improved and the resolution can be improved.
The content of the polymerizable group in the photosensitive layer is preferably 1.0mmol/g or more, more preferably 2.0mmol/g or more, and further preferably 3.0mmol/g or more from the viewpoint of further excellent effect of the present invention. The upper limit is preferably 10.0mmol/g or less. The solution may be prepared by replacing the polymerizable content with the double bond content.
The acid value of the photosensitive 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 60 to 80mgKOH/g.
Examples of the method for measuring the acid value include a method for measuring the acid value in the above resin and a method for calculating the acid value from the content of the known resin.
[ intermediate layer ]
The transfer film may have an intermediate layer between the temporary support and the photosensitive layer.
For example, the intermediate layer is preferably disposed between the temporary support and the photosensitive 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-blocking layer from the viewpoints of improving sensitivity at the time of exposure, reducing time load of an exposure machine, and improving productivity. The oxygen blocking layer is more preferably an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22 ℃).
Hereinafter, each component that can be contained in the intermediate layer will be described.
< Water-soluble resin >
The intermediate layer may contain a water-soluble resin.
Examples of the water-soluble resin include polyvinyl alcohol resins, 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, and 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.
The water-soluble resin may be, for example, a copolymer of (meth) acrylic acid and a vinyl compound, preferably a copolymer of (meth) acrylic acid and (meth) acrylic acid allyl, and more preferably a copolymer of methacrylic acid and methacrylic acid allyl ester.
When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the composition ratio ((mol% of (meth) acrylic acid)/(mol% of vinyl compound)) is preferably 90/10 to 20/80, more preferably 80/20 to 30/70.
The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and still more 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 of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
The water-soluble resin may be used alone or in combination of 1 kind or 2 or more kinds.
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 99.99 mass% or less, and still more preferably 99.9 mass% or less, relative to the total mass of the intermediate layer.
< other ingredients >
The intermediate layer may contain other components in addition to the above resin.
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 alcohol include glycerin, diglycerin, and diethylene glycol.
The number of hydroxyl groups in the polyol is preferably 2 to 10.
Examples of the alkylene oxide adducts of the polyols include compounds obtained by adding an ethyleneoxy group, a propyleneoxy group, and the like to the above-mentioned polyols.
The average addition amount of the alkyleneoxy groups is preferably 1 to 100, more preferably 2 to 50, still more preferably 2 to 20.
Examples of the phenol derivative include bisphenol a and bisphenol S.
The amide compound may be, for example, N-methylpyrrolidone.
The intermediate layer preferably contains at least 1 selected from the group consisting of water-soluble cellulose derivatives, polyols, alkylene oxide adducts of polyols, polyether resins, phenol derivatives and amide compounds.
The molecular weight of the other component is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, particularly preferably 2,000 or less, and most preferably 1,500 or less. The lower limit is preferably 60 or more.
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 still 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.
< impurity >
The intermediate layer may contain impurities.
Examples of the impurities include impurities contained in the photosensitive layer.
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 0.3 μm or more, more preferably 1.0 μm or more.
[ other parts ]
The transfer film may have other members in addition to the above members.
Examples of the other member include a protective film.
Examples of the protective film include a resin film having heat resistance and solvent resistance. Specifically, examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films and polystyrene films. As the protective film, a resin film made of the same material as the temporary support can be used.
Among them, the protective film is preferably a polyolefin film, more preferably a polypropylene film or 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 preferably 100 μm or less from the viewpoint of relatively low cost.
The number of fish eyes with a diameter of 80 μm or more contained in the protective film is preferably 5/m 2 The following is given. The lower limit is preferably 0/m 2 The above.
"fish eyes" refers to defects in which impurities, undissolved substances, oxidized degradation products, and the like of a material are incorporated into a film when the material is hot-melted, kneaded, extruded, and a film is produced by a biaxial stretching and casting method 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 of the above range, defects caused by transfer of irregularities due to particles contained in the protective film to the photosensitive layer or the conductive layer can be suppressed.
From the viewpoint of imparting windability, the arithmetic average roughness Ra of the surface of the protective film opposite to the surface in contact with the photosensitive layer or the surface in contact therewith is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. The upper limit is preferably less than 0.50. Mu.m, more preferably 0.40. Mu.m, still more preferably 0.30. Mu.m.
[ method for producing transfer film ]
As a method for producing the transfer film, for example, a known method is given.
As a method for producing the transfer film 10, for example, a method including the steps of: a step of forming a coating film by applying the intermediate layer forming composition to the surface of the temporary support 11, and further drying the coating film to form an intermediate layer 13; and a step of forming a coating film by applying the photosensitive composition to the surface of the intermediate layer 13 and further drying the coating film to form the photosensitive layer 15.
As a method for producing the transfer film, a method including a step of forming a coating film by applying a photosensitive composition to the surface of a temporary support and then drying the coating film to form a photosensitive layer is also mentioned. In this case, the transfer film does not have the intermediate layer 13.
The transfer film 10 is manufactured by pressing the protective film 19 against the photosensitive 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 layer 15, and the protective film 19 by a process including providing the protective film 19 so that the surface of the photosensitive layer 15 opposite to the temporary support 11 is in contact with each other.
Further, as a method for producing the transfer film, it is also preferable to produce the transfer film 10 including the temporary support 11, the intermediate layer 13, the photosensitive layer 15, and the protective film 19 by including a step of providing the protective film 19 so as to bring the surface of the photosensitive layer 15 opposite to the temporary support 11 side into contact.
The transfer film 10 produced by the above-described production method is wound up, whereby a transfer film in the form of a roll can be produced and stored. The transfer film in the form of a roll can be directly supplied to a step of bonding a substrate (a substrate with a metal layer) to be described later in a roll-to-roll manner.
[ photosensitive composition and method for Forming photosensitive layer ]
As a method for forming the photosensitive layer, a coating method in which a photosensitive composition containing components (for example, a resin, a polymerizable compound, a polymerization initiator, and the like) and a solvent contained in the photosensitive layer is used for coating is preferable.
As a method for forming the photosensitive layer, for example, a method of forming a coating film by applying a photosensitive composition onto an intermediate layer and drying the coating film at a predetermined temperature as needed is preferable. The amount of the residual solvent is adjusted by a drying treatment of the coating film.
The photosensitive composition preferably contains a component and a solvent contained in the photosensitive layer. The content of each component contained in the photosensitive layer is as described above.
The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the photosensitive layer other than the solvent.
Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., N-propyl acetate), amide solvents, lactone solvents, and mixed solvents combining these solvents.
The solvent preferably contains at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.
Among these, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least three 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 still more 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 the solvents described in paragraphs [0092] to [0094] of Japanese patent application laid-open No. 2018/179640 and the 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 photosensitive composition.
Examples of the method for applying the photosensitive composition include known methods.
Specifically, printing, spraying, roll coating, bar coating, curtain coating, spin coating, and die coating (slit coating) are mentioned.
The method for drying the coating film of the photosensitive composition is preferably heat drying or reduced pressure drying.
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, as the drying method, a method of continuously changing the drying temperature may be used.
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.
The transfer film may be manufactured by bonding a protective film to the photosensitive layer.
As a method for bonding the protective film to the photosensitive layer, for example, a known method is given. Examples of the means for bonding the protective film to the photosensitive layer include known laminators such as vacuum laminators and automatic cutting laminators.
The laminator is preferably a laminator provided with any heatable roller such as a rubber roller and capable of pressurizing and heating.
[ composition for Forming an intermediate layer and method for Forming an intermediate layer ]
As a method for forming the intermediate layer, a coating method of coating with a composition for forming an intermediate layer containing a component (for example, a water-soluble resin or the like) contained in the intermediate layer and a solvent is preferable.
As a method for forming the intermediate layer, for example, a method of forming a coating film by applying the intermediate layer-forming composition to a temporary support and drying the coating film at a predetermined temperature as necessary is preferable. The amount of the residual solvent is adjusted by a drying treatment of the coating film.
The intermediate layer-forming composition preferably contains a component and a solvent contained in the intermediate layer.
The content of the component contained in the intermediate layer is as described above.
The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the intermediate layer.
The solvent is preferably at least 1 selected from water and water-miscible organic solvents, more preferably water or a mixed solvent of water and water-miscible organic solvents.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, glycerin, and a mixed solvent of these, preferably alcohols having 1 to 3 carbon atoms, 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 intermediate layer-forming composition.
As a method for forming the intermediate layer, for example, a known coating method is given.
Specifically, slit coating, spin coating, curtain coating, and inkjet coating are mentioned.
The method of drying the coating film of the intermediate layer-forming composition is preferably heat drying or reduced pressure drying.
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, as the drying method, a method of continuously changing the drying temperature may be used.
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.
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 in a limiting manner by the examples shown below.
Unless otherwise specified, "parts" and "%" are mass basis.
In the following examples, the weight average molecular weight of the resin was determined by conversion to polystyrene by Gel Permeation Chromatography (GPC). The theoretical acid value was used as the acid value.
[ Material for producing transfer film ]
The materials (photosensitive composition and intermediate layer forming composition) used for producing the transfer film used in the examples will be described.
[ Components of photosensitive composition ]
The photosensitive layer of the transfer film is formed using a photosensitive composition.
The components used for preparing the photosensitive compositions were as follows, and the respective components shown below were mixed by blending in the table shown below, to obtain the respective photosensitive compositions used in examples or comparative examples.
< resin >
Compounds 1 to 4: resins (compounds) having the characteristics shown below, respectively
Compounds 1 to 4 correspond to alkali-soluble resins.
TABLE 1
In the above table, the column "composition" shows the types of the structural units of the resins (compounds) and the mass ratio of the contents of the structural units in parentheses.
The names of the monomers from which the respective structural units originate are shown as the types of the respective structural units.
For example, the compound 1 is a resin having a styrene-based structural unit, a methyl methacrylate-based structural unit, and a methacrylic acid-based structural unit, respectively, in a mass ratio of 52:19:29.
The structural unit labeled "glycidyl methacrylate" refers to a structural unit obtained by reacting glycidyl methacrylate with a carboxyl group of a structural unit based on methacrylic acid.
The structural unit labeled "methacrylic acid" is a structural unit that does not correspond to the structural unit labeled "methacrylic acid-glycidyl methacrylate".
< polymerizable Compound >
SR454: ethoxylated (3) trimethylolpropane triacrylate, TOMOE Engineering co., ltd
BPE-500: ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd
BPE-100 ethoxylated bisphenol A dimethacrylate, shin-Nakamura Chemical Co., ltd
M-270: ARONIX M-270, polypropylene glycol diacrylateTOAGOSEI co., ltd. Manufactured
4G: NK ESTER 4G, polyethylene glycol #200 dimethacrylate, shin-Nakamura Chemical Co., ltd
< photopolymerization initiator >
2- (O-chlorophenyl) -4, 5-diphenylimidazole dimer
< sensitizer >
4,4' -bis (diethylamino) benzophenone
< polymerization inhibitor >
Phenothiazine
< antioxidant >
Phenanthrone
< color former >
Diamond green: tokyo Chemical Industry Co., ltd
Colorless crystal violet: tokyo Chemical Industry Co., ltd
< rust inhibitor >
CBT-1: carboxybenzotriazole, johoku Chemical co., ltd
< surfactant >
F552: MEGAFACE F-552 DIC CORPORATION
< solvent >
MMPGAc: 1-methoxy-2-propyl acetate
MEK: methyl ethyl ketone
[ Components of composition for Forming an intermediate layer ]
The intermediate layer of the transfer film is formed using the intermediate layer-forming composition.
The components for preparing the intermediate layer-forming composition were mixed in the following manner with blending in the table shown below, and the intermediate layer-forming compositions used in examples or comparative examples were obtained.
< resin >
PVA: polyvinyl alcohol, product name "KURARAY POVAL PVA-205", kuraray co., ltd
PVP: polypyrrolidone, product name "polyvinylpyrrolidone K-30", NIPPON SHOKUBIAI CO., LTD. Preparation
HPMC: hydroxypropyl methylcellulose, product name "METOLOSE 60SH-03", shin-Etsu Chemical Co., ltd
< surfactant >
F444: MEGAFACE F444A and B/C (DIC CORPORATION) of 444 and fluorinated surfactant
< solvent >
Water
Methanol
[ test ]
The photosensitive composition and the intermediate layer-forming composition were used, and the following steps were performed.
[ production of transfer film ]
Each transfer film composed of a temporary support, an intermediate layer, and a photosensitive layer was produced. Specifically, the following is mentioned.
First, the intermediate layer-forming composition was applied to a temporary support (polyethylene terephthalate film (manufactured by TORAY INDUSTR IES, INC. System) having a thickness of 16 μm) 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.
The photosensitive composition was applied to the intermediate layer by a bar coater so that the thickness after drying became 3.0 μm, and dried at 80℃by an oven to form a photosensitive layer (negative photosensitive layer).
Polyethylene terephthalate (16 KS40, made by tolay INDUSTRIES, INC.) having a thickness of 16 μm was pressure-bonded to the obtained photosensitive layer as a protective film, and transfer films used in the respective examples and comparative examples were produced.
[ measurement of X ]
A PET substrate with a copper layer was used, which was prepared by sputtering a PET film (polyethylene terephthalate film) having a thickness of 188 μm to a copper layer having a thickness of 500 nm.
The transfer film thus produced was cut into 50cm square, and the protective film was peeled off, and laminated on a PET substrate with a copper layer under a lamination condition of a roll temperature of 90℃and a line pressure of 0.8MPa and a line speed of 3.0m/min so that the photosensitive layer was in contact with the copper layer on the surface of the PET substrate, to obtain a laminate.
In this case, the laminate has a structure of "PET film-copper layer-photosensitive layer-intermediate layer-temporary support".
This is the stage of laminate manufacture.
Then, the temporary support is peeled off from the obtained laminate, and the intermediate layer is exposed on the surface of the laminate. A photomask having a pattern of 10/10 lines (μm)/spaces (μm) was brought into close contact with the intermediate layer exposed on the surface of the laminate. Light was irradiated using a high-pressure mercury lamp exposure machine (MAP-1200L, japan Science Engineering co., ltd., dominant wavelength: 365 nm). The exposure amount is set to an exposure amount at which the resist pattern obtained after development shows the line and space shapes of the photomask.
Thereafter, development was performed using a 28 ℃ 1.0% aqueous sodium carbonate solution as a developer. Specifically, the development was performed by spraying for 30 seconds, air knife (air knife) treatment, removal of the developer, spraying with pure water for 30 seconds, and air knife treatment.
Thus, a laminate of a resist pattern having a line and space shape with an average line width of 10 μm (line width: space width=1:1) was obtained.
This is the 1 st patterning stage.
At this time, the laminate has a structure of "PET film-copper layer-resist pattern".
The obtained laminate was cut perpendicularly to the longitudinal direction of the wire, and the cross section was observed to obtain the penetration length X (unit: μm) of the developer.
Specifically, X was obtained by observation using the method described in the specification.
[ measurement of Y ]
The double bond equivalent (Ammol/g) of the photosensitive layer before exposure was determined by measuring the photosensitive layer of each transfer film using FT-IR (Fourier Transform Infrared Spectroscopy).
Further, the laminate having a structure of "PET film-copper layer-photosensitive layer-intermediate layer-temporary support" was obtained in the same manner as in the laminate production stage in [ measurement X ].
After the temporary support of the laminate was peeled off, a photomask was brought into close contact with the intermediate layer exposed on the surface of the laminate, and light was irradiated (exposure) using a high-pressure mercury lamp exposure machine (MAP-1200L, japan Science Engineering co., ltd., dominant wavelength: 365 nm). At this time, the exposure to light at a wavelength of 365nm was 20mJ/cm 2 Exposure (full-face exposure) was performed in the manner of (a) was performed. The ratio of the carbon-carbon double bonds reacted by exposure was obtained by observing the photosensitive layer after exposure with FT-IR, and the double bond reaction ratio (B%) was calculated when the amount of carbon-carbon double bonds in the photosensitive layer before exposure was taken as 100%.
The crosslinking reaction amount (= (a×b)/(100) (unit: mmol/g) was obtained from the obtained values of a and B.
[ evaluation of conductor Pattern Linearity (LWR) ]
The step 1 of patterning was performed in the same manner as above in [ measurement X ], and a substrate (laminate having a resist pattern) on which a resist pattern was formed was obtained.
Next, the substrate (laminate having a resist pattern) on which the resist pattern was formed was etched with a copper etching solution (Cu-02:KANTO CHEMICAL CO, inc.) at 23 ℃ for 30 seconds, and then the resist pattern was peeled off using PGMEA, whereby a substrate (laminate having a conductor pattern) on which the copper wiring was patterned was obtained.
The line width of randomly selected sites of 100 sites was measured from copper wiring lines formed in a line and space shape pattern. The standard deviation (unit: nm) of the obtained line width was determined, and the value of the standard deviation was defined as LWR (Line Width Roughness ).
The linearity of the conductor pattern was evaluated based on the LWR value obtained by the following discrimination classification.
The smaller the LWR, the smaller the line width variation, and thus preferable.
A: LWR is less than 150nm
B: LWR is 150nm or more and less than 200nm
C: LWR is 200nm or more and less than 300nm
D: LWR is 300nm or more
[ evaluation of conductor Pattern resolution (minimum resolution linewidth) ]
Copper wirings (conductor patterns) having various line widths were formed on the substrate in the same manner as in the above-described step in [ evaluation of conductor pattern Linearity (LWR) ], except that the exposure amount at the time of exposure was varied. The minimum line width (minimum resolution line width) of a copper wiring (conductor pattern) that can be formed without causing pattern collapse or the like was obtained, and the resolution of the conductor pattern was evaluated.
Results (results)
The following table shows the evaluation results of each example or comparative example. The blends of the photosensitive composition and the intermediate layer forming composition used for producing the transfer film used in each example or comparative example are shown.
The compounds 1 to 4 (resins) were blended in the photosensitive composition in a state of containing a solution (resin solution) of the compound as a resin, and the amounts (parts by mass) added as the resin solution are shown in the table. For example, the photosensitive composition used in example 1 contains a resin solution having a solid content (compound 1) of 25.2 parts by mass and a content of 30% by mass relative to the total mass. The solvent in the resin solution was PGMEA (propylene glycol monomethyl ether acetate).
The viscosity of the polymerizable compound was measured at a temperature of 25℃using a Brookfield-type viscometer (TOKI SANGYO CO., LTD. TVB-15, etc.).
TABLE 2
From the results shown in the table, it was confirmed that according to the method of the present invention, a conductor pattern excellent in linearity and resolution was obtained.
From the comparison of examples 1 to 7, it was confirmed that the effect of the present invention is more excellent if the penetration length X of the developer obtained by measuring X is 0.6 μm or less, and the effect of the present invention is more excellent if it is 0.4 μm or less.
From comparison of examples 5 and 7, it was confirmed that the effect of the present invention is more excellent in the case where the photosensitive layer of the transfer film used in the method of the present invention contains a resin having a polymerizable group.
From comparison of examples 1 and 7, comparison of examples 2 and 4, and the like, it was confirmed that the effect of the present invention is more excellent when the photosensitive layer of the transfer film used in the method of the present invention contains a polymerizable compound having 3 or more polymerizable groups.
From comparison of examples 2 and 3, it was confirmed that the effect of the present invention is more excellent in the case where the photosensitive layer of the transfer film used in the method of the present invention contains a resin having an I/O value of less than 0.70.
From comparison of examples 2, 5 and 6, it was confirmed that the effect of the present invention is more excellent when the photosensitive layer of the transfer film used in the method of the present invention contains a polymerizable compound having a clogP of 5.0 or more, and the effect of the present invention is more excellent when the photosensitive layer contains a polymerizable compound having a clogP of more than 5.5.
[ additional test ]
In the examples and comparative examples described in the previous paragraph, a laminate having a conductor pattern was formed by performing an etching step.
Further, using the same transfer film as the user in examples 1 to 7, a plating process was performed instead of an etching process, and a laminate having a conductor pattern was produced. As a result of evaluating the resolution and linearity of the conductor pattern of the laminate produced through the plating step, it was confirmed that the same tendency as in the examples and comparative examples described in the previous paragraph was observed.
Specifically, a laminate having a conductor pattern was produced as follows.
First, a substrate (laminate having a resist pattern) on which a resist pattern was formed was obtained by performing the same process up to the 1 st pattern formation stage in the above [ measurement X ]. (wherein, in the case of evaluating the resolution (minimum resolution line width) of the conductor pattern, the exposure amount at the time of exposure is varied, and the line width of the finally formed conductor pattern is adjusted)
The laminate has a structure of "PET film-copper layer-resist pattern", and a copper layer is used as a seed layer.
The laminate was added to a Copper sulfate plating solution (75 g/L of Copper sulfate, 190g/L of sulfuric acid, 50 mass ppm of chloride ion, manufactured by Meltex Inc., co Grim PCM, 5 mL/L), at 1A/dm 2 Copper plating treatment was performed under the conditions of (3).
After washing and drying the laminate after the copper plating treatment, the resist pattern was peeled off by immersing the laminate in a stripping solution (MITSUBISHI GAS CHEMICAL compound, inc., "R-100", 0.2 vol%) at 50 ℃, and the copper layer (seed layer) included in the laminate was removed by using an aqueous solution containing 0.1 mass% sulfuric acid and 0.1 mass% hydrogen peroxide.
Thus, a substrate (laminate having a conductor pattern) on which copper wiring was patterned was obtained, and the conductor pattern Linearity (LWR) and the conductor pattern resolution (minimum resolution line width) were evaluated in the same manner as described above.
Symbol description
101-a substrate having a metal layer on a surface, 103-a substrate, 105-a metal layer, 107-a linear resist pattern, 109-a region where alkali metal infiltration occurs, 111-a region where alkali metal infiltration does not occur, x-length, 10-a transfer film, 11-a temporary support, 13-an intermediate layer, 15-a photosensitive layer, 17-a composition layer, and 19-a protective film.

Claims (21)

1. A method for manufacturing a laminate having a conductor pattern, comprising:
a bonding step of bonding a transfer film having a temporary support and a photosensitive layer to a substrate having a metal layer on a surface thereof, such that the photosensitive layer side is in contact with the metal layer of the substrate;
an exposure step of performing pattern exposure on the photosensitive layer;
a developing step of developing the exposed photosensitive layer with an aqueous solution containing an alkali metal salt to form a resist pattern;
an etching process step of etching the metal layer located in a region where the resist pattern is not located or a plating process step of plating the metal layer;
a resist stripping step of stripping the resist pattern; a kind of electronic device with high-pressure air-conditioning system
A removing step of removing the exposed metal layer by the resist stripping step, and forming a conductor pattern on the substrate,
A temporary support peeling step of peeling off the temporary support is further provided between the bonding step and the exposure step or between the exposure step and the developing step,
the length X of the photosensitive layer obtained by the following measurement X is 1.0 μm or less,
measurement of X: a cross section of a resist pattern obtained by exposing the photosensitive layer to a line pattern having a line width and a space width of 1:1 and then developing the exposed resist pattern with the aqueous solution used in the developing step was observed, and an alkali metal penetration length of a side surface of the resist pattern was set to be a length X.
2. The method for producing a laminate having a conductor pattern as claimed in claim 1, wherein,
the crosslinking reaction amount of the photosensitive layer obtained by the formula Y of the photosensitive layer is more than 0.20mmol/g,
formula Y:
crosslinking reaction amount= (a×b)/(100)
Wherein the double bond equivalent of the photosensitive layer before exposure is Ammol/g, and the exposure amount of light with a wavelength of 365nm by using a high-pressure mercury lamp exposure machine is 20mJ/cm by FT-IR observation 2 The double bond reaction ratio obtained by exposing the photosensitive layer after the exposure is set to be B%,
the film thickness of the photosensitive layer exposed by the high-pressure mercury lamp exposure machine was set to 3 μm.
3. The method for producing a laminate having a conductor pattern according to claim 1 or 2, wherein,
the photosensitive layer contains a polymerization initiator and a polymerizable compound.
4. The method for producing a laminate having a conductor pattern as claimed in claim 3, wherein,
the polymerizable compound contains a polymerizable compound having 2 or more functions.
5. The method for producing a laminate having a conductor pattern according to claim 3 or 4, wherein,
the polymerizable compound contains a polymerizable compound having 3 or more functions.
6. The method for producing a laminate having a conductor pattern according to any one of claims 3 to 5, wherein,
the polymerizable compound includes a polymerizable compound having an ethyleneoxy group.
7. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 6, wherein,
the photosensitive layer contains a resin having an I/O value of less than 0.70.
8. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 7, wherein,
the photosensitive layer contains a resin having a polymerizable group.
9. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 8, wherein,
The photosensitive layer contains a resin having a weight average molecular weight of 5000 to 30000.
10. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 9, wherein,
the photosensitive layer contains a resin having an acid value of 80mgKOH/g to 200 mgKOH/g.
11. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 10, wherein,
the photosensitive layer has a film thickness of 5 μm or less.
12. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 11, wherein,
the transfer film has an intermediate layer between the temporary support and the photosensitive layer.
13. The method for producing a laminate having a conductor pattern as claimed in claim 12, wherein,
the intermediate layer contains a water-soluble resin.
14. The method for manufacturing a laminate with a conductor pattern according to claim 12 or 13, wherein,
the intermediate layer contains at least 1 selected from the group consisting of water-soluble cellulose derivatives, polyols, alkylene oxide adducts of polyols, polyethers, phenol derivatives, and amide compounds.
15. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 11, wherein,
The temporary support peeling step is provided between the bonding step and the exposing step,
the exposure step is a step of exposing a pattern through a photomask.
16. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 11, wherein,
the temporary support peeling step is provided between the bonding step and the exposing step,
the exposure step is a step of exposing the exposed surface of the photosensitive layer to a photomask to expose the pattern.
17. The method for manufacturing a laminate with a conductor pattern according to any one of claims 12 to 14, wherein,
the temporary support peeling step is provided between the bonding step and the exposing step,
the exposure step is a step of exposing the exposed surface of the intermediate layer to a photomask to expose the pattern.
18. The method for producing a laminate having a conductor pattern according to any one of claims 1 to 11, wherein,
the temporary support peeling step is provided between the exposure step and the development step,
the exposure step is a step of exposing a pattern through a photomask.
19. The method for manufacturing a laminate with a conductor pattern according to any one of claims 15 to 18, wherein,
the photomask includes light shielding portions arranged in a grid.
20. The method for manufacturing a laminate with a conductor pattern according to any one of claims 15 to 18, wherein,
the photomask includes light shielding portions arranged in a circular dot shape.
21. The method for manufacturing a laminate with a conductor pattern according to any one of claims 15 to 18, wherein,
the photomask includes openings arranged in a circular dot shape.
CN202280016396.1A 2021-02-26 2022-02-21 Method for manufacturing laminate with conductor pattern Pending CN116917806A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021-031151 2021-02-26
JP2021069681 2021-04-16
JP2021-069681 2021-04-16
PCT/JP2022/006927 WO2022181539A1 (en) 2021-02-26 2022-02-21 Method for manufacturing laminate having conductor pattern

Publications (1)

Publication Number Publication Date
CN116917806A true CN116917806A (en) 2023-10-20

Family

ID=88361384

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280016396.1A Pending CN116917806A (en) 2021-02-26 2022-02-21 Method for manufacturing laminate with conductor pattern

Country Status (1)

Country Link
CN (1) CN116917806A (en)

Similar Documents

Publication Publication Date Title
CN116802558A (en) Method for producing laminated body, method for producing circuit wiring, method for producing electronic device, and photosensitive transfer material
CN116472494A (en) Method for producing laminate, method for producing circuit wiring board, and transfer film
CN116157741A (en) Transfer film, method for producing laminate, and method for producing circuit wiring
CN116917806A (en) Method for manufacturing laminate with conductor pattern
CN116981997A (en) Method for manufacturing laminate with conductor pattern
WO2022181611A1 (en) Production method for laminate having conductor pattern
WO2022181539A1 (en) Method for manufacturing laminate having conductor pattern
WO2022181485A1 (en) Method for manufacturing laminate and method for manufacturing circuit wiring
WO2023145156A1 (en) Transfer film and method for forming conductor pattern
WO2023119998A1 (en) Method for producing laminate having conductor pattern, photosensitive composition, and transfer film
CN116868125A (en) Method for manufacturing laminate and method for manufacturing circuit wiring
CN115729036A (en) Transfer film and method for manufacturing laminate having conductor pattern
CN116601566A (en) Photosensitive transfer material, method for producing resin pattern, method for producing laminate, method for producing circuit wiring, and method for producing electronic device
CN116670593A (en) Method for producing laminate, method for producing circuit wiring, and transfer film
CN116917122A (en) Transfer film and method for producing conductor pattern
CN116149139A (en) Photosensitive composition, transfer film, pattern forming method, and method for manufacturing circuit wiring
CN116670588A (en) Photosensitive transfer material, method for producing resin pattern, method for producing laminate, method for producing circuit wiring, and method for producing electronic device
CN115685672A (en) Transfer film and method for manufacturing laminate having conductor pattern
CN115729044A (en) Method for manufacturing laminate having conductor pattern, and transfer film
CN115685701A (en) Transfer film, method for manufacturing laminate having conductor pattern, and photosensitive composition
CN115729045A (en) Method for manufacturing laminate having conductor pattern, and transfer film
CN115826352A (en) Photosensitive composition, transfer film, and method for producing laminate having conductor pattern
CN116710845A (en) Transfer material and method for producing laminate
CN116635790A (en) Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, method for producing electronic device, and method for producing laminate
CN118235091A (en) Transfer film, laminate having conductor pattern, method for producing laminate having conductor pattern, and method for producing transfer film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination