JPWO2020174767A1 - Patterned board manufacturing method, circuit board manufacturing method, touch panel manufacturing method, and laminate - Google Patents

Abstract

The temporary support, the photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher, the photosensitive resin composition layer in the photosensitive transfer material, and the polyimide substrate are brought into contact with each other. The present invention provides a method for manufacturing a patterned substrate having a step of bonding the photosensitive transfer material and the polyimide substrate, and an application thereof.

Description

The present disclosure relates to a method for manufacturing a patterned substrate, a method for manufacturing a circuit board, a method for manufacturing a touch panel, and a laminate.

Techniques for forming conductive patterns such as metal wiring are widely used, for example, in the manufacture of touch panels and the manufacture of printed wiring boards.

In a display device having a touch panel such as a capacitance type input device (for example, an organic electroluminescence (EL) display device and a liquid crystal display device), various conductive patterns are provided inside the touch panel. Examples of the conductive pattern include an electrode pattern corresponding to a sensor in the visual recognition portion, peripheral wiring, and take-out wiring. In forming a conductive pattern, for example, a technique for forming a desired pattern through pattern exposure, development, and etching after bonding a photosensitive transfer material to a substrate is available because the number of steps is small. (For example, see JP-A-2017-156735).

As the substrate on which the conductive pattern is formed on the touch panel, a polyethylene terephthalate (PET) film or the like is usually used from the viewpoint of visibility.

On the other hand, in the printed wiring board, a heat-resistant insulating film such as an aromatic polyimide film is used (see, for example, Japanese Patent Application Laid-Open No. 2006-212802).

However, for example, a photosensitive transfer material having a photosensitive resin composition layer containing a polymer having a low glass transition temperature, such as the photosensitive transfer material described in JP-A-2017-156735, is used as a substrate. When a pattern is formed on the substrate, when the substrate is left from the exposure step to the next step (for example, a developing step), the line width of the obtained pattern decreases with the passage of time from the exposure step to the next step. The problem of doing so may occur. This problem is also referred to as PED (Post Exposure Delay).

Further, when the conventional photosensitive transfer material and the substrate are bonded at a high temperature, for example, the adhesion between the photosensitive transfer material and the substrate may be lowered, and the substrate may be deformed (for example, elongation and wrinkles). The above-mentioned problems tend to occur particularly when the photosensitive transfer material and the substrate are bonded by the roll-to-roll method.

Moreover, for example, since the conventional polyimide film described in Japanese Patent Application Laid-Open No. 2006-212802 is colored, it is considered difficult to apply it to a display device provided with a touch panel. Therefore, the polyimide film has not been studied as a substrate for pattern formation used in a touch panel.

This disclosure has been made in view of the above circumstances.
One aspect of the present disclosure is to provide a method for producing a patterned substrate, which can suppress a decrease in the line width of a pattern with the passage of time after exposure and has excellent laminating suitability under high temperature conditions.
Another aspect of the present disclosure is to provide a method for manufacturing a circuit board which can suppress a decrease in the line width of a circuit wiring due to the passage of time after exposure and has excellent laminating suitability under high temperature conditions. ..
Another aspect of the present disclosure is to provide a method for manufacturing a touch panel including the method for manufacturing the circuit board.
Another aspect of the present disclosure is to provide a method for manufacturing a touch panel using a circuit board manufactured by the above method for manufacturing a circuit board.
Another aspect of the present disclosure is to provide a laminate capable of suppressing a decrease in the line width of a pattern with the passage of time after exposure.

Means for solving the above problems include the following aspects.
<1> The above-mentioned photosensitive resin composition layer and a polyimide substrate in a photosensitive transfer material having a temporary support and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. A method for producing a patterned substrate, which comprises a step of adhering the photosensitive transfer material and the polyimide substrate to each other.
<2> The glass transition temperature of the acid-decomposable resin is 50 ° C. to 90 ° C., and in the step of bonding the photosensitive transfer material and the polyimide substrate, the heating temperature is 120 ° C. to 150 ° C. The method for manufacturing a patterned substrate according to <1>, wherein the transport speed is 2.5 m / min to 5.0 m / min.
<3> The method for producing a patterned substrate according to <1> or <2>, wherein the glass transition temperature of the acid-decomposable resin is 55 ° C. to 90 ° C.
<4> The method for producing a patterned substrate according to any one of <1> to <3>, wherein the acid value of the acid-degradable resin is 0 mgKOH / g to 10 mgKOH / g.
<5> The acid-decomposable resin has a (meth) acrylate compound having a linear alkyl group having 1 to 3 carbon atoms at the ester position and a branched alkyl group having 1 to 3 carbon atoms at the ester position (meth). It is selected from the group consisting of an acrylate compound, a (meth) acrylate compound having a cyclic alkyl group having 4 to 20 carbon atoms at an ester position, and a (meth) acrylate compound having a cyclic ether group having 4 to 20 carbon atoms at an ester position. At least one selected from the group consisting of acrylic acid and an acrylate compound containing 90% by mass or more of a structural unit derived from at least one (meth) acrylate compound with respect to the total mass of the acid-degradable resin. The method for producing a patterned substrate according to any one of <1> to <4>, wherein the structural unit derived from the acrylic compound is contained in an amount of 0% by mass to 30% by mass based on the total mass of the acid-degradable resin.
<6> The method for manufacturing a patterned substrate according to any one of <1> to <5>, wherein the haze of the polyimide substrate is 0.5% or less.
<7> The method for manufacturing a patterned substrate according to any one of <1> to <6>, wherein the total light transmittance of the polyimide substrate is 85% or more.
<8> A step of pattern-exposing the photosensitive resin composition layer after the bonding step, and a step of developing the pattern-exposed photosensitive resin composition layer to form a pattern of the photosensitive resin composition layer. The method for manufacturing a patterned substrate according to any one of <1> to <7>.
<9> The method for manufacturing a patterned substrate according to any one of <1> to <8>, wherein the polyimide substrate has a conductive layer.
<10> The step of manufacturing the patterned substrate by the method for manufacturing the patterned substrate according to <9>, and the conductivity exposed in the region where the pattern of the photosensitive resin composition layer is not formed in the patterned substrate. A method for manufacturing a circuit board, which comprises a step of etching a sex layer and a step of removing a pattern of the photosensitive resin composition layer in this order.
<11> The method for manufacturing a circuit board according to <10>, which comprises a step of exposing the entire surface of the photosensitive resin composition layer between the etching step and the removing step.
<12> The method for manufacturing a circuit board according to <10> or <11>, wherein the conductive layer is a copper layer or a silver layer.
<13> A method for manufacturing a touch panel, which comprises the method for manufacturing a circuit board according to any one of <10> to <12>.
<14> A method for manufacturing a touch panel, which comprises a step of preparing a circuit board manufactured by the method for manufacturing a circuit board according to any one of <10> to <12>.
<15> A laminate having a polyimide substrate and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher.

According to one aspect of the present disclosure, it is possible to provide a method for producing a patterned substrate which can suppress a decrease in the line width of a pattern due to the passage of time after exposure and is excellent in laminating suitability under high temperature conditions.
According to another aspect of the present disclosure, it is possible to provide a method for manufacturing a circuit board which can suppress a decrease in the line width of a circuit wiring due to the passage of time after exposure and has excellent laminating suitability under high temperature conditions. ..
According to another aspect of the present disclosure, it is possible to provide a method for manufacturing a touch panel including the method for manufacturing the circuit board.
According to another aspect of the present disclosure, it is possible to provide a method for manufacturing a touch panel using a circuit board manufactured by the above method for manufacturing a circuit board.
According to another aspect of the present disclosure, it is possible to provide a laminate capable of suppressing a decrease in the line width of the pattern with the passage of time after exposure.

FIG. 1 is a schematic view showing an example of the layer structure of the photosensitive transfer material according to the present disclosure. FIG. 2 is a schematic view showing an example of the pattern. FIG. 3 is a schematic view showing an example of the pattern.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the purpose of the present disclosure.

In the present disclosure, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value. In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present disclosure, "(meth) acrylic" means both acrylic and methacrylic, or either one, and "(meth) acrylate" means both acrylate and methacrylate, or either one. do.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. ..
In the present disclosure, the term "process" is included in the term "process" as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes. ..
In the notation of a group (atomic group) in the present disclosure, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, the chemical structural formula may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. The light used for exposure is not particularly limited, but for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other active rays (activity). Energy rays).

<Manufacturing method of patterned substrate>
The method for producing a patterned substrate according to the present disclosure is a photosensitive transfer material having a temporary support and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature (Tg) of 50 ° C. or higher. The above-mentioned photosensitive resin composition layer and the polyimide substrate are brought into contact with each other to bond the photosensitive transfer material and the polyimide substrate (hereinafter, also referred to as “bonding step”).

The method for manufacturing a patterned substrate according to the present disclosure can suppress a decrease in the line width of a pattern due to the passage of time after exposure, and is excellent in laminating suitability under high temperature conditions. Although the reason why the method for manufacturing a patterned substrate according to the present disclosure exerts the above effect is not clear, it is presumed as follows.

It is considered that the decrease in the line width of the pattern with the passage of time after the exposure is caused by the excessive decomposition of the photosensitive resin composition layer. The photosensitive transfer material applied to the method for producing a patterned substrate according to the present disclosure has a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher, and thus after exposure. Since the excessive diffusion of the acid in the photosensitive resin composition layer can be suppressed, the excessive acid decomposition reaction of the photosensitive resin composition layer can be suppressed. A method for producing a patterned substrate according to the present disclosure is a photosensitive transfer material having a temporary support and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. By having the step of bringing the photosensitive resin composition layer and the polyimide substrate into contact with each other and bonding the photosensitive transfer material and the polyimide substrate, the polyimide substrate is not deformed even under high temperature conditions. It is considered that the photosensitive transfer material and the polyimide substrate can be adhered to each other. Therefore, the adhesion between the photosensitive transfer material and the polyimide substrate can be improved. Therefore, it is considered that the method for manufacturing a patterned substrate according to the present disclosure can suppress a decrease in the line width of the pattern due to the passage of time after exposure, and is excellent in laminating suitability under high temperature conditions.

[Lasting process]
The method for producing a patterned substrate according to the present disclosure is the above-mentioned photosensitive transfer material having a temporary support and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. It has a step of bringing the sex resin composition layer and the polyimide substrate into contact with each other to bond the photosensitive transfer material and the polyimide substrate.

The method of bonding the photosensitive transfer material and the polyimide substrate is not limited, and a known method can be applied. The bonding of the photosensitive transfer material and the polyimide substrate is preferably performed by pressurizing and heating using, for example, a roll or the like. Further, in the bonding step, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used. The bonding step is preferably a roll-to-roll method, that is, a method of bonding a roll-shaped photosensitive transfer material and a roll-shaped polyimide substrate.

In the bonding step, the heating temperature is preferably 100 ° C. to 150 ° C., more preferably 110 ° C. to 150 ° C., further preferably 120 ° C. to 150 ° C., and 120 ° C. to 140 ° C. It is particularly preferable to have. When the heating temperature is 100 ° C. or higher, the photosensitive transfer material can be easily attached to the polyimide substrate. When the heating temperature is 150 ° C. or lower, deterioration of the film quality of the polyimide substrate can be suppressed.

When a contact-type heating means (for example, a roll) is used in the bonding step, the heating temperature in the bonding step refers to the surface temperature of the contact-type heating means.
When a non-contact heating means (for example, a heater) is used in the bonding step, the heating temperature in the bonding step is the photosensitive transfer material and the polyimide substrate up to the contact point between the photosensitive transfer material and the polyimide substrate. Refers to the temperature reached on each surface of.

In the bonding step, the transport speed is preferably 2.5 m / min to 5.0 m / min, more preferably 3.0 m / min to 5.0 m / min. The transfer speed refers to each transfer speed of the photosensitive transfer material and the polyimide substrate transferred in the bonding process.

Among the above, when the photosensitive transfer material and the polyimide substrate are bonded together, the heating temperature is 120 ° C. to 150 ° C. and the transport speed is 2.5 m / min to 5.0 m / min. More preferably, the heating temperature is 120 ° C. to 140 ° C. and the transport speed is 2.5 m / min to 5.0 m / min.

The method for producing a patterned substrate according to the present disclosure includes, in addition to the above-mentioned bonding step, a step of pattern-exposing the above-mentioned photosensitive resin composition layer after the above-mentioned bonding step (hereinafter, also referred to as “exposure step”). It is preferable to have a step of developing the photosensitive resin composition layer exposed to the pattern to form a pattern of the photosensitive resin composition layer (hereinafter, also referred to as “development step”).

Hereinafter, the exposure process and the developing process will be described.

[Exposure process]
The method for producing a patterned substrate according to the present disclosure preferably includes a step of pattern-exposing the photosensitive resin composition layer after the bonding step.

As the light source used for exposure, a light source capable of irradiating the photosensitive resin composition layer with light in a wavelength range in which it can be exposed (for example, 365 nm or 405 nm) is preferable. Examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

Exposure ^is preferably ^{5mJ / cm 2 ~200mJ / cm 2} , more preferably ^{10mJ / cm 2 ~100mJ / cm 2} .

Further, the pattern exposure may be an exposure through a mask or a direct exposure using a laser or the like.

In the exposure step, the temporary support may be peeled off from the photosensitive resin composition layer and then the pattern exposure may be performed. Before the temporary support is peeled off, the pattern is exposed through the temporary support, and then the temporary support is exposed. May be peeled off. When exposing through a mask, in order to prevent mask contamination due to contact between the photosensitive resin composition layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, the temporary support should not be peeled off. Pattern exposure is preferred.

In the present disclosure, the detailed arrangement and specific size of the pattern are not limited and may be appropriately set according to the purpose. For example, in a display device such as a touch panel, at least a part of the pattern (particularly the electrode pattern of the touch panel and the part of the take-out wiring) is a thin line of 100 μm or less from the viewpoint of improving the display quality and minimizing the area occupied by the take-out wiring. It is preferable that the wire is 70 μm or less, and more preferably 70 μm or less.

[Development process]
The method for producing a patterned substrate according to the present disclosure preferably includes a step of developing the photosensitive resin composition layer exposed to the pattern to form a pattern of the photosensitive resin composition layer.

When the photosensitive transfer material has an intermediate layer described later, the exposed intermediate layer is removed together with the exposed photosensitive resin composition layer in the developing step. Further, in the developing step, the intermediate layer of the unexposed portion may also be removed by dissolving or dispersing in the developing solution.

The pattern-exposed photosensitive resin composition layer can be developed using a developing solution.
The developing solution is not limited as long as it can remove the exposed photosensitive resin composition layer, and for example, a known developing solution such as the developing solution described in JP-A-5-72724 can be used. The developing solution is preferably a developing solution in which the exposed portion (in the case of the positive type) of the photosensitive resin composition layer has a dissolution type developing behavior. The developer is preferably an alkaline aqueous solution-based developer containing, for example, a compound having pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L. The developer may further contain a water-soluble organic solvent and a surfactant. Examples of the developer preferably used in the present disclosure include the developer described in paragraph 0194 of International Publication No. 2015/093271.
As the developing solution, it is also possible to use a developing solution in which the unexposed portion (in the case of the negative type) of the photosensitive resin composition layer has a dissolution type developing behavior. Examples of such a developing solution include an organic solvent such as butyl acetate.

The developing method may be, for example, paddle development, shower development, shower and spin development, or dip development. Here, the shower development will be described. By spraying the developing solution on the photosensitive resin composition layer after exposure by a shower, the exposed portion can be removed. Further, after the development, it is preferable to spray a cleaning agent or the like with a shower and rub with a brush or the like to remove the development residue. The liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.

The method for producing a patterned substrate according to the present disclosure may include a post-baking step of heat-treating a pattern containing a photosensitive resin composition layer obtained by development.
The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
Post-baking may be performed in an air environment or a nitrogen substitution environment.

When the photosensitive transfer material has a protective film described later, the method for manufacturing a patterned substrate according to the present disclosure is a step of peeling the protective film of the photosensitive transfer material (hereinafter, "protective film peeling"), if necessary. It may also have a "process"). The protective film peeling step will be described in the section “Method for manufacturing a circuit board” described later.

The patterned substrate produced by the method for producing a patterned substrate according to the present disclosure has at least a polyimide substrate and a photosensitive resin composition layer in this order.

Next, the polyimide substrate and the photosensitive transfer material applied to the method for manufacturing a patterned substrate according to the present disclosure will be described.

[substrate]
In the method for manufacturing a patterned substrate according to the present disclosure, a polyimide substrate is applied as the substrate. In the method for producing a patterned substrate according to the present disclosure, excellent laminating suitability can be realized under high temperature conditions by laminating a polyimide substrate and a photosensitive transfer material described later.

The polyimide constituting the polyimide substrate is not limited as long as it is a polymer compound containing an imide bond, and a known polyimide can be used. Moreover, the polyimide substrate may be a commercially available product. The polyimide substrate is, for example, FORMED (registered trademark) TypeX (manufactured by IST Co., Ltd.), FORMED TypeS (manufactured by IST Co., Ltd.), or Kapton (registered trademark) 100H (manufactured by Toray DuPont Co., Ltd.). ) Is available. Among the above-mentioned commercially available products, the polyimide substrate is preferably FORMED TypeX or FORMED TypeS from the viewpoint of optical characteristics.

The haze of the polyimide substrate is preferably 3.0% or less, more preferably 2.0% or less, further preferably 1.0% or less, and preferably 0.5% or less. Especially preferable. When the haze of the polyimide substrate is 3.0% or less, light scattering can be suppressed. Therefore, for example, the display characteristics (for example, brightness) in the display device can be improved. The lower limit of the haze of the polyimide substrate is not limited. The haze of the polyimide substrate may be appropriately set in the range of 0% or more, for example.

The haze of the polyimide substrate is measured using a haze meter (for example, NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

The total light transmittance of the polyimide substrate is preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 95% or more. When the total light transmittance of the polyimide substrate is 85% or more, the light transmittance of the polyimide substrate can be improved. Therefore, for example, the display characteristics (for example, brightness) in the display device can be improved. The upper limit of the total light transmittance of the polyimide substrate is not limited. The total light transmittance of the polyimide substrate may be appropriately set in the range of 100% or less, for example.

The total light transmittance of the polyimide substrate is measured using a spectrophotometer (for example, UV-2100, manufactured by Shimadzu Corporation).

The polyimide substrate may have a conductive layer. When the polyimide substrate has a conductive layer, the polyimide substrate preferably has a conductive layer on at least one surface. When the polyimide substrate has a conductive layer, it is preferable that the polyimide substrate has at least conductivity on the surface on the side to which the photosensitive transfer material is bonded. When the polyimide substrate has a conductive layer, for example, a conductive pattern can be formed.

In the present disclosure, "conductivity" means that the volume resistivity is less than ^{1 × 10 6} Ωcm, and the volume resistivity is preferably less than ^{1 × 10 4 Ωcm.}

Examples of the conductive layer formed on the polyimide base material include any conductive layer used for general circuit wiring or touch panel wiring.

As the conductive layer, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. It is more preferable that it is at least one layer selected from the group consisting of a metal layer and a conductive metal oxide layer, further preferably it is a metal layer, and it is a copper layer or a silver layer. Is particularly preferable.

Examples of the material constituting the metal layer include aluminum, zinc, copper, iron, nickel, chromium, molybdenum, silver, and gold.

Examples of the material constituting the conductive metal oxide layer include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ .

The polyimide substrate may have one conductive layer, or may have two or more conductive layers. When the polyimide substrate has two or more conductive layers, it is preferable that the polyimide substrates have conductive layers made of different materials. Further, when the polyimide substrate has two or more conductive layers, it is preferable that at least one of the two or more conductive layers contains a conductive metal oxide.

As the conductive layer, it is preferable that the electrode pattern corresponds to the sensor of the visual recognition portion used in the capacitive touch panel or the wiring of the peripheral extraction portion.

The thickness of the polyimide substrate is not limited and may be appropriately set according to the application. The average thickness of the polyimide substrate is preferably 10 μm to 200 μm, more preferably 10 μm to 100 μm, and particularly preferably 10 μm to 60 μm from the viewpoint of strength, pattern linearity, and PED suppression. ..

The average thickness of the polyimide substrate is measured by the following method.
Using a scanning electron microscope (SEM), observe the cross section of the polyimide substrate in the thickness direction, and measure the thickness of the polyimide substrate at 10 points. The arithmetic mean value of the obtained measured values is taken as the average thickness of the polyimide substrate.

[Photosensitive transfer material]
In the method for producing a patterned substrate according to the present disclosure, the photosensitive transfer material includes a temporary support and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. In the method for producing a patterned substrate according to the present disclosure, since the excessive diffusion of acid in the photosensitive resin composition layer after exposure can be suppressed by using the above-mentioned photosensitive transfer material, the photosensitive resin composition layer can be suppressed. Excessive acid decomposition reaction can be suppressed. Therefore, it is possible to suppress a decrease in the line width of the pattern due to the passage of time after exposure.

Hereinafter, each configuration of the photosensitive transfer material will be described.

[Temporary support]
The photosensitive transfer material has a temporary support. The temporary support is a support that supports the photosensitive resin composition layer and can be peeled off from the photosensitive resin composition layer.

The temporary support preferably has light transmittance from the viewpoint that the photosensitive resin composition layer can be exposed through the temporary support when the photosensitive resin composition layer is exposed to a pattern. Here, having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is the exposure sensitivity. From the viewpoint of improvement, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method of measuring using a spectrophotometer (for example, MCPD Series manufactured by Otsuka Electronics Co., Ltd.).

Examples of the temporary support include a glass substrate, a resin film, and paper, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film, and polyimide film. Among the above, a biaxially stretched polyethylene terephthalate film is particularly preferable as the temporary support.

The thickness of the temporary support depends on the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, light transmission required in the first exposure process, and the like. It may be set appropriately. The average thickness of the temporary support is preferably 5 μm to 200 μm, and more preferably 10 μm to 150 μm in terms of ease of handling, versatility, and the like. The average thickness of the temporary support is measured by a method according to the method for measuring the average thickness of the polyimide substrate.

Preferred embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643. The description of the above literature is incorporated herein by reference.

[Photosensitive resin composition layer]
The photosensitive transfer material has a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. When the photosensitive transfer material has a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher, it is possible to suppress a decrease in the line width of the pattern due to the passage of time after exposure.

In the photosensitive resin composition layer, the material other than the acid-decomposable resin having a glass transition temperature of 50 ° C. or higher is not limited, and a known material used in the known acid-decomposable photosensitive resin composition layer is used. can.

From the viewpoint of sensitivity and resolution, the photosensitive resin composition layer preferably contains an acid-decomposable resin and a photoacid generator, and is a structural unit having an acid group protected by an acid-decomposable group (hereinafter referred to as a structural unit). , It is more preferable to contain a polymer containing (also referred to as "constituent unit A") (hereinafter, also referred to as "polymer X") and a photoacid generator. That is, the photosensitive resin composition layer is preferably a chemically amplified photosensitive resin composition layer.

When the photosensitive resin composition layer contains a photoacid generator such as an onium salt or an oxime sulfonate compound described later, the acid generated in response to active radiation (active light) is protected in the polymer. It acts as a catalyst for the deprotection of acid groups. Since the acid generated by the action of one photon contributes to many deprotection reactions, the quantum yield exceeds 1, and becomes a large value such as a power of 10, as a result of so-called chemical amplification. High sensitivity can be obtained. On the other hand, when a quinonediazide compound is used as a photoacid generator that is sensitive to active light, a carboxy group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less, and it does not correspond to the chemically amplified type.

(Acid-degradable resin)
The photosensitive resin composition layer contains an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. When the photosensitive resin composition layer contains an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher, it is possible to suppress a decrease in the line width of the pattern due to the passage of time after exposure.

The acid-decomposable resin is not limited as long as it has a glass transition temperature of 50 ° C. or higher and can be decomposed by action with an acid. Here, the term "decomposition" is not limited to a reaction involving breaking of a chemical bond, but includes a reaction involving a conversion of a chemical structure. The polarity of the acid-degradable resin changes due to the action with the acid, so that, for example, the solubility in a developing solution described later is increased.

From the viewpoint of sensitivity and resolution, the acid-degradable resin is preferably a polymer (polymer X) containing a structural unit (constituent unit A) having an acid group protected by an acid-degradable group.

The acid group protected by the acid-degradable group is converted into an acid group through a deprotection reaction by the action of an acidic substance such as an acid in a catalytic amount generated by exposure. The acid group enables the photosensitive resin composition layer to be dissolved in a developing solution.

The polymer X is preferably an addition polymerization type polymer, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof. Even if the polymer X has a structural unit other than the structural unit derived from (meth) acrylic acid or an ester thereof (for example, a structural unit derived from a styrene compound or a structural unit derived from a vinyl compound). good.

Hereinafter, preferred embodiments of the structural unit A will be described.

-Constituent unit A-
The structural unit A is a structural unit having an acid group protected by an acid-degradable group.

In the present disclosure, the "acid group" means a proton dissociative group having a pKa of 12 or less. The pKa of the acid group is preferably 10 or less, more preferably 6 or less, from the viewpoint of improving sensitivity. Further, the pKa of the acid group is preferably −5 or more. The acid group is preferably a carboxy group or a phenolic hydroxyl group.

The acid-degradable group is not limited, and a known acid-degradable group can be used. Examples of the acid-degradable group include a group that is relatively easily decomposed by an acid (for example, an acetal-type protective group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group), and a group that is relatively difficult to decompose by an acid. Examples include a group (for example, a tertiary alkyl group such as a tert-butyl group, a tertiary alkyloxycarbonyl group such as a tert-butyloxycarbonyl group (that is, a carbonate ester type protective group)).

Among the above, the acid-degradable group is preferably a group having a protected structure in the form of an acetal. From the viewpoint of sensitivity, the acid-degradable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, and a group having a tetrahydrofuran ring structure. Is more preferable, and a tetrahydrofuranyl group is particularly preferable. Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in the line width of the conductive wiring when applied to the formation of a conductive pattern.

The structural unit A is at least one selected from the group consisting of the structural unit represented by the following formula A1, the structural unit represented by the formula A2, and the structural unit represented by the formula A3 from the viewpoint of sensitivity and resolution. It is preferable that it is a constituent unit of.

In formula A1, R ¹¹ and R ¹² independently represent a hydrogen atom, an alkyl group, or an aryl group ^{, at least one of R 11} and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group. A group or an aryl group may be represented, and R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ is a single bond. , Or a divalent linking group, R ¹⁵ represents a substituent, and n represents an integer from 0 to 4.
In formula A2, R ²¹ and R ²² independently represent a hydrogen atom, an alkyl group, or an aryl group ^{, at least one of R 21} and R ²² is an alkyl group or an aryl group, and R ²³ is an alkyl group. A group or aryl group may be represented, and R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, and R ²⁴ may independently form a hydroxy group, a halogen atom, an alkyl group, or an alkoxy. It represents a group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cycloalkyl group, and m represents an integer of 0 to 3.
In formula A3, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group, or an aryl group ^{, at least one of R 31} and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group. , Or an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ is a single bond. Or represents a divalent linking group.

Among the above, the structural unit A is more preferably the structural unit represented by the formula A3. The structural unit represented by the formula A3 is a structural unit having a carboxy group protected by an acetal-type acid-degradable group. By including the structural unit represented by the formula A3 in the polymer X, the sensitivity at the time of pattern formation is excellent, and the resolution is more excellent.

In the formula A3, when R ³¹ or R ³² is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. In the formula A3, when R ³¹ or R ³² is an aryl group, the aryl group is preferably a phenyl group. R ³¹ and R ³² are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
In the formula A3, R ³³ represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Further, the alkyl group and the aryl group in ^{R 31 to} R ^{33 may have a substituent.}

In the formula A3, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and it is preferable that ^{R 31} or R ³² and R ^{33 are linked to form a cyclic ether.} The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.

In formula A3, X ⁰ is preferably a single bond or an arylene group, and more preferably a single bond. Arylene group for X ⁰ may have a substituent.

In the formula A3, ^R34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer X can be lowered.

^{The content of the structural unit in which R 34} is a hydrogen atom in the formula A3 is preferably 20% by mass or more with respect to the total amount of the structural unit A contained in the polymer X.
The content (content ratio: mass ratio) of the structural unit in which R ^{34 is a hydrogen atom in the structural unit A is calculated by a conventional method from 13} C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.

Further, as a preferred embodiment of the formulas A1 to A3, paragraphs 0044 to 0058 of International Publication No. 2018/179640 can be referred to.

In formulas A1 to A3, the acid-degradable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, and a tetrahydrofuran ring. It is more preferably a group having a structure, and particularly preferably a tetrahydrofuranyl group.

The polymer X may contain one type of individual structural unit A, or may contain two or more types of structural unit A.

The content of the structural unit A in the polymer X is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, and 20% by mass, based on the total mass of the polymer X. It is particularly preferably from mass% to 40% by mass. Within the above range, the resolution is further improved.
When the polymer X contains two or more kinds of structural units A, the content of the above-mentioned structural unit A shall represent the total content of two or more kinds of structural units A.
The content (content ratio: mass ratio) of the structural unit A in the polymer X can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-NMR measurement.}

-Constituent unit having an acid group-
The polymer X may contain a structural unit having an acid group (hereinafter, also referred to as “constituent unit B”). The structural unit B is an acid group that is not protected by an acid-degradable group, that is, a structural unit that has an acid group that does not have a protecting group. When the polymer X contains the structural unit B, the sensitivity at the time of pattern formation is improved, the polymer X is easily dissolved in an alkaline developer in the developing process after pattern exposure, and the developing time can be shortened.

Examples of the acid group in the structural unit B include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among the above, the acid group is preferably a carboxy group or a phenolic hydroxyl group, and more preferably a carboxy group.

The polymer X may contain one type of constituent unit B alone, or may contain two or more types of structural unit B.

The content of the structural unit B in the polymer X is preferably 0.01% by mass to 20% by mass, and preferably 0.01% by mass to 10% by mass, based on the total mass of the polymer X. It is more preferable, and it is particularly preferable to contain 0.1% by mass to 5% by mass. Within the above range, the resolution becomes better.
When the polymer X contains two or more kinds of structural units B, the content of the above-mentioned structural unit B shall represent the total content of two or more kinds of structural units B.
The content (content ratio: mass ratio) of the structural unit B in the polymer X can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-NMR measurement.}

-Other building blocks-
In addition to the above-mentioned structural unit A and structural unit B, the polymer X uses other structural units (hereinafter, also referred to as “constituent unit C”) to impair the effect of the method for producing a patterned substrate according to the present disclosure. It is preferable to include it in a range that does not exist.

The monomer forming the structural unit C is not limited, and includes, for example, a styrene compound, a (meth) acrylic acid alkyl ester, a (meth) acrylic acid cyclic alkyl ester, a (meth) acrylic acid aryl ester, an unsaturated dicarboxylic acid diester, and the like. Bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated compounds with an aliphatic cyclic skeleton, and others. Unsaturated compounds of.

Various properties of the polymer X can be adjusted by adjusting at least one of the type and content of the structural unit C. In particular, by including the structural unit C, the glass transition temperature, acid value, and hydrophilicity or hydrophobicity of the polymer X can be easily adjusted.

Examples of the constituent unit C include styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, and ethyl (meth) acrylate. , (Meta) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate 2-hydroxyethyl, (meth) acrylate Polymerized 2-hydroxypropyl, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetate acetate mono (meth) acrylate Examples include the building blocks that are formed. Further, as the structural unit C, a structural unit formed by polymerizing the compounds described in paragraphs 0021 to 0024 of JP2004-246623A can be mentioned.

From the viewpoint of resolution, the structural unit C preferably contains a structural unit having a basic group.
Examples of the basic group include a group having a nitrogen atom. Examples of the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic ring group, and an aliphatic amino group is preferable.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a tertiary amino group may be used. A secondary amino group is preferred.

Examples of the monomer forming the structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, and 2,2, acrylic acid. 6,6-Tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2-(2-( Diethylamino) ethyl, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N methacrylate -(3-Diethylamino) propyl, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethyl) Amino) Propyl] acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, and 1-vinyl- 1,2,4-triazole may be mentioned. Among the above, methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl is preferable.

Further, the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton from the viewpoint of improving the electrical properties of the photosensitive transfer material. Examples of the monomer forming each of the above constituent units include styrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth). Examples thereof include meta) acrylate, and cyclohexyl (meth) acrylate is preferable.

Further, the monomer forming the structural unit C is preferably a (meth) acrylic acid alkyl ester from the viewpoint of adhesion. Among the above, a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The polymer X may contain one type of constituent unit C alone, or may contain two or more types of structural unit C.

The content of the structural unit C is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less, based on the total mass of the polymer X. The content of the structural unit C is preferably 10% by mass or more, and more preferably 20% by mass or more. Within the above range, the resolution and adhesion are further improved.
When the polymer X contains two or more kinds of structural units C, the content of the above-mentioned structural unit C shall represent the total content of two or more kinds of structural units C.

Hereinafter, preferred examples of the polymer X in the present disclosure will be given, but the present disclosure is not limited to the following examples. The ratio of the structural units and the weight average molecular weight in the following exemplified compounds are appropriately selected in order to obtain preferable physical properties.

-Method for producing polymer X-
The method for producing the polymer X (synthesis method) is not limited. The polymer X starts polymerization in an organic solvent containing, for example, a monomer for forming the structural unit A, and, if necessary, a monomer for forming the structural unit B and a monomer for forming the structural unit C. It can be synthesized by polymerizing with an agent. Further, the polymer X can also be synthesized by a so-called polymer reaction.

Further, the acid-decomposable resin (preferably polymer X) is a (meth) acrylate compound having a linear alkyl group having 1 to 3 carbon atoms at the ester position from the viewpoint of resolution, and has 1 to 3 carbon atoms. It has a (meth) acrylate compound having a branched alkyl group at the ester position, a (meth) acrylate compound having a cyclic alkyl group having 4 to 20 carbon atoms at the ester position, and a cyclic ether group having 4 to 20 carbon atoms at the ester position. It preferably contains a structural unit derived from at least one (meth) acrylate compound selected from the group consisting of (meth) acrylate compounds.

Here, the term "ester" used in the present disclosure will be described below. The expression "having A at the ester position" means that A is bonded to the bond site (-O-) on the oxygen atom side of the ester bond (-C (= O) -O-), that is, "-". It means that it has a structure represented by "C (= O) -OA". For example, "having a linear alkyl group having 1 to 3 carbon atoms at the ester position" means that the linear alkyl group having 1 to 3 carbon atoms is bonded to the bond site on the oxygen atom side of the ester bond. Means. When a linear alkyl group having 1 to 3 carbon atoms is represented by X, "having a linear alkyl group having 1 to 3 carbon atoms at the ester position" means "-C (= O) -O-". It means that it has a structure represented by "X".

In the structural unit derived from the (meth) acrylate compound, the cyclic alkyl group having 4 to 20 carbon atoms is preferably a cyclic alkyl group having 4 to 10 carbon atoms, and is a cyclic alkyl group having 5 to 8 carbon atoms. Is more preferable, and a cyclohexyl group is particularly preferable.

In the structural unit derived from the (meth) acrylate compound, the cyclic ether group having 4 to 20 carbon atoms is preferably a cyclic ether group having 4 to 10 carbon atoms, and is a cyclic ether group having 5 to 8 carbon atoms. Is more preferable, a tetrahydrofuranyl group or a tetrahydropyranyl group is further preferable, and a tetrahydrofuranyl group is particularly preferable.

The content of the structural unit derived from the (meth) acrylate compound is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total mass of the acid-decomposable resin. The upper limit of the content of the structural unit derived from the (meth) acrylate compound is not limited. The content of the structural unit derived from the (meth) acrylate compound may be appropriately set in the range of, for example, 100% by mass or less with respect to the total mass of the acid-decomposable resin.

From the viewpoint of resolution, the acid-decomposable resin (preferably polymer X) preferably contains a structural unit derived from at least one acrylic compound selected from the group consisting of acrylic acid and an acrylate compound.

The structural unit derived from the acrylate compound is not limited, and examples thereof include the structural units derived from the various acrylate compounds described above.

The content of the structural unit derived from the acrylic compound is preferably 0% by mass to 40% by mass, more preferably 0% by mass to 30% by mass, based on the total mass of the acid-degradable resin. It is particularly preferably 5% by mass to 30% by mass.

Among the above, the acid-degradable resin (preferably polymer X) contains a (meth) acrylate compound having a linear alkyl group having 1 to 3 carbon atoms at the ester position, and a branched alkyl group having 1 to 3 carbon atoms. A (meth) acrylate compound having an ester position, a (meth) acrylate compound having a cyclic alkyl group having 4 to 20 carbon atoms at the ester position, and a (meth) acrylate compound having a cyclic ether group having 4 to 20 carbon atoms at the ester position. A constituent unit derived from at least one (meth) acrylate compound selected from the group consisting of 90% by mass or more based on the total mass of the acid-degradable resin, and consisting of acrylic acid and an acrylate compound. It is preferable that the structural unit derived from at least one selected acrylic compound is contained in an amount of 0% by mass to 30% by mass based on the total mass of the acid-degradable resin. When the acid-decomposable resin contains the above-mentioned structural units in a specific ratio, the resolution can be improved, and the glass transition temperature of the acid-decomposable resin can be adjusted to a desired numerical range.

(Glass-transition temperature)
The glass transition temperature of the acid-decomposable resin (preferably polymer X) is 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher. It is preferably 80 ° C. or higher, and particularly preferably 80 ° C. or higher. When the glass transition temperature of the acid-degradable resin is 50 ° C. or higher, the diffusion of acid in the photosensitive resin composition layer can be suppressed after exposure, so that an excessive acid decomposition reaction of the photosensitive resin composition layer can be suppressed. can. Therefore, it is possible to suppress a decrease in the line width of the pattern due to the passage of time after exposure.

The glass transition temperature of the acid-decomposable resin is preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and even more preferably 90 ° C. or lower. It is particularly preferably 85 ° C. or lower, and most preferably 80 ° C. or lower. When the glass transition temperature of the acid-decomposable resin is 110 ° C. or lower, the laminating suitability can be improved under high temperature conditions.

Among the above, the glass transition temperature of the acid-degradable resin is preferably 50 ° C. to 90 ° C., more preferably 55 ° C. to 90 ° C., further preferably 55 ° C. to 85 ° C., 60 ° C. The temperature is particularly preferably ° C. to 85 ° C., and most preferably 60 ° C. to 80 ° C. When the glass transition temperature of the degradable resin is within the above numerical range, it is possible to suppress a decrease in the line width of the pattern due to the passage of time after exposure, and it is possible to improve the laminating suitability under high temperature conditions.

The glass transition temperature of the acid-decomposable resin is measured by a method according to the method described in JIS K 7121: 1987. As the glass transition temperature in the present disclosure, the extrapolation glass transition start temperature (hereinafter, also referred to as “Tig”) is used.
When measuring the glass transition temperature, the glass transition is completed at a heating rate of 20 ° C / min after holding the measuring device at a temperature about 50 ° C lower than the expected glass transition temperature of the acid-degradable resin until the measuring device stabilizes. It is heated to a temperature about 30 ° C. higher than the above temperature, and a differential thermal analysis (DTA) curve or a differential scanning calorimetry (DSC) curve is drawn. The extra glass transition start temperature (Tig), that is, the glass transition temperature in the present disclosure, is the straight line extending the baseline on the low temperature side of the DTA curve or DSC curve to the high temperature side and the curve of the stepwise change portion of the glass transition. It is calculated as the temperature at the intersection with the tangent line drawn at the point where the gradient is maximized.

In the present disclosure, as a method of adjusting the glass transition temperature of the acid-decomposable resin, for example, a method of adjusting the glass transition temperature using the FOX equation as a guideline can be mentioned. According to the FOX equation, the glass transition temperature of the acid-degradable resin can be adjusted based on the glass transition temperature of the homopolymer of each constituent unit constituting the target acid-degradable resin and the mass ratio of each constituent unit. ..

Hereinafter, the FOX formula will be described by taking a copolymer containing a first structural unit and a second structural unit as an example.

The Tg of the homopolymer of the first structural unit is Tg1, the mass fraction of the first structural unit in the copolymer is W1, and the Tg of the homopolymer of the second structural unit is Tg2. Assuming that the mass fraction of the constituent unit 2 is W2, the Tg0 (K: Kelvin) of the copolymer containing the first constituent unit and the second constituent unit can be estimated according to the following formula. Is.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
Using the FOX formula described above, the type and mass fraction of each structural unit constituting the copolymer can be adjusted to obtain a copolymer having a desired glass transition temperature.

It is also possible to adjust the glass transition temperature of the acid-degradable resin by adjusting the weight average molecular weight of the acid-decomposable resin.

-Acid value-
The acid value of the acid-degradable resin (preferably polymer X) is preferably 0 mgKOH / g to 50 mgKOH / g, more preferably 0 mgKOH / g to 20 mgKOH / g, and 0 mgKOH / g to 10 mgKOH / g. Is particularly preferable. When the acid value of the acid-decomposable resin is within the above numerical range, water does not easily penetrate into the photosensitive resin composition layer, so that an excessive hydrolysis reaction of the unexposed photosensitive resin composition layer can be suppressed. .. Therefore, it is possible to suppress a decrease in the line width of the pattern.

In the present disclosure, the acid value represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the measurement sample. Specifically, it was obtained by dissolving the measurement sample in a mixed solvent of tetrahydrofuran / water = 9/1 (volume ratio) and then using a potentiometric titrator (for example, AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.). The solution is neutralized and titrated with 0.1 mol / L aqueous sodium hydroxide solution at 25 ° C. The acid value is calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
Formula: A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)
f: Titer of 0.1 mol / L sodium hydroxide aqueous solution w: Mass (g) of measurement sample (in terms of solid content)

-Molecular weight-
The molecular weight of the acid-degradable resin (preferably polymer X) is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. Since the weight average molecular weight of the acid-decomposable resin is 60,000 or less, the photosensitive transfer material is attached in a temperature range (for example, 150 ° C. or less) in which deterioration of the film quality of the polyimide substrate can be suppressed when the photosensitive transfer material is attached to the polyimide substrate. Matching can be achieved.
The weight average molecular weight of the acid-degradable resin is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
The ratio (dispersity) of the number average molecular weight of the polymer X to the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.0 to 3.5.

In the present disclosure, the weight average molecular weight of the acid-degradable resin is measured by GPC (gel permeation chromatography). As the measuring device, various commercially available devices can be used, and the contents of the device and the measuring technique are known to those skilled in the art.
In the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220 GPC (manufactured by Tosoh Corporation) is used as the measuring device. The columns include TSKgel (registered trademark) Super HZM-M (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation). One each of Tosoh Corporation) and Super HZ2000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation) connected in series is used. THF (tetrahydrofuran) is used as the eluent.
The measurement conditions are a sample concentration of 0.2% by mass, a flow rate of 0.35 mL / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C. A differential refractive index (RI) detector is used as the detector.
The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A". It can be prepared using any of 7 samples of "-2500" and "A-1000".

(Content)
The photosensitive resin composition layer may contain one kind of acid-decomposable resin alone, or may contain two or more kinds of acid-decomposable resins. The content of the acid-decomposable resin is preferably 50% by mass to 99.9% by mass, preferably 70% by mass to 98% by mass, based on the total mass of the photosensitive resin composition layer from the viewpoint of adhesion. It is preferable to have.

(Other polymers)
The photosensitive resin composition layer contains, in addition to the acid-decomposable resin, a polymer having an acid group protected by an acid-decomposable group and containing no structural unit (hereinafter, also referred to as “another polymer”). May be. In the present disclosure, the acid-degradable resin and other polymers are also collectively referred to as "polymer component". The compounds corresponding to the cross-linking agent, the dispersant and the surfactant described later are not included in the polymer component even if they are polymer compounds.

Examples of other polymers include polyhydroxystyrene. Examples of commercially available polyhydroxystyrenes include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all manufactured by Sartmer), ARUFON UC-3000, and ARUFON UC-3510. , ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all manufactured by Toagosei Co., Ltd.), and Jonclyl 690, Jonclyl 678, Jonclyl 67, and Jonclyl 58 (manufactured by Toagosei Co., Ltd.). ).

The photosensitive resin composition layer may contain one type of other polymer alone, or may contain two or more types of other polymers.

When the photosensitive resin composition layer contains another polymer, the content of the other polymer is preferably 50% by mass or less, preferably 30% by mass or less, based on the total mass of the polymer components. It is more preferable that there is, and it is particularly preferable that it is 20% by mass or less.

When the photosensitive resin composition layer contains another polymer, the content of the polymer component is 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin composition layer from the viewpoint of adhesion. %, More preferably 70% by mass to 98% by mass.

(Photoacid generator)
The photosensitive resin composition layer preferably contains a photoacid generator.

The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiating with active rays such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams.
As the photoacid generator, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm and generates an acid is preferable, but its chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to active light having a wavelength of 300 nm or more can be used as a sensitizer if it is a compound that is sensitive to active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
As the photoacid generator, a photoacid generator that generates an acid having a pKa of 4 or less is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a light that generates an acid having a pKa of 2 or less is preferable. Acid generators are particularly preferred. The lower limit of pKa is not specified. The pKa is preferably -10.0 or more, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salt compounds and triarylsulfonium salt compounds, and quaternary ammonium salt compounds. Among the above, onium salt compounds are preferable, and diaryliodonium salts or triarylsulfonium salt compounds are particularly preferable.
As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

Examples of the nonionic photoacid generator include a trichloromethyl-s-triazine compound, a diazomethane compound, an imide sulfonate compound, and an oxime sulfonate compound. Among the above, the oxime sulfonate compound is preferable from the viewpoint of sensitivity, resolution, and adhesion. Specific examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A.

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be preferably used.

From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably contains an oxime sulfonate compound.
Moreover, as a preferable photoacid generator, for example, a photoacid generator having the following structure can be mentioned.

The photosensitive resin composition layer may contain one kind of photoacid generator alone, or may contain two or more kinds of photoacid generators.

The content of the photoacid generator in the photosensitive resin composition layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin composition layer from the viewpoint of sensitivity and resolution. , 0.5% by mass to 5% by mass, more preferably.

(Other additives)
The photosensitive resin composition layer can contain other additives, if necessary.

As other additives, known additives can be used, and examples thereof include plasticizers, sensitizers, heterocyclic compounds, alkoxysilane compounds, basic compounds, rust preventives, and surfactants.

Examples of the plasticizer, the sensitizer, the heterocyclic compound and the alkoxysilane compound include the plasticizer, the sensitizer, the heterocyclic compound and the alkoxysilane compound described in paragraphs 097 to 0119 of International Publication No. 2018/179640. Can be mentioned.

Further, the photosensitive resin composition layer may contain a solvent. When the photosensitive resin composition layer is formed by the photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin composition layer.

The content of the solvent in the photosensitive resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, and 1% by mass or less, based on the total mass of the photosensitive resin composition layer. Is more preferable.

-Basic compound-
The photosensitive resin composition layer preferably contains a basic compound.

As the basic compound, it can be arbitrarily selected and used from the basic compounds used in the chemically amplified resist. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of the basic compound include the compounds described in paragraphs 0204 to 0207 of JP2011-221494A, the contents of which are incorporated in the present specification.

Further, as the basic compound, N-cyclohexyl-N'-[2- (4-morpholinyl) ethyl] thiourea (CMTU) can be preferably used. Moreover, as a commercial product of CMTU, CMTU manufactured by Toyo Kasei Kogyo Co., Ltd. can be mentioned.

As the basic compound, a benzotriazole compound is preferable from the viewpoint of the linearity of the conductive wiring when applied to the formation of a conductive pattern.
The benzotriazole compound is not limited as long as it is a compound having a benzotriazole skeleton, and known benzotriazole compounds can be used.
Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 5-carboxybenzotriazole, 1- (hydroxymethyl) -1H. -Benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, 9- (1H-benzotriazole-1-ylmethyl) -9H-carbazotriazole, 1-chloro-1H-benzotriazole, 1- (2-) Pyrizinyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1'-hydroxyethyl) benzotriazole, 1- (2'-hydroxyethyl) benzotriazole, 1-propyl Benzotriazole, 1- (1'-hydroxypropyl) benzotriazole, 1- (2'-hydroxypropyl) benzotriazole, 1- (3'-hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzotriazole, 5- Methyl-1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethylbenzotriazole-5-carboxylate, t-butyl-benzotriazole-5-carboxylate, cyclopentylethyl-benzotriazole-5-carboxylate, 1H- Benzotriazole-1-acetorate, 1H-benzotriazole-1-carboxyaldehyde, 2-methyl-2H-benzotriazole, 2-ethyl-2H-benzotriazole and the like can be mentioned.

The photosensitive resin composition layer may contain one kind of basic compound alone, or may contain two or more kinds of basic compounds.

The content of the basic compound is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 3% by mass, based on the total mass of the photosensitive resin composition layer. preferable.

-Surfactant-
The photosensitive resin composition layer preferably contains a surfactant from the viewpoint of thickness uniformity.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants. Preferred surfactants are nonionic surfactants.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ether-based surfactants, polyoxyethylene higher alkylphenyl ether-based surfactants, polyoxyethylene glycol higher fatty acid diester-based surfactants, and silicone-based surfactants. Surfactants and fluorine-based surfactants can be mentioned.

As the surfactant, for example, the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640 can be used.

As a commercially available surfactant, for example, Megafvck (registered trademark) F-552 or F-554 (all manufactured by DIC Corporation) can be used.

In addition, the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362 can also be used.

The photosensitive resin composition layer may contain one type of surfactant alone, or may contain two or more types of surfactants.

The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin composition layer. preferable.

In addition, the photosensitive resin composition layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, and thermal radical polymerization as additives other than the above. It can contain known additives such as initiators, thermoacid generators, UV absorbers, thickeners, crosslinkers, and organic or inorganic anti-precipitation agents.
Preferred embodiments of these components are described in paragraphs 0165 to 0184 of JP2014-85643, respectively, and the contents of this publication are incorporated in the present specification.

(Average thickness of photosensitive resin composition layer)
The average thickness of the photosensitive resin composition layer is preferably 0.5 μm to 20 μm. When the thickness of the photosensitive resin composition layer is 20 μm or less, the resolution of the pattern is more excellent, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
The average thickness of the photosensitive resin composition layer is more preferably 0.8 μm to 15 μm, and particularly preferably 1.0 μm to 10 μm.
The average thickness of the photosensitive resin composition layer is measured by a method according to the method for measuring the average thickness of the polyimide substrate.

(Method of forming photosensitive resin composition layer)
The photosensitive resin composition layer can be formed by using a photosensitive resin composition containing a component used for forming the photosensitive resin composition layer and a solvent. It is also possible to prepare a composition by preparing a solution in which each component is previously dissolved in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above may be filtered using, for example, a filter having a pore size of 0.2 μm to 30 μm.
In the present disclosure, for example, the photosensitive resin composition layer in the present disclosure can be formed by applying the photosensitive resin composition on a temporary support or a protective film and drying it.
The coating method is not limited, and examples thereof include slit coating, spin coating, curtain coating, and inkjet coating.
Further, a photosensitive resin composition layer may be formed on the intermediate layer or another layer described later on the temporary support or the protective film.

As the solvent, a known solvent can be used, and for example, the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 can be used.

Further, the solvent having a vapor pressure of 1 kPa or more and 16 kPa or less at 20 ° C. described in paragraph 0014 of JP-A-2018-177789 can be preferably used.
The solvent that can be used in the present disclosure may be used alone or in combination of two.

The content of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. Is more preferable.

[Middle layer]
The photosensitive transfer material according to the present disclosure preferably has an intermediate layer between the temporary support and the photosensitive resin composition layer.

(Polymer)
The intermediate layer preferably contains a polymer. As the polymer, a water-soluble resin or an alkali-soluble resin is preferable. When the polymer contained in the intermediate layer is a water-soluble resin, the water-soluble resin may be further alkaline-soluble. When the polymer contained in the intermediate layer is an alkali-soluble resin, the alkali-soluble resin may be further water-soluble.

In the present disclosure, "water-soluble" means that the solubility in 100 g of water at pH 7.0 at 22 ° C. is 0.1 g or more, and "alkali-soluble" means 1 mass of sodium carbonate at 22 ° C. It means that the solubility in 100 g of the% aqueous solution is 0.1 g or more.

Further, the solubility of the polymer in 100 g of water having a pH of 7.0 at 22 ° C. is preferably 1 g or more, and more preferably 5 g or more.

Examples of the water-soluble resin include cellulose resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, acrylamide resin, (meth) acrylate resin, polyethylene oxide resin, gelatin, vinyl ether resin, polyamide resin, and copolymers thereof. Among the above, the water-soluble resin is preferably a cellulose resin, and more preferably at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose.

As the alkali-soluble resin, an alkali-soluble acrylic resin is preferable, and an acrylic resin having an acid group that may form a salt is more preferable.

The intermediate layer may contain one kind of polymer alone, or may contain two or more kinds of polymers.

From the viewpoint of adhesion, the content of the polymer is preferably 20% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, based on the total mass of the intermediate layer.

(PH-sensitive dye)
From the viewpoint of easy confirmation of the exposure pattern, the intermediate layer preferably contains a pH-sensitive dye having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development and whose maximum absorption wavelength changes depending on pH.
Here, "the maximum absorption wavelength changes" means that the dye in the color-developing state is decolorized, the dye in the decolorized state is colored, and the dye in the color-developed state is in the color-developed state of another hue. It may refer to any aspect of the changing aspect.

From the viewpoint of visibility, the pH-sensitive dye is more preferably a latent dye that is decolorized by an acid generated from a photoacid generator.

Confirmation that it is a pH-sensitive dye can be performed by the following method.
0.1 g of the dye is dissolved in 100 mL of a mixed solution of ethanol and water (ethanol / water = 1/2 [mass ratio]), and a 0.1 mol / L (1N) hydrochloric acid aqueous solution is added to adjust the pH to 1. Titrate with a 0.01 mol / L (0.01 N) sodium hydroxide aqueous solution, and confirm the color change and the pH at the time when the color change appears. The pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by DKK-TOA CORPORATION).

The method for measuring the maximum absorption wavelength in the present disclosure is to measure the transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25 ° C. in an atmospheric atmosphere. The wavelength at which the intensity of the light is minimized (maximum absorption wavelength) shall be measured.

Examples of dyes that are decolorized by exposure include leuco compounds, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

Among the above, as the dye, a leuco compound is preferable from the viewpoint of visibility.
Examples of the leuco compound include leuco compounds such as triarylmethane type (for example, triphenylmethane type), spiropyran type, fluorane type, diphenylmethane type, rhodamine lactam type, indrillphthalide type and leucooramine type. Among them, a leuco compound having a triarylmethane skeleton (that is, a triarylmethane dye) is preferable, and a triphenylmethane dye is more preferable.
The leuco compound preferably has a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened or closed, and has a sultone ring. However, it is more preferable that the sultone ring is a leuco compound that closes and decolorizes.

The dye is preferably a water-soluble compound for the purpose of preventing defects due to precipitation of the dye.
Further, the dye has a solubility of 1 g or more in 100 g of water having a pH of 7.0 at 22 ° C., more preferably 5 g or more.

The intermediate layer may contain one kind of dye alone or may contain two or more kinds of dyes.

From the viewpoint of visibility, the content of the dye is preferably 0.01% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on the total mass of the intermediate layer. , 1.0% by mass to 3.0% by mass is particularly preferable.

(Surfactant)
The intermediate layer preferably contains a surfactant from the viewpoint of thickness uniformity. As the surfactant, any of a surfactant having a fluorine atom, a surfactant having a silicon atom, and a surfactant having no fluorine atom and a silicon atom can be used. Among the above, the surfactant is preferably a surfactant having a fluorine atom from the viewpoint of suppressing the generation of streaks in the photosensitive resin composition layer and the intermediate layer and the adhesion, and is preferably a perfluoroalkyl group and poly. More preferably, it is a surfactant having an alkyleneoxy group.

Further, as the surfactant, any of anionic surfactant, cationic surfactant, nonionic (nonionic surfactant), and amphoteric surfactant can be used, but it is preferable. Is a nonionic surfactant.

The surfactant is preferably a surfactant having a solubility of 1 g or more in 100 g of water at 25 ° C. from the viewpoint of suppressing precipitation of the surfactant.

The intermediate layer may contain one type of surfactant alone, or may contain two or more types of surfactants.

The content of the surfactant in the intermediate layer is 0.05% by mass to 2. It is preferably 0% by mass, more preferably 0.1% by mass to 1.0% by mass, and particularly preferably 0.2% by mass to 0.5% by mass.

(Inorganic filler)
The intermediate layer can contain an inorganic filler. Examples of the inorganic filler include silica particles, aluminum oxide particles, and zirconium oxide particles, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle size are preferable, and an inorganic filler having an average particle size of 100 nm or less is more preferable. For example, if it is a commercially available product, Snowtex (registered trademark) is preferably used.

The volume fraction of the particles in the intermediate layer (the volume ratio occupied by the particles in the intermediate layer) shall be 5% to 90% of the total product of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. Is preferable, 10% to 80% is more preferable, and 20% to 60% is particularly preferable.

(PH regulator)
The intermediate layer can contain a pH regulator. When the intermediate layer contains a pH adjuster, the color-developed state or decolorized state of the dye in the intermediate layer can be maintained more stably, and the adhesion between the photosensitive resin composition layer and the intermediate layer is improved. improves.

Examples of the pH adjuster include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, and organic ammonium salts. The pH adjuster is preferably sodium hydroxide from the viewpoint of water solubility. The pH adjuster is preferably an organic ammonium salt from the viewpoint of adhesion between the photosensitive resin composition layer and the intermediate layer.

(Average thickness of intermediate layer)
The average thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and 0.3 μm from the viewpoint of adhesion between the photosensitive resin composition layer and the intermediate layer and pattern formation property. ~ 2 μm is particularly preferable.
Further, the average thickness of the intermediate layer is preferably thinner than the average thickness of the photosensitive resin composition layer.
The average thickness of the intermediate layer is measured by a method according to the method for measuring the average thickness of the polyimide substrate.

The intermediate layer can have two or more layers.
When the intermediate layer has two or more layers, the average thickness of each layer is not limited as long as it is within the above range, but among the two or more layers in the intermediate layer, the layer closest to the photosensitive resin composition layer. The average thickness is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and 0.3 μm to 2 μm from the viewpoint of adhesion between the intermediate layer and the photosensitive resin composition layer and pattern formation property. Especially preferable.

(Method of forming the intermediate layer)
The intermediate layer can be formed by using a composition for forming an intermediate layer containing a component used for forming the intermediate layer and a water-soluble solvent. It is also possible to prepare a composition by preparing a solution in which each component is previously dissolved in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above may be filtered using a filter having a pore size of 3.0 μm or the like.
In the present disclosure, for example, an intermediate layer can be formed on the temporary support by applying the composition for forming an intermediate layer to the temporary support and drying it. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

Examples of the water-soluble solvent include water and alcohols having 1 to 6 carbon atoms, and preferably contain water. Examples of alcohols having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol. Among the above, at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol is preferable.

〔Protective film〕
The photosensitive transfer material preferably has a protective film on the surface of the photosensitive transfer material opposite to the surface on which the temporary support is provided.
Examples of the protective film include a resin film and paper, and a resin film is preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include an ethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among the above, the protective film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

The average thickness of the protective film is not limited and is preferably, for example, 1 μm to 2 mm. The average thickness of the protective film is measured by a method according to the method for measuring the average thickness of the polyimide substrate.

[Other layers]
The photosensitive transfer material may have a layer other than the above (hereinafter, also referred to as “another layer”). Examples of other layers include a contrast enhancement layer and a thermoplastic resin layer.
A preferred embodiment of the contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018/179640, and a preferred embodiment of the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643, and other layers are preferable. Aspects are described in paragraphs 0194 to 0196 of JP2014-85643, respectively, and the contents of this publication are incorporated in the present specification.

Here, with reference to FIG. 1, an example of the layer structure of the photosensitive transfer material is schematically shown.
In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 12, a transfer layer 14 formed by laminating a photosensitive resin composition layer 14-1 and an intermediate layer 14-2, and a protective film 16 are laminated in this order. Has been done. The transfer layer 14 is a layer that is transferred (that is, laminated) onto a polyimide substrate by undergoing the bonding step described above.

[Manufacturing method of photosensitive transfer material]
The method for producing the photosensitive transfer material is not limited, and a known production method, for example, a known method for forming each layer can be used.

As a method for producing a photosensitive transfer material, a method including a step of applying a photosensitive resin composition on a temporary support and drying it to form a photosensitive resin composition layer is preferably mentioned. When the photosensitive transfer material has an intermediate layer, a step of applying and drying the composition for forming the intermediate layer on the temporary support to form the intermediate layer, and applying the photosensitive resin composition on the intermediate layer. And a method including a step of drying to form a photosensitive resin composition layer is preferable.
Further, the method for producing a photosensitive transfer material according to the present disclosure preferably further includes a step of providing a protective film on the photosensitive resin composition layer after the step of forming the photosensitive resin composition layer.

<Manufacturing method of circuit board>
The method for manufacturing a circuit board according to the present disclosure is not limited as long as it is a method for manufacturing a circuit board by using a polyimide substrate having a conductive layer and applying the above-mentioned manufacturing method for a patterned substrate. The circuit board manufacturing method according to the present disclosure includes a step of manufacturing a patterned substrate by the above-mentioned manufacturing method of a patterned substrate (hereinafter, also referred to as a "board manufacturing process") and the above-mentioned photosensitive resin composition in the above-mentioned patterned substrate. A step of etching the conductive layer exposed in a region where the pattern of the material layer is not formed (hereinafter, also referred to as “etching step”) and a step of removing the pattern of the photosensitive resin composition layer (hereinafter, also referred to as “etching step”). It is preferable to have "removal step") in this order. By having the above steps, the circuit board manufacturing method according to the present disclosure can suppress a decrease in the line width of the circuit wiring due to the passage of time after exposure, and is excellent in laminating suitability under high temperature conditions.

Further, as a preferred embodiment of the method for manufacturing a circuit board according to the present disclosure, after the removal step, the four steps of the bonding step, the exposure step, the developing step, and the etching step are set as one set, and the set is made. There is a method of repeating it multiple times. By the above method, for example, two or more conductive patterns different from each other can be formed.

As a preferred embodiment of the method for manufacturing a circuit board according to the present disclosure, the exposure step is performed on the pattern of the photosensitive resin composition layer before the etching step and the removing step, and then the developing step. There is a way to do more. By the above method, for example, two or more conductive patterns different from each other can be formed.

Moreover, the polyimide substrate can be reused (reworked). In the photosensitive resin composition layer, by irradiating with active rays, for example, a photosensitive agent that generates acid by being irradiated with active rays is used to increase the solubility of the exposed portion. If none of the exposed parts are cured and the obtained pattern shape is defective, the substrate can be reused (reworked) by full exposure or the like.

As an embodiment of the method for manufacturing a circuit board according to the present disclosure, International Publication No. 2006/190405 can be referred to, and the contents thereof are incorporated in the present specification.

[Substrate manufacturing process]
The circuit board manufacturing method according to the present disclosure preferably includes a step of manufacturing a patterned substrate by the above-mentioned method for manufacturing a patterned substrate. In the above step, it is preferable that the polyimide substrate included in the patterned substrate has a conductive layer and has a conductive layer on at least one surface. The method for manufacturing the patterned substrate and the embodiment of each material used in the above method are as described in the above section “Method for manufacturing the patterned substrate”, and the preferred embodiment is also the same.

[Etching process]
The method for manufacturing a circuit board according to the present disclosure preferably includes a step of etching the conductive layer exposed in a region where the pattern of the photosensitive resin composition layer is not formed on the patterned substrate.

In the etching step, the pattern of the photosensitive resin composition layer formed by the developing step (that is, the resin pattern) is used as an etching resist, and the conductive layer is etched.

The method of etching treatment is not limited, and a known method can be applied. Examples of the etching treatment method include the methods described in paragraphs 0048 to 0054 of JP-A-2010-152155, and dry etching methods such as known plasma etching.

Examples of the etching treatment method include a commonly used wet etching method of immersing in an etching solution. As the etching solution used for wet etching, an acidic type or alkaline type etching solution may be appropriately selected according to the etching target.
Examples of the acidic type etching solution include an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and a mixture of the acidic component and a salt such as ferric chloride, ammonium fluoride, and potassium permanganate. An aqueous solution is exemplified. As the acidic component, a component in which a plurality of acidic components are combined may be used.
Examples of the alkaline type etching solution include an aqueous solution of an alkaline component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine such as tetramethylammonium hydroxide, and an alkaline component and permanganate. Examples thereof include a mixed aqueous solution with a salt such as potassium. As the alkaline component, a component in which a plurality of alkaline components are combined may be used.

The temperature of the etching solution is not limited, but is preferably 45 ° C. or lower. The resin pattern used as the etching mask (etching pattern) in the present disclosure preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the photosensitive resin composition layer is prevented from peeling off during the etching step, and the portion where the photosensitive resin composition layer does not exist is selectively etched.
After the etching step, in order to prevent contamination of the process line, a cleaning step of cleaning the etched substrate and a drying step of drying the cleaned substrate may be performed, if necessary.

[Removal process]
The method for manufacturing a circuit board according to the present disclosure preferably includes a step of removing the pattern of the photosensitive resin composition layer.
The removing step is not particularly limited and can be performed as needed, but it is preferably performed after the etching step.
The method for removing the remaining photosensitive resin composition layer is not particularly limited, and examples thereof include a method for removing by chemical treatment, and it is particularly preferable to use a removing solution.
As a method for removing the photosensitive resin composition layer, a substrate having a photosensitive resin composition layer or the like in a removing liquid being stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to A method of immersing for 30 minutes can be mentioned.

Examples of the removing liquid include inorganic alkaline components such as sodium hydroxide and potassium hydroxide, or organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Examples thereof include a removal solution in which the components are dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
Further, the removing liquid may be used and removed by a spray method, a shower method, a paddle method or the like.

[Full exposure process]
The circuit board manufacturing method according to the present disclosure is a step of completely exposing the photosensitive resin composition layer between the etching step (etching step) and the removing step (removing step) (hereinafter, "whole surface"). It is preferable to have an "exposure step").

Further, the method for manufacturing a circuit board according to the present disclosure may include a step of heating a fully exposed photosensitive resin composition layer (hereinafter, also referred to as a “heating step”), if necessary. .. The full exposure step and the heating step are preferably performed after the etching step and before the removing step.

By exposing the entire surface of the photosensitive resin composition layer used as an etching mask after the etching step, the solubility in the removing solution and the permeability of the removing solution are improved, and the removing property is removable even when the removing solution is used for a long time. Excellent for. Further, when the heating step is included, the reaction rate of the photoacid generator and the reaction rate of the generated acid and the photosensitive resin can be further improved by the heating step, and as a result, the removal performance is improved.

The light source used for exposure in the full exposure step is not limited, and a known exposure light source can be used. From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as that in the exposure step.

Exposure amount in the overall exposure step, from the viewpoint of removability ^is preferably ^{5mJ / cm 2 ~1,000mJ / cm 2} , more preferably ^{10mJ / cm 2 ~800mJ / cm 2} , 100mJ / cm It is particularly preferably ^{2 to} 500 mJ / cm ^2.

From the viewpoint of removability, the exposure amount in the entire surface exposure step is preferably equal to or more than the exposure amount in the exposure step, and more preferably larger than the exposure amount in the exposure step.

[Other processes]
The circuit board manufacturing method according to the present disclosure may include steps other than the above (hereinafter, also referred to as “other steps”). Examples of other steps include, but are not limited to, the steps shown below.
Further, as an example of the exposure step, the developing step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.

(Protective film peeling process)
When the photosensitive transfer material has a protective film, the circuit board manufacturing method according to the present disclosure preferably includes a step of peeling off the protective film of the photosensitive transfer material. The method of peeling the protective film is not limited, and a known method can be applied.

(Step to reduce visible light reflectance)
The method for manufacturing a circuit board according to the present disclosure can include a step of reducing the visible light reflectance of a part or all of the conductive layer on the polyimide substrate.
Examples of the treatment for lowering the visible light reflectance include an oxidation treatment. For example, by converting copper into copper oxide by an oxidation treatment, it is possible to reduce the visible light reflectance by blackening the copper.
Preferable embodiments of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Laid-Open No. 2013-206315. There is a description, and the contents of this publication are incorporated herein by reference.

(Step of forming an insulating film and step of forming a new conductive layer on the insulating film)
The method for manufacturing a circuit board according to the present disclosure includes a step of forming an insulating film on a conductive pattern formed on a polyimide substrate and a step of forming a new conductive layer on the insulating film. Is also preferable.
With the above configuration, a new conductive layer can be formed while being insulated from the previously formed conductive pattern.
The step of forming the insulating film is not limited, and examples thereof include a known method of forming a permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
The step of forming a new conductive layer on the insulating film is not limited, and a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

In the method for manufacturing a circuit board according to the present disclosure, a polyimide substrate having a plurality of conductive layers on both surfaces is used, and circuits are sequentially or simultaneously formed on the conductive layers formed on both surfaces of the polyimide substrate. It is also preferable to do so. With the above configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a polyimide substrate and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having the above configuration on both sides of the polyimide substrate by roll-to-roll.

The circuit board manufactured by the method for manufacturing a circuit board according to the present disclosure can be applied to various devices. Examples of the device provided with the circuit board manufactured by the method for manufacturing the circuit board according to the present disclosure include an input device, preferably a touch panel, and more preferably a capacitance type touch panel. Further, the input device can be applied to a display device such as an organic EL display device or a liquid crystal display device, for example.

<Manufacturing method of touch panel>
One embodiment of the touch panel manufacturing method according to the present disclosure includes the circuit board manufacturing method.

In addition, another embodiment of the touch panel manufacturing method according to the present disclosure includes a step of preparing a circuit board manufactured by the above circuit board manufacturing method. In the above embodiment, the touch panel is manufactured by using the circuit board manufactured by the circuit board according to the present disclosure.

In each of the above embodiments, the embodiment of the method for manufacturing the circuit board is as described in the section of "Method for manufacturing the circuit board", and the preferred embodiment is also the same.

Regarding the touch panel manufacturing method according to the present disclosure, known touch panel manufacturing methods can be referred to except for the above items.
Further, the touch panel manufacturing method according to the present disclosure may have an arbitrary process (other process) other than the above items.

2 and 3 show an example of a mask pattern used in the touch panel manufacturing method according to the present disclosure.
In the pattern shown in FIG. 2 and the pattern shown in FIG. 3, SL and G are non-image parts (light-shielding parts), and DL is a virtual representation of the alignment frame. In the method for manufacturing a touch panel according to the present disclosure, for example, by exposing the photosensitive resin composition layer through a mask having the pattern shown in FIG. 2, a circuit wiring having a pattern corresponding to SL and G is formed. Can manufacture touch panels. Specifically, it can be produced by the method shown in FIG. 1 of International Publication No. 2016/0190405. In an example of the manufactured touch panel, G is a portion where a transparent electrode (touch panel electrode) is formed, and SL is a portion where wiring of a peripheral take-out portion is formed.

The touch panel according to the present disclosure is a touch panel having at least a circuit board manufactured by the method for manufacturing a circuit board according to the present disclosure. Further, the touch panel according to the present disclosure preferably has at least a transparent substrate, electrodes, and an insulating layer or a protective layer.
As the detection method in the touch panel according to the present disclosure, any known method such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among the above, the capacitance method is preferable.
The touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-517501), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125). The one described in FIG. 19 of the publication, the one described in FIGS. 1 and 5 of Japanese Patent Application Laid-Open No. 2012-89102), OGS (One Glass Solution) type, TOR (Touch-on-Lens) type (for example, Japanese Patent Application Laid-Open No. (The one described in FIG. 2 of 2013-54727), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), various out-selling types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.) and the like.

<Laminated body>
The laminate according to the present disclosure includes a polyimide substrate and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. Since the laminate according to the present disclosure has the above structure, it is possible to suppress excessive diffusion of acid in the photosensitive resin composition layer after exposure when the laminate according to the present disclosure is exposed. Therefore, the photosensitive resin composition Excessive acid decomposition reaction of the material layer can be suppressed. Therefore, it is possible to suppress a decrease in the line width of the pattern due to the passage of time after exposure.

In the laminate according to the present disclosure, the embodiments of the polyimide substrate and the photosensitive resin composition layer are as described in the above-mentioned "Method for manufacturing a patterned substrate", and the preferred embodiments are also the same.

In the laminate according to the present disclosure, the photosensitive resin composition layer is preferably a layer formed by transfer. The layer formed by transfer can be formed by a method using a photosensitive transfer material described later (that is, a method of bonding the photosensitive transfer material and the polyimide substrate).

When the polyimide substrate has conductivity, the laminate according to the present disclosure is a photosensitive resin composition layer containing a polyimide substrate, a conductive layer, and an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher. And, preferably in this order.

The method for producing the laminate according to the present disclosure is not limited, and examples thereof include a method for producing the laminate by the "bonding step" described in the above "method for producing a patterned substrate". That is, the photosensitive resin composition layer in the photosensitive transfer material having a temporary support and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature (Tg) of 50 ° C. or higher, and The laminate according to the present disclosure can be produced by bringing the polyimide substrates into contact with each other and bonding the photosensitive transfer material and the polyimide substrate. Further, the laminate according to the present disclosure may be produced by applying the above-mentioned photosensitive resin composition on a polyimide substrate.

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. Unless otherwise specified, "parts" and "%" are based on mass.

<Abbreviation>
The following abbreviations used in the examples represent the following compounds, respectively.
"MATTH": 2-tetrahydrofuranyl methacrylate (synthetic product, methacrylate compound having a cyclic ether group at the ester position)
-"THHHS": 4- (2-tetrahydrofuranyloxy) styrene (synthetic product)
"ATHF": 2-tetrahydrofuranyl acrylate (synthetic product, acrylate compound having a cyclic ether group at the ester position)
・ "MAA": Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
-"MMA": Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., a methacrylate compound having a linear alkyl group at the ester position)
-"CHMA": Cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., a methacrylate compound having a cyclic alkyl group at the ester position)
-"EA": Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., an acrylate compound having a linear alkyl group at the ester position)
-"EHMA": 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., a methacrylate compound having a branched alkyl group at the ester position)
-"MPMP": 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by ADEKA Corporation)
-"MEHQ": 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
-"V-601": 2,2'-azobis (2-methylpropionate) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Synthesis of MATTH>
Methacrylic acid (86.1 parts by mass, 1.0 molar equivalent) and hexane (86.1 parts by mass) were added to the three-necked flask and cooled to 20 ° C. After dropping camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mol equivalent) into the above three-necked flask, 20 ° C. ± 2 The mixture was stirred in a temperature range of ° C. for 1.5 hours. Next, the liquid temperature was raised to 35 ° C., and then the mixture was stirred for 2 hours. Kyoward 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) were spread on Nutche in this order, and then the reaction solution was filtered to obtain a filtered solution. MEHQ (4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.0012 parts by mass) was added to the obtained filtrate, and the mixture was concentrated under reduced pressure at 40 ° C. to 2-tetrahydrofuranyl methacrylate (MATH, methacrylic). 156.2 parts by mass of tetrahydro-2H-furan-2-yl acidate was obtained as a colorless oil (yield 98.0%).

<Synthesis of THFHS>
4-Hydroxystyrene (120.2 parts by mass, 1.0 molar equivalent) and hexane (120.2 parts by mass) were added to a three-necked flask and cooled to 20 ° C. Camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent) were added dropwise to the three-necked flask, and then the temperature was raised to 80 ° C. It was warmed and stirred for 5 hours. Kyoward 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) were spread on Nutche in this order, and then the reaction solution was filtered to obtain a filtered solution. MEHQ (0.0019 parts by mass) was added to the obtained filtrate, and the mixture was concentrated under reduced pressure at 40 ° C. to 4- (2-tetrahydrofuranyloxy) styrene (THHS, 4- (2-tetrahydrofuranyloxy). 185.0 parts by mass of styrene) was obtained as a colorless oil (yield 97.3%).

<Synthesis of ATHF>
Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to the three-necked flask and cooled to 20 ° C. After dropping camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 mol equivalent) into the above three-necked flask, 20 ° C. ± 2 The mixture was stirred in a temperature range of ° C. for 1.5 hours. Next, the liquid temperature was raised to 35 ° C. and the mixture was stirred for 2 hours. Kyoward 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) were spread on Nutche in this order, and then the reaction solution was filtered to obtain a filtered solution. MEHQ (0.0012 parts by mass) was added to the obtained filtrate, and the mixture was concentrated under reduced pressure at 40 ° C. to obtain 2-tetrahydrofuranyl acrylate (ATHF, tetrahydro-2H-furan-2-yl acrylate) 140. 8 parts by mass was obtained as a colorless oil (yield 99.0%).

<Synthesis of polymer A-1>
Propyl acetate (75.0 parts by mass, manufactured by Showa Denko KK) was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. MATHF (40 parts by mass), MMA (15 parts by mass), CHMA (15 parts by mass), EA (30 parts by mass), V-601 (4.0 parts by mass), and propyl acetate (75.0 parts by mass). The containing solution was added dropwise to the solution in the three-necked flask maintained at a temperature range of 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropping, the mixture was stirred in a temperature range of 90 ° C. ± 2 ° C. for 2 hours to obtain a solution containing the polymer A-1 (solid content concentration: 40.0%).

<Synthesis example of polymer A-2 to polymer A-11>
Solutions containing Polymers A-2 to A-11 were obtained in the same manner as in Polymer A-1, except that the types and amounts of monomers used were changed according to Table 1 below. The solid content concentration in the solution was 40.0% by mass.

In Table 1, "monomer A" means a monomer forming a structural unit having an acid group protected by an acid-degradable group. In Table 1, "monomer B" means a monomer forming a structural unit other than the structural unit having an acid group protected by an acid-degradable group. In Table 1, "-" means that the corresponding monomer is not used. The glass transition temperature (Tg), acid value, and weight average molecular weight (Mw) shown in Table 1 were measured by the above-mentioned methods.

<Examples 1 to 12 and Comparative Examples 1 to 2>
[Preparation of photosensitive transfer material]
After weighing the solution containing each polymer (A-1 to A-11), the photoacid generator, the basic compound, and the surfactant so as to have the solid content mass ratio shown in Table 2 below, each of the above. A mixed solution having a solid content concentration of 10% by mass was obtained by dissolving and mixing the components and propyl acetate. A photosensitive resin composition (composition for a photosensitive transfer material) was obtained by filtering the mixed solution with a filter made of polytetrafluoroethylene having a diameter of 0.2 μm. The photosensitive resin composition was applied as a temporary support on a polyethylene terephthalate film having a thickness of 30 μm using a slit-shaped nozzle so that the dry film thickness was 4.0 μm. Then, the photosensitive resin composition layer was formed on the temporary support by passing through a drying zone having an average temperature of 85 ° C. for 50 seconds. Finally, a polyethylene film (OSM-N, manufactured by Tredegar) as a protective film is pressure-bonded onto the photosensitive resin composition layer to prepare photosensitive transfer materials of Examples 1 to 12 and Comparative Examples 1 and 2, respectively. bottom.

[Preparation of substrate]
A substrate with a copper layer was produced by laminating a copper layer having a thickness of 500 nm on each of the substrates listed in Table 2 below by a sputtering method.

[Sensitivity (exposure sensitivity) evaluation]
Each of the produced photosensitive transfer materials was bonded to a substrate with a copper layer under laminating conditions of a roll temperature of 130 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min. After exposing the photosensitive resin composition layer using an ultra-high pressure mercury lamp through a line-and-space pattern (duty ratio = 1: 1) mask with a line width of 20 μm without peeling off the temporary support, and then leaving it for 1 hour. The temporary support was peeled off and developed. Development was carried out by shower development for 40 seconds using a 0.9% sodium carbonate aqueous solution at 22 ° C. When a line-and-space pattern having a line width of 20 μm was formed by the above method, the residue in the space portion of 20 μm was observed with a scanning electron microscope (SEM) to determine the exposure amount from which the residue was completely eliminated. The above exposure amount was used as the exposure amount to be applied by the following evaluations (resolution evaluation, pattern width change rate).

[evaluation]
(Laminating suitability (roll-to-roll method))
After peeling off the protective film from each of the prepared photosensitive transfer materials, the photosensitive transfer material is provided with a copper layer under laminating conditions of a roll temperature of 130 ° C., a linear pressure of 0.8 MPa, and a linear velocity (conveyance speed) of 3.0 m / min. It was attached to the substrate by a roll-to-roll method. A 50 cm square test piece was cut out from the rolled roll after bonding, and the state of adhesion between the photosensitive resin composition and the copper layer was visually confirmed. The ratio (%) of the area where the photosensitive resin composition layer is in close contact with the copper layer in the test piece without bubbles and floating is determined by the following formula, and the suitability for laminating under high temperature and high speed conditions is determined according to the following criteria. evaluated. The evaluation results are shown in Table 2. It can be said that the larger the adhesion area (%) of the photosensitive resin composition layer, the better the laminating suitability under high temperature and high speed conditions.
Formula: Area (%) = [(Adhesion area of photosensitive resin composition layer) / (Area of test piece)] × 100

− Criteria −
The area (%) is 95% or more, and the photosensitive resin composition layer is not cracked: 5
The area (%) is 95% or more, but the photosensitive resin composition layer is cracked: 4
Area (%) is 85% or more and less than 95%: 3
Area (%) is less than 85%: 2

(Resolution)
Each of the produced photosensitive transfer materials was bonded to a substrate with a copper layer under laminating conditions of a roll temperature of 130 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min.
Exposure of the photosensitive resin composition layer obtained by the above sensitivity evaluation using an ultra-high pressure mercury lamp via a line-and-space pattern (duty ratio = 1: 1) mask with a line width of 3 μm to 20 μm without peeling off the temporary support. After exposure to a large amount, the mixture was left for 3 hours, and then the temporary support was peeled off and developed. Development was carried out by shower development for 40 seconds using a 1.0% sodium carbonate aqueous solution at 22 ° C. Among the line-and-space patterns obtained in this way, the pattern with the smallest line width was defined as the ultimate resolution. Further, when determining the ultimate resolution, the pattern was observed using a scanning electron microscope (SEM), and if the side wall portion of the pattern had a large roughness, it was determined that the resolution could not be achieved. Based on the obtained ultimate resolution, the resolution was evaluated according to the following criteria. The evaluation results are shown in Table 2. It can be said that the smaller the ultimate resolution, the more excellent the resolution can be obtained even when the pattern is left unattended after exposure.

− Criteria −
Reach resolution is less than 6 μm: 5
Reach resolution is less than 8 μm, more than 6 μm: 4.5
Reach resolution is less than 10 μm, 8 μm or more: 4
Reach resolution is less than 15 μm and more than 10 μm: 3
Reach resolution is less than 20 μm, 15 μm or more: 2
The ultimate resolution is 20 μm or more: 1.

(Pattern width change rate)
Each of the produced photosensitive transfer materials was bonded to a substrate with a copper layer under laminating conditions of a roll temperature of 130 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min.
The photosensitive resin composition layer was exposed to the exposure amount determined by the sensitivity evaluation using an ultra-high pressure mercury lamp via a line-and-space pattern (Duty ratio 1: 1) mask having a line width of 6 μm without peeling off the temporary support. After that, after leaving it for 3 hours and after leaving it for 24 hours, the temporary support was peeled off and developed. Development was carried out by shower development for 40 seconds using a 1.0% sodium carbonate aqueous solution at 22 ° C. A substrate with a line-and-space pattern thus obtained was obtained. The pattern width after 3 hours and the pattern width after 24 hours in the 6 μm pattern (resin pattern) on the substrate were determined, respectively. The rate of change of the pattern width after 24 hours with respect to the pattern width after 3 hours was calculated according to the following formula. Based on the obtained pattern width change rate, the pattern width change rate was evaluated according to the following criteria. The evaluation results are shown in Table 2. It can be said that the smaller the value of the rate of change is, the more the decrease in the line width due to the passage of time after exposure is suppressed, and the more stable the performance is.
Formula: Pattern width change rate (%) = {[Pattern width after 24 hours (μm)] / [Pattern width after 3 hours (μm)]} × 100

− Criteria −
Less than 2%: 3
Less than 5%, 2% or more: 2
5% or more: 1

(Copper wire width change rate)
Each of the produced photosensitive transfer materials was bonded to a substrate with a copper layer under laminating conditions of a roll temperature of 130 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min.
The photosensitive resin composition layer was exposed to the exposure amount determined by the sensitivity evaluation using an ultra-high pressure mercury lamp through a line-and-space pattern (Duty ratio 1: 1) mask with a line width of 6 μm without peeling off the temporary support. After that, the temporary support was peeled off and developed after being left for 3 hours and after being left for 24 hours. Development was carried out by shower development for 40 seconds using a 1.0% sodium carbonate aqueous solution at 22 ° C. The line-and-space pattern thus obtained was obtained. Next, the copper layer was etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.) to obtain a substrate drawn with copper (solid line SL). The copper wire width after 3 hours and the copper wire width after 24 hours in the 6 μm pattern (copper pattern) on the substrate were determined, respectively. The rate of change of the copper wire width after 24 hours with respect to the copper wire width after 3 hours was calculated according to the following formula. Based on the obtained rate of change in copper wire width, the rate of change in copper wire width was evaluated according to the following criteria. The evaluation results are shown in Table 2. It can be said that the smaller the value of the rate of change is, the more the decrease in the line width due to the passage of time after exposure is suppressed, and the more stable the performance is.
Formula: Copper wire width change rate (%) = {[Copper wire width after 24 hours (μm)] / [Copper wire width after 3 hours (μm)]} × 100

− Criteria −
Less than 5%: 3
Less than 10%, 5% or more: 2
10% or more: 1

[Display characteristics (brightness)]
Luminance was evaluated as one index of display characteristics.
An indium tin oxide (ITO) layer (thickness 150 nm) was formed by sputtering on various polyimide substrates and a polyethylene terephthalate substrate as a second conductive layer, and then on the ITO layer. A substrate was produced by forming a copper layer (thickness 200 nm) as a conductive layer of the first layer by a vacuum vapor deposition method.
Each of the prepared photosensitive transfer materials was bonded onto the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 130 ° C.). The contact pattern was exposed using a photomask provided with the pattern shown in FIG. 2, which had a structure in which the conductive layer pads were connected in one direction without peeling off the temporary support.
In the pattern shown in FIG. 2, the solid line portion SL and the gray portion G are light-shielding portions, and the dotted line portion DL is a virtual representation of the alignment alignment frame.
After that, the temporary support was peeled off, developed, and washed with water to obtain the pattern shown in FIG. Next, the copper layer was etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer was etched with an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) to obtain copper (Copper (Cu-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which both the solid line portion SL) and the ITO (gray portion G) were drawn in the pattern shown in FIG. 2 was obtained.
Next, the pattern was exposed using a photomask provided with an opening of the pattern shown in FIG. 3 in an aligned state, and the pattern was developed and washed with water.
In the pattern shown in FIG. 3, the gray portion G is the light-shielding portion, and the dotted line portion DL is a virtual representation of the alignment alignment frame.
Then, the copper layer was etched with Cu-02, and the remaining photosensitive resin composition layer was peeled off with a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit board.
The obtained circuit board was irradiated from the back side with a fluorescent lamp (wavelength range 380 to 780 nm), and the transmitted light intensity was measured with a luminance meter LS-100 (manufactured by MINOLTA).
The light intensity A when the circuit board is not sandwiched (that is, the intensity of the light emitted from the fluorescent lamp) is defined as the light intensity B (that is, the intensity of the light transmitted through the circuit board) when the circuit board is sandwiched. , The brightness maintenance rate was calculated according to the following formula. Based on the obtained brightness maintenance rate, the display characteristics were evaluated according to the following criteria. The evaluation results are shown in Table 2. The larger the value of the luminance maintenance rate, the better the display characteristics of the display device when the obtained circuit board is provided in the display device.
Formula: Brightness maintenance rate (%) = [light intensity B / light intensity A] x 100

− Criteria −
60% or more: 2
60% or less: 1

The following abbreviations used in Table 2 represent the following materials, respectively.

<Photoacid generator>
"B-1": A compound having the structure shown below (synthesized according to the method described in paragraph 0227 of JP2013-47765A).

"B-2": A compound having the structure shown below (trade name: PAG-103, manufactured by BASF).

<Surfactant>
"C-1": A compound having the structure shown below.

<Basic compound>
"D-1": A compound having the structure shown below (CMTU)

<Board>
-"Polyimide 1": FORMED (registered trademark) TypeX (manufactured by IST Co., Ltd., haze 0.4%, total light transmittance 90%, thickness 50 μm)
-"Polyimide 2": FORMED TypeS (manufactured by IST Co., Ltd., haze 3.0%, total light transmittance 88%, thickness 25 μm)
-"Polyimide 3": Kapton (registered trademark) 100H (manufactured by Toray DuPont Co., Ltd., total light transmittance 85% or less, thickness 25 μm)
-"Polyethylene terephthalate": Lumirror (registered trademark) 16QS60 (manufactured by Toray Industries, Inc., haze 0.4%, total light transmittance 90%, thickness 16 μm)

From Table 2, it was found that Examples 1 to 12 had a smaller rate of change in pattern width and copper wire width than Comparative Examples 1 and 2, and were excellent in laminating suitability under high temperature and high speed conditions. Further, it was found that Examples 1 to 10 using polyimide 1 having a small haze and high total light transmittance were superior in display characteristics to Examples 11 to 12.

The disclosure of Japanese Patent Application No. 2019-036429, filed February 28, 2019, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (15)

The temporary support, the photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher, the photosensitive resin composition layer in the photosensitive transfer material having the glass transition temperature, and the polyimide substrate are brought into contact with each other. A method for manufacturing a patterned substrate, which comprises a step of bonding the photosensitive transfer material and the polyimide substrate. The glass transition temperature of the acid-decomposable resin is 50 ° C. to 90 ° C., the heating temperature is 120 ° C. to 150 ° C., and the transport speed is high in the step of bonding the photosensitive transfer material and the polyimide substrate. The method for manufacturing a patterned substrate according to claim 1, wherein the temperature is 2.5 m / min to 5.0 m / min. The method for producing a patterned substrate according to claim 1 or 2, wherein the glass transition temperature of the acid-decomposable resin is 55 ° C. to 90 ° C. The method for producing a patterned substrate according to any one of claims 1 to 3, wherein the acid value of the acid-decomposable resin is 0 mgKOH / g to 10 mgKOH / g. The acid-decomposable resin has a (meth) acrylate compound having a linear alkyl group having 1 to 3 carbon atoms at the ester position, a (meth) acrylate compound having a branched alkyl group having 1 to 3 carbon atoms at the ester position, and the like. At least one selected from the group consisting of a (meth) acrylate compound having a cyclic alkyl group having 4 to 20 carbon atoms at an ester position and a (meth) acrylate compound having a cyclic ether group having 4 to 20 carbon atoms at an ester position. Derived from at least one acrylic compound selected from the group consisting of acrylic acid and an acrylate compound, which contains 90% by mass or more of the structural unit derived from the (meth) acrylate compound with respect to the total mass of the acid-degradable resin. The method for producing a patterned substrate according to any one of claims 1 to 4, wherein the constituent unit of the above is 0% by mass to 30% by mass with respect to the total mass of the acid-degradable resin. The method for manufacturing a patterned substrate according to any one of claims 1 to 5, wherein the haze of the polyimide substrate is 0.5% or less. The method for manufacturing a patterned substrate according to any one of claims 1 to 6, wherein the total light transmittance of the polyimide substrate is 85% or more. A step of pattern-exposing the photosensitive resin composition layer after the bonding step, and a step of pattern-exposing the photosensitive resin composition layer.
The step of developing the photosensitive resin composition layer exposed to the pattern to form a pattern of the photosensitive resin composition layer, and
The method for manufacturing a patterned substrate according to any one of claims 1 to 7. The method for manufacturing a patterned substrate according to any one of claims 1 to 8, wherein the polyimide substrate has a conductive layer. A step of manufacturing a patterned substrate by the method for manufacturing a patterned substrate according to claim 9.
A step of etching the conductive layer exposed in a region where the pattern of the photosensitive resin composition layer is not formed on the patterned substrate, and a step of etching the conductive layer.
The step of removing the pattern of the photosensitive resin composition layer and
A method of manufacturing a circuit board having the above in this order. The method for manufacturing a circuit board according to claim 10, further comprising a step of exposing the entire surface of the photosensitive resin composition layer between the etching step and the removing step. The method for manufacturing a circuit board according to claim 10 or 11, wherein the conductive layer is a copper layer or a silver layer. A method for manufacturing a touch panel, which comprises the method for manufacturing a circuit board according to any one of claims 10 to 12. A method for manufacturing a touch panel, comprising a step of preparing a circuit board manufactured by the method for manufacturing a circuit board according to any one of claims 10 to 12. A laminate having a polyimide substrate and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ° C. or higher.

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