阅读说明：本技术 带图案的基板的制造方法、电路基板的制造方法、触控面板的制造方法及层叠体 (Method for manufacturing substrate with pattern, method for manufacturing circuit substrate, method for manufacturing touch panel, and laminate ) 是由 山田悟 于 2019-11-12 设计创作，主要内容包括：本发明提供一种带图案的基板的制造方法及其应用,所述带图案的基板的制造方法具有使感光性转印材料中的感光性树脂组合物层和聚酰亚胺基板接触,以将上述感光性转印材料与上述聚酰亚胺基板贴合的工序,该感光性转印材料具有临时支承体和含有玻璃化转变温度为50℃以上的酸分解性树脂的上述感光性树脂组合物层。(The invention provides a method for manufacturing a substrate with a pattern and an application thereof, the method for manufacturing the substrate with the pattern comprises a step of contacting a photosensitive resin composition layer in a photosensitive transfer material with a polyimide substrate so as to bond the photosensitive transfer material with the polyimide substrate, wherein the photosensitive transfer material comprises a temporary support and the photosensitive resin composition layer containing an acid-decomposable resin with a glass transition temperature of 50 ℃ or higher.)

1. A method for manufacturing a patterned substrate, comprising a step of bringing a photosensitive resin composition layer in a photosensitive transfer material into contact with a polyimide substrate to bond the photosensitive transfer material to the polyimide substrate, wherein the photosensitive transfer material comprises a temporary support and the photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher.

2. The method of manufacturing a patterned substrate according to claim 1,

the glass transition temperature of the acid-decomposable resin is 50 to 90 ℃, and in the step of bonding the photosensitive transfer material to the polyimide substrate, the heating temperature is 120 to 150 ℃, and the conveying speed is 2.5 to 5.0 m/min.

3. The method for manufacturing a patterned substrate according to claim 1 or 2,

the glass transition temperature of the acid-decomposable resin is 55 to 90 ℃.

4. The method for manufacturing a patterned substrate according to any one of claims 1 to 3,

the acid value of the acid-decomposable resin is from 0mgKOH/g to 10 mgKOH/g.

5. The method of manufacturing a patterned substrate according to any one of claims 1 to 4,

the acid-decomposable resin contains 90 mass% or more of structural units derived from at least one (meth) acrylate compound selected from the group consisting of 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, 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, based on the total mass of the acid-decomposable resin, and the acid-decomposable resin contains a structural unit derived from at least one acrylic compound selected from the group consisting of acrylic acid and an acrylic ester compound in an amount of 0 to 30% by mass based on the total mass of the acid-decomposable resin.

6. The method of manufacturing a patterned substrate according to any one of claims 1 to 5,

the polyimide substrate has a haze of 0.5% or less.

7. The method of manufacturing a patterned substrate according to any one of claims 1 to 6,

the total light transmittance of the polyimide substrate is more than 85%.

8. The method for manufacturing a patterned substrate according to any one of claims 1 to 7, comprising the steps of:

a step of pattern-exposing the photosensitive resin composition layer after the step of bonding; and

and a step of forming a pattern of the photosensitive resin composition layer by developing the photosensitive resin composition layer exposed to the pattern.

9. The method of manufacturing a patterned substrate according to any one of claims 1 to 8,

the polyimide substrate has a conductive layer.

10. A method for manufacturing a circuit board, comprising the following steps in this order:

a step of manufacturing a patterned substrate by the method for manufacturing a patterned substrate according to claim 9;

etching the conductive layer exposed in a region of the patterned substrate where the photosensitive resin composition layer is not formed; and

and removing the pattern of the photosensitive resin composition layer.

11. The method of manufacturing a circuit substrate according to claim 10,

the step of exposing the entire surface of the photosensitive resin composition layer is provided between the step of etching and the step of removing.

12. The method of manufacturing a circuit substrate according to claim 10 or 11,

the conductive layer is a copper layer or a silver layer.

13. A method of manufacturing a touch panel, comprising the method of manufacturing a circuit substrate according to any one of claims 10 to 12.

14. 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.

15. A laminate comprising a polyimide substrate and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher.

Technical Field

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

Background

A technique for forming a conductive pattern such as a metal wiring is widely used in, for example, manufacturing of a touch panel and manufacturing of a printed wiring board.

In a display device including a touch panel such as a capacitive 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 of the viewing portion, a peripheral wiring, and a lead wiring. In the formation of the conductive pattern, since the number of steps is small, for example, a technique of attaching a photosensitive transfer material to a substrate, and then forming a desired pattern by pattern exposure, development and etching can be used (for example, refer to japanese patent application laid-open No. 2017 and 156735).

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

On the other hand, a heat-resistant insulating film such as an aromatic polyimide film is used for the printed wiring board (for example, see japanese patent laid-open publication No. 2006-212802).

Disclosure of Invention

Technical problem to be solved by the invention

However, when 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 japanese patent application laid-open No. 2017-156735, is used to form a pattern on a substrate, there is a problem that the line width of the pattern to be obtained may decrease as the time from the exposure step to the next step elapses, when the substrate is placed from the exposure step to the next step (for example, the development step). This problem is also known as Post Exposure Delay (PED).

Further, if the conventional photosensitive transfer material and the substrate are bonded at a high temperature, for example, a decrease in adhesion between the photosensitive transfer material and the substrate and deformation (e.g., elongation and wrinkle) of the substrate may occur. In particular, when the photosensitive transfer material and the substrate are bonded by a Roll-to-Roll (Roll) method, the above-described problem tends to occur.

Further, since a conventional polyimide film described in, for example, japanese patent application laid-open No. 2006-212802 is colored, it is considered that it is difficult to apply the film 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.

The present invention has been made in view of the above circumstances.

An object of one embodiment of the present invention is to provide a method for manufacturing a patterned substrate, which can suppress a decrease in pattern line width with time after exposure and has excellent lamination suitability under high temperature conditions.

Another object of the present invention is to provide a method for manufacturing a circuit board, which can suppress a decrease in line width of circuit wiring due to the passage of time after exposure and has excellent lamination suitability under high temperature conditions.

Another object of the present invention is to provide a method for manufacturing a touch panel including the method for manufacturing a circuit board.

Another object of the present invention is to provide a method for manufacturing a touch panel using the circuit board manufactured by the method for manufacturing a circuit board.

Another object of another embodiment of the present invention is to provide a laminate that can suppress a decrease in pattern line width with time after exposure.

Means for solving the technical problem

The method for solving the above problem includes the following means.

< 1 > A method for producing a patterned substrate, comprising a step of bringing a photosensitive resin composition layer in a photosensitive transfer material into contact with a polyimide substrate to bond the photosensitive transfer material to the polyimide substrate, wherein the photosensitive transfer material comprises a temporary support and the photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher.

< 2 > the method for producing a patterned substrate according to < 1 >, wherein the glass transition temperature of the acid-decomposable resin is 50 to 90 ℃, the heating temperature is 120 to 150 ℃ and the transport speed is 2.5 to 5.0 m/min in the step of bonding the photosensitive transfer material to the polyimide substrate.

< 3 > the method for producing a patterned substrate according to < 1 > or < 2 >, wherein the glass transition temperature of the acid-decomposable resin is from 55 ℃ to 90 ℃.

< 4 > the method for producing a patterned substrate according to any one of < 1 > to < 3 >, wherein the acid value of the acid-decomposable resin is from 0mgKOH/g to 10 mgKOH/g.

< 5 > the method for producing a patterned substrate according to any one of < 1 > to < 4 >, wherein the acid-decomposable resin contains 90% by mass or more of a structural unit derived from at least one (meth) acrylate compound selected from the group consisting of 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, 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, based on the total mass of the acid-decomposable resin, and the acid-decomposable resin contains 0% by mass to 30% by mass of at least one structural unit derived from the group consisting of acrylic acid and an acrylate compound, based on the total mass of the acid-decomposable resin Structural units of acrylic compounds.

< 6 > the method for producing a patterned substrate according to any one of < 1 > to < 5 >, wherein the polyimide substrate has a haze of 0.5% or less.

< 7 > the method for producing a patterned substrate according to any one of < 1 > to < 6 >, wherein the polyimide substrate has a total light transmittance of 85% or more.

< 8 > the method for producing a patterned substrate according to any one of < 1 > to < 7 > comprising the steps of: a step of pattern-exposing the photosensitive resin composition layer after the step of bonding; and a step of forming a pattern of the photosensitive resin composition layer by developing the photosensitive resin composition layer exposed to the pattern.

< 9 > the method for producing a patterned substrate according to any one of < 1 > to < 8 >, wherein the polyimide substrate has a conductive layer.

< 10 > a method for manufacturing a circuit board, comprising the following steps in this order: a step of manufacturing a patterned substrate by the method of manufacturing a patterned substrate described in < 9 >; etching the conductive layer exposed in a region of the patterned substrate where the photosensitive resin composition layer is not formed; and removing the pattern of the photosensitive resin composition layer.

< 11 > the method for manufacturing a circuit board according to < 10 >, wherein a step of exposing the entire surface of the photosensitive resin composition layer is provided between the step of etching and the step of removing.

< 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, comprising the method for manufacturing a circuit substrate of any one of < 10 > to < 12 >.

< 14 > 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 < 10 > to < 12 >.

< 15 > a laminate comprising a polyimide substrate and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher.

Effects of the invention

According to an embodiment of the present invention, it is possible to provide a method for manufacturing a patterned substrate which can suppress a decrease in pattern line width with time after exposure and has excellent lamination suitability under high temperature conditions.

According to another aspect of the present invention, there is provided a method for manufacturing a circuit board, which can suppress a decrease in line width of circuit wiring due to a lapse of time after exposure and has excellent lamination suitability under high temperature conditions.

According to another aspect of the present invention, there is provided a method for manufacturing a touch panel including the method for manufacturing a circuit board.

According to another aspect of the present invention, there is provided a method of manufacturing a touch panel using the circuit board manufactured by the method of manufacturing a circuit board.

According to another aspect of the present invention, a laminate can be provided in which a decrease in pattern line width due to the passage of time after exposure can be suppressed.

Drawings

Fig. 1 is a schematic view showing an example of a layer structure of a photosensitive transfer material according to the present invention.

Fig. 2 is a schematic diagram showing an example of a pattern.

Fig. 3 is a schematic diagram showing an example of a pattern.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented by making appropriate changes within the scope of the object of the present invention.

In the present invention, the numerical range represented by "to" means a range in which the numerical values before and after "to" are included as the lower limit value and the upper limit value. In the numerical ranges recited in the present invention, the upper limit or the lower limit recited in a certain numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In addition, in the numerical ranges of the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.

In the present invention, "(meth) acrylic acid" means both or either of acrylic acid and methacrylic acid, and "(meth) acrylate" means both or either of acrylate and methacrylate.

In the present invention, when a plurality of substances corresponding to each ingredient are present in the composition, the amount of each ingredient in the composition refers to the total amount of the plurality of substances present in the composition, unless otherwise specified.

In the present invention, the term "step" includes not only an independent step but also a step that can achieve a desired purpose even when it is not clearly distinguished from other steps.

In the labeling of the group (atomic group) in the present invention, the label which is not described as substituted or unsubstituted includes a group having a substituent in addition to a group having no substituent. For example, "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 invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, a more preferable mode is a combination of 2 or more preferable modes.

In the present invention, the chemical structural formula may be described by a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. The light used for exposure is not particularly limited, and examples thereof include active rays (active energy rays) such as a bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

< method for manufacturing substrate with pattern >

The method for manufacturing a patterned substrate according to the present invention includes a step of bringing a photosensitive resin composition layer in a photosensitive transfer material into contact with a polyimide substrate to bond the photosensitive transfer material to the polyimide substrate (hereinafter, also referred to as a "bonding step"), the photosensitive transfer material including a temporary support and the photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature (Tg) of 50 ℃ or higher.

The method for manufacturing a patterned substrate according to the present invention can suppress a decrease in the line width of a pattern due to the passage of time after exposure, and is excellent in lamination suitability under high-temperature conditions. The reason why the method for producing a patterned substrate according to the present invention exerts the above-described effects is not clear, but is presumed as follows.

The decrease in the line width of the pattern due to the passage of time after exposure is considered to occur due to excessive decomposition of the photosensitive resin composition layer. The photosensitive transfer material suitable for the method for producing a patterned substrate according to the present invention has a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher, and can suppress excessive diffusion of an acid in the photosensitive resin composition layer after exposure, and therefore can suppress excessive acid decomposition reaction of the photosensitive resin composition layer. Further, it is considered that the method for manufacturing a patterned substrate according to the present invention includes a step of bringing a photosensitive resin composition layer in a photosensitive transfer material into contact with a polyimide substrate to bond the photosensitive transfer material to the polyimide substrate, and thereby the polyimide substrate is not deformed even under high temperature conditions, and the photosensitive transfer material and the polyimide substrate can be brought into close contact with each other, the photosensitive transfer material having a temporary support; and the photosensitive resin composition layer contains an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher. 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 invention can suppress a decrease in the line width of a pattern with the passage of time after exposure, and is excellent in lamination suitability under high temperature conditions.

[ bonding Process ]

The method for manufacturing a patterned substrate according to the present invention includes a step of bringing a photosensitive resin composition layer in a photosensitive transfer material into contact with a polyimide substrate to bond the photosensitive transfer material to the polyimide substrate, the photosensitive transfer material including a temporary support and the photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher.

The method for bonding the photosensitive transfer material to the polyimide substrate is not limited, and a known method can be applied. The photosensitive transfer material and the polyimide substrate are preferably bonded to each other by applying pressure and heat using, for example, a roller. In the bonding step, for example, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving 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 to a roll-shaped polyimide substrate.

In the bonding step, the heating temperature is preferably 100 to 150 ℃, more preferably 110 to 150 ℃, still more preferably 120 to 150 ℃, and particularly preferably 120 to 140 ℃. When the heating temperature is 100 ℃ or higher, the photosensitive transfer material can be easily bonded to the polyimide substrate. When the heating temperature is 150 ℃ or lower, deterioration of the film quality of the polyimide substrate can be suppressed.

When a contact type heating mechanism (e.g., a roller) is used in the bonding step, the heating temperature in the bonding step is the surface temperature of the contact type heating mechanism.

When a non-contact heating mechanism (e.g., a heater) is used in the bonding step, the heating temperature in the bonding step is an arrival temperature at which the respective surfaces of the photosensitive transfer material and the polyimide substrate reach a contact point between the photosensitive transfer material and the polyimide substrate.

In the bonding step, the conveying speed is preferably 2.5 m/min to 5.0 m/min, and more preferably 3.0 m/min to 5.0 m/min. The transfer speeds are transfer speeds of the photosensitive transfer material and the polyimide substrate transferred in the bonding step.

Among the above, when the photosensitive transfer material is bonded to the polyimide substrate, the heating temperature is preferably 120 to 150 ℃ and the carrying rate is 2.5 to 5.0 m/min, and the heating temperature is more preferably 120 to 140 ℃ and the carrying rate is 2.5 to 5.0 m/min.

The method for manufacturing a patterned substrate according to the present invention preferably includes, in addition to the bonding step, a step of pattern-exposing the photosensitive resin composition layer after the bonding step (hereinafter also referred to as "exposure step"), and a step of developing the photosensitive resin composition layer subjected to the pattern exposure to form a pattern of the photosensitive resin composition layer (hereinafter also referred to as "development step").

The exposure step and the development step are explained below.

[ Exposure Process ]

The method for producing a patterned substrate according to the present invention 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 light in a wavelength region (for example, 365nm or 405nm) capable of exposing the photosensitive resin composition layer is preferable. Examples of the Light source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

The exposure amount is preferably 5mJ/cm²～200mJ/cm²More preferably 10mJ/cm²～100mJ/cm²。

The pattern exposure may be exposure through a mask or may be direct exposure using a laser or the like.

In the exposure step, pattern exposure may be performed after the temporary support is peeled from the photosensitive resin composition layer, or pattern exposure may be performed through the temporary support before the temporary support is peeled, and then the temporary support may be peeled. In the case of performing exposure through a mask, it is preferable to perform pattern exposure without peeling off the temporary support in order to prevent contamination of the mask due to contact between the photosensitive resin composition layer and the mask and to avoid influence of foreign matters adhering to the mask on the exposure.

In the present invention, the detailed configuration and specific dimensions 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, an electrode pattern and a lead line portion of the touch panel) is preferably a thin line of 100 μm or less, and more preferably a thin line of 70 μm or less, from the viewpoint of improving display quality and minimizing an area occupied by the lead line.

[ developing Process ]

The method for producing a patterned substrate according to the present invention 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.

In the case where 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. In the developing step, the intermediate layer in the unexposed portion may be removed by dissolving or dispersing in a developer.

The development of the pattern-exposed photosensitive resin composition layer may be performed using a developer.

The developing solution is not limited as long as it can remove the exposed photosensitive resin composition layer, and a known developing solution such as the one described in japanese patent application laid-open No. 5-72724 can be used. The developer is preferably a developer in which an exposed portion (in the case of a positive type) of the photosensitive resin composition layer undergoes dissolution-type development. The developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of, for example, 0.05mol/L (liter) to 5 mol/L. The developer may further contain a water-soluble organic solvent and a surfactant. The developer preferably used in the present invention includes, for example, the developer described in section 0194 of international publication No. 2015/093271.

In addition, as the developer, a developer in which an unexposed portion (in the case of a negative type) of the photosensitive resin composition layer is subjected to a dissolution type developing action may be used. Examples of such a developer include organic solvents such as butyl acetate.

The developing method may be any of, for example, spin-on immersion development, shower and spin development, and immersion development. Here, the shower development is explained, and the exposed portion can be removed by spraying a developing solution to the exposed photosensitive resin composition layer with a shower. After development, it is preferable to remove the development residue by spraying a cleaning agent or the like with a shower while wiping it with a brush or the like. The solution temperature of the developer is preferably 20 to 40 ℃.

The method for manufacturing a patterned substrate according to the present invention may include a post-baking step of performing a heat treatment on a pattern including the photosensitive resin composition layer obtained by development.

The post-baking temperature is preferably from 80 ℃ to 250 ℃, more preferably from 110 ℃ to 170 ℃, and particularly preferably from 130 ℃ to 150 ℃.

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.

The post-baking may be performed in an air atmosphere or in a nitrogen replacement atmosphere.

When the photosensitive transfer material has a protective film described later, the method for producing a patterned substrate according to the present invention may further include a step of peeling off the protective film of the photosensitive transfer material (hereinafter, also referred to as "protective film peeling step") as needed. The protective film peeling step will be described in the section "method for manufacturing a circuit board" to be described later.

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

Next, a polyimide substrate and a photosensitive transfer material which are suitable for use in the method for producing a patterned substrate according to the present invention will be described.

[ base plate ]

In the method for manufacturing a patterned substrate according to the present invention, a polyimide substrate is used as the substrate. In the method for producing a patterned substrate according to the present invention, a polyimide substrate is bonded to a photosensitive transfer material described later, whereby excellent lamination suitability can be achieved under high-temperature conditions.

The polyimide constituting the polyimide substrate is not limited as long as it is a polymer compound having an imide bond, and known polyimides can be used. The polyimide substrate may be a commercially available one. The polyimide substrate may be obtained in the form of, for example, a toned (registered trademark) type x (manufactured by i.s.t Corporation), a toned type s (manufactured by i.s.t Corporation), or Kapton (registered trademark) 100H (manufactured by DU PONT-TORAY co. Among the above commercially available products, the polyimide substrate is preferably a tommed type x or a tommed type s from the viewpoint of optical characteristics.

The haze of the polyimide substrate is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, and particularly preferably 0.5% or less. When the haze of the polyimide substrate is 3.0% or less, scattering of light can be suppressed. Therefore, for example, display characteristics (e.g., luminance) 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 can be appropriately set, for example, in the range of 0% or more.

The haze of the polyimide substrate was measured using a haze meter (e.g., 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. The total light transmittance of the polyimide substrate is 85% or more, and thus the light transmittance of the polyimide substrate can be improved. Therefore, for example, display characteristics (e.g., luminance) 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 can be set appropriately within a range of 100% or less, for example.

The total light transmittance of the polyimide substrate was measured using a spectrophotometer (e.g., UV-2100, manufactured by shimadzuorroporation).

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, the polyimide substrate preferably has conductivity at least on the surface to which the photosensitive transfer material is bonded. The polyimide substrate has a conductive layer, and thus, for example, a conductive pattern can be formed.

In the present invention, "conductivity" means that the volume resistivity is less than 1X 10⁶Omega cm, preferably having a volume resistivity of less than 1X 10⁴Ωcm。

The conductive layer formed on the polyimide substrate may be any conductive layer used for general circuit wiring or touch panel wiring.

The conductive layer is preferably 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, more preferably at least one layer selected from the group consisting of a metal layer and a conductive metal oxide layer, even more preferably a metal layer, and particularly preferably a copper layer or a silver layer, from the viewpoint of conductivity and thin line formability.

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) and IZO (Indium tin oxide) (IZO)Indium Zinc Oxide) and SiO₂。

The polyimide substrate may have 1 conductive layer, or 2 or more conductive layers. When the polyimide substrate has 2 or more conductive layers, the polyimide substrate preferably has conductive layers of different materials from each other. When the polyimide substrate has 2 or more conductive layers, it is preferable that at least 1 conductive layer of the 2 or more conductive layers contains a conductive metal oxide.

The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition unit used in the capacitive touch panel or a wiring of a peripheral lead-out unit.

The thickness of the polyimide substrate is not limited, and can be set as appropriate depending on the application. The average thickness of the polyimide substrate is preferably 10 to 200 μm, more preferably 10 to 100 μm, and particularly preferably 10 to 60 μm from the viewpoints of strength, pattern linearity, and PED suppression.

The average thickness of the polyimide substrate was measured by the following method.

The thickness of the polyimide substrate at 10 places was measured by observing a cross section in the thickness direction of the polyimide substrate using a Scanning Electron Microscope (SEM). The arithmetic mean of the obtained measurement values was taken as the average thickness of the polyimide substrate.

[ photosensitive transfer Material ]

In the method for manufacturing a patterned substrate according to the present invention, 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 ℃ or higher. In the method for producing a patterned substrate according to the present invention, the use of the photosensitive transfer material can suppress excessive diffusion of an acid in the photosensitive resin composition layer after exposure, and thus can suppress excessive acid decomposition reaction of the photosensitive resin composition layer. Therefore, the decrease in the pattern line width due to the passage of time after exposure can be suppressed.

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

[ temporary support body ]

The photosensitive transfer material has a temporary support. The temporary support is a support that supports the photosensitive resin composition layer and can be detached 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 subjected to pattern exposure. Here, the term "to have light transmittance" means that the transmittance of the dominant wavelength of light used for pattern exposure is 50% or more, and from the viewpoint of improving exposure sensitivity, the transmittance of the dominant wavelength of light used for pattern exposure is preferably 60% or more, and more preferably 70% or more. As a method for measuring the transmittance, there is a method of measuring with 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 the resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, and a polyimide film. Among the above, the biaxially stretched polyethylene terephthalate film is particularly preferable as the temporary support.

The thickness of the temporary support may be appropriately set depending on the material, from the viewpoints of the strength of the support, the flexibility required for bonding to the circuit wiring forming substrate, the light transmittance required in the first exposure step, and the like. The average thickness of the temporary support is preferably 5 to 200 μm, and more preferably 10 to 150 μm from the viewpoint of ease of handling, versatility, and the like. The average thickness of the temporary support is measured by a method based on the above-described method for measuring the average thickness of the polyimide substrate.

Preferable embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643. The descriptions of the above documents are incorporated by reference into this specification.

[ 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 ℃ or higher. By providing the photosensitive transfer material with a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher, it is possible to suppress a decrease in the line width of the pattern with 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 ℃ or higher is not limited, and known materials used for known acid-decomposable photosensitive resin composition layers can be used.

From the viewpoint of sensitivity and resolution, the photosensitive resin composition layer preferably contains an acid-decomposable resin and a photoacid generator, and more preferably contains: a polymer (hereinafter, also referred to as "polymer X") containing a structural unit (hereinafter, also referred to as "structural unit a") having an acid group protected by an acid-decomposable group, 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, an acid generated by reaction with active rays (active rays) acts as a catalyst for deprotection of a protected acid group in the polymer. Since the acid generated by the action of 1 photon contributes to many deprotection reactions, the quantum yield exceeds 1, and is a large value such as several powers of 10, for example, and high sensitivity is obtained as a result of so-called chemical amplification. On the other hand, when a quinonediazide compound is used as a photoacid generator which is sensitive to active light, a carboxyl group is generated by a sequential photochemical reaction, but the quantum yield thereof must be 1 or less, and a chemically amplified type is not satisfied.

(acid-decomposable resin)

The photosensitive resin composition layer contains an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher. When the photosensitive resin composition layer contains an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher, the decrease in the line width of the pattern due to the passage of time after exposure can be suppressed.

The acid-decomposable resin is not limited as long as it has a glass transition temperature of 50 ℃ or higher and can be decomposed by the action of an acid. Here, the term "decomposition" is not limited to a reaction simply accompanied by cleavage of a chemical bond, but also includes a reaction accompanied by conversion of a chemical structure. The acid-decomposable resin changes its polarity by the action of an acid, thereby increasing the solubility in a developer to be described later, for example.

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

The acid group protected by the acid-decomposable group is converted into an acid group by deprotection reaction by the action of a catalytic amount of an acidic substance such as an acid generated by exposure. The photosensitive resin composition layer can be dissolved in a developer by the acid group.

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. The polymer X may have a structural unit other than a 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).

Preferred embodiments of the structural unit a are described below.

Structural unit A-

The structural unit a is a structural unit having an acid group protected by an acid-decomposable group.

In the present invention, "acid group" means a proton-dissociable group having a pKa of 12 or less. From the viewpoint of improving the sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Also, the pKa of the acid group is preferably-5 or more. The acid group is preferably a carboxyl group or a phenolic hydroxyl group.

The acid-decomposable group is not limited, and a known acid-decomposable group can be used. Examples of the acid-decomposable group include a group which is relatively easily decomposed by an acid (for example, an acetal-type protecting group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group) and a group which is relatively hardly decomposed by an acid (for example, a tertiary alkyl group such as a tertiary butyl group or a tertiary alkyl chlorocarbonyl group such as a tertiary butyloxycarbonyl group (that is, a carbonate-type protecting group)).

Among the above, the acid-decomposable group is preferably a group having a structure protected in the form of acetal. From the viewpoint of sensitivity, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, still more preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group. In addition, 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 line width of the conductive wiring suitable for use in the formation of the conductive pattern.

From the viewpoint of sensitivity and resolution, the structural unit a is preferably at least one structural unit selected from the group consisting of a structural unit represented by formula a1, a structural unit represented by formula a2, and a structural unit represented by formula A3, which are described below.

[ chemical formula 1]

In the formula A1, R¹¹And R¹²Each independently represents a hydrogen atom, an alkyl group or an aryl group, R¹¹And R¹²At least one of which is alkyl or aryl, R¹³Represents alkyl or aryl, R¹¹Or R¹²And R¹³May be linked to form a cyclic ether, R¹⁴Represents a hydrogen atom or a methyl group, X¹Represents a single bond or a 2-valent linking group, R¹⁵Represents a substituent, and n represents an integer of 0 to 4.

In the formula A2, R²¹And R²²Each independently represents a hydrogen atom, an alkyl group or an aryl group, R²¹And R²²At least one of which is alkyl or aryl, R²³Represents alkyl or aryl, R²¹Or R²²And R²³May be linked to form a cyclic ether, R²⁴Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy 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 the formula A3, R³¹And R³²Each independently represents a hydrogen atom, an alkyl group or an aryl group, R³¹And R³²At least one of which is alkyl or aryl, R³³Represents alkyl or aryl, R³¹Or R³²And R³³May be linked to form a cyclic ether, R³⁴Represents a hydrogen atom or a methyl group, X⁰Represents a single bond or a 2-valent linking group.

Among the above, the structural unit a is more preferably a structural unit represented by formula a 3. The structural unit represented by formula a3 is a structural unit having a carboxyl group protected by an acetal type acid-decomposable group. By the polymer X including the structural unit represented by the formula a3, sensitivity at the time of pattern formation is excellent and resolution is more excellent.

In the formula A3, when R is³¹Or R³²When the alkyl group is used, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. In the formula A3, when R is³¹Or R³²When aryl, aryl is preferably phenyl. R³¹And R³²Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3, R³³The alkyl or aryl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

And, R³¹～R³³The alkyl group and the aryl group in (1) may have a substituent.

In the formula A3, R³¹Or R³²And R³³May be linked to form a cyclic ether, preferably R³¹Or R³²And R³³Linked to form a cyclic ether. The number of cyclic elements of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.

In the formula A3, X⁰Preferably a single bond or an arylene group, more preferably a single bond. X⁰The arylene group in (1) may have a substituent.

In the formula A3, R³⁴Represents 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 further lowered.

R in the formula A3 in relation to the total amount of structural units A contained in the polymer X³⁴The content of the structural unit which is a hydrogen atom is preferably 20% by mass or more.

In addition, R in the structural unit A and in the formula A3³⁴The content (content ratio: mass ratio) of the structural unit which is a hydrogen atom may be determined by¹³C-nuclear magnetic resonance spectroscopy (NMR) measurement was confirmed by measuring the intensity ratio of peak intensities calculated by a conventional method.

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

In the formulae a1 to A3, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, still more preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group, from the viewpoint of sensitivity.

The polymer X may contain 1 kind of the individual structural unit a, or may contain 2 or more kinds of the structural unit a.

The content of the structural unit a in the polymer X is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass, based on the total mass of the polymer X. If within the above range, the resolution is further improved.

When the polymer X contains 2 or more kinds of the structural unit a, the content of the above structural unit a represents the total content of 2 or more kinds of the structural unit a.

The content (content ratio: mass ratio) of the structural unit A in the polymer X can be determined by¹³The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by the conventional method.

Structural units having acid groups

The polymer X may contain a structural unit having an acid group (hereinafter, also referred to as "structural unit B"). The structural unit B is an acid group which is not protected by an acid-decomposable group, that is, a structural unit having an acid group without a protecting group. Since the polymer X contains the structural unit B, the sensitivity at the time of pattern formation is improved, and the polymer X is easily dissolved in an alkaline developer in a developing step after pattern exposure, and thus the developing time can be shortened.

Examples of the acid group in the structural unit B include a carboxyl group, a sulfone amide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonimide group. Among the above, the acid group is preferably a carboxyl group or a phenolic hydroxyl group, and more preferably a carboxyl group.

The polymer X may contain 1 kind of the structural unit B alone, or may contain 2 or more kinds of the structural unit B.

The content of the structural unit B in the polymer X is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, based on the total mass of the polymer X. If within the above range, the resolution becomes better.

When the polymer X contains 2 or more kinds of the structural units B, the content of the above structural unit B represents the total content of 2 or more kinds of the structural units B.

The content (content ratio: mass ratio) of the structural unit B in the polymer X can be determined by¹³The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by the conventional method.

Other structural units-

In addition to the structural unit a and the structural unit B, the polymer X preferably contains another structural unit (hereinafter, also referred to as "structural unit C") within a range that does not impair the effects of the method for producing a patterned substrate according to the present invention.

The monomer forming the structural unit C is not limited, and examples thereof include a styrene compound, an alkyl (meth) acrylate, a cyclic alkyl (meth) acrylate, an aryl (meth) acrylate, an unsaturated dicarboxylic acid diester, a bicyclic unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic anhydride, an unsaturated compound having an aliphatic ring skeleton, and other unsaturated compounds.

By adjusting at least any one of the kind and the content of the structural unit C, various characteristics of the polymer X can be adjusted. In particular, the inclusion of the structural unit C makes it possible to easily adjust the glass transition temperature, acid value, hydrophilicity, or hydrophobicity of the polymer X.

As the structural unit C, for example, examples thereof include a structural unit obtained by polymerizing styrene, a-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol (meth) acrylate Mono (meth) acrylate. Further, examples of the structural unit C include structural units obtained by polymerizing the compounds described in paragraphs 0021 to 0024 of Japanese patent laid-open No. 2004-264623.

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 is preferable.

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, 2, 2, 6, 6-tetramethyl-4-piperidyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-dimethylamino) propyl methacrylate, and mixtures thereof, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) 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. Among the above, 1, 2, 2, 6, 6-pentamethyl-4-piperidine methacrylate is preferable.

In addition, the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an alicyclic skeleton, from the viewpoint of improving the electrical characteristics of the photosensitive transfer material. Examples of the monomer forming each structural unit include styrene, α -methylstyrene, dicyclopentyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate, with cyclohexyl (meth) acrylate being preferred.

In addition, the monomer forming the structural unit C is preferably an alkyl (meth) acrylate from the viewpoint of adhesion. Among the above, from the viewpoint of adhesion, an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable. 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 1 kind of the individual structural unit C, or may contain 2 or more kinds of the 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, relative to 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. When the content is within the above range, the resolution and adhesion are further improved.

When the polymer X contains 2 or more kinds of the structural unit C, the content of the above structural unit C represents the total content of 2 or more kinds of the structural unit C.

Preferred examples of the polymer X in the present invention will be described below, but the present invention is not limited to the following examples. In addition, in order to obtain preferable physical properties, the ratio of the structural units and the weight average molecular weight in the following exemplary compounds can be appropriately selected.

[ chemical formula 2]

Process for the preparation of polymers X

The method for producing the polymer X (synthesis method) is not limited. The polymer X can be synthesized, for example, by polymerizing the monomer for forming the structural unit a, and further, if necessary, the monomer for forming the structural unit B and the monomer for forming the structural unit C in an organic solvent using a polymerization initiator. The polymer X may be synthesized by a so-called polymer reaction.

In view of resolution, the acid-decomposable resin (preferably the polymer X) preferably contains a structural unit derived from at least one (meth) acrylate compound selected from the group consisting of 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, 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.

Here, the term "ester site" used in the present invention is explained below. The expression "having A at an ester position" means that A is bonded to A bonding site (-0-) on the oxygen atom side of an ester bond (-C (═ O) -O-), that is, it means that A has A structure represented by "-C (═ 0) -O-A". For example, "a linear alkyl group having 1 to 3 carbon atoms at the ester position" means a bonding position where a linear alkyl group having 1 to 3 carbon atoms is bonded to the oxygen atom side of an ester bond. Further, if X represents a linear alkyl group having 1 to 3 carbon atoms, the expression "having a linear alkyl group having 1 to 3 carbon atoms at the ester position" means having a structure represented by "— C (═ O) -O-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, more preferably a cyclic alkyl group having 5 to 8 carbon atoms, and particularly preferably a cyclohexyl group.

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, more preferably a cyclic ether group having 5 to 8 carbon atoms, still more preferably a tetrahydrofuranyl group or a tetrahydropyranyl group, and particularly preferably a tetrahydrofuranyl group.

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

From the viewpoint of resolution, the acid-decomposable resin (preferably the 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 structural units derived from the above-described various acrylate compounds.

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

Among the above, the acid-decomposable resin (preferably the polymer X) preferably contains 90 mass% or more of a structural unit derived from at least one (meth) acrylate compound selected from the group consisting of 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, 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, based on the total mass of the acid-decomposable resin, and contains a structural unit derived from at least one acrylic compound selected from the group consisting of acrylic acid and acrylic ester compounds in an amount of 0 to 30% by mass based on the total mass of the acid-decomposable 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 value range.

(glass transition temperature)

The glass transition temperature of the acid-decomposable resin (preferably the polymer X) is 50 ℃ or higher, preferably 55 ℃ or higher, more preferably 60 ℃ or higher, still more preferably 70 ℃ or higher, and particularly preferably 80 ℃ or higher. When the glass transition temperature of the acid-decomposable resin is 50 ℃ or higher, the diffusion of an acid in the photosensitive resin composition layer after exposure can be suppressed, and therefore, an excessive acid decomposition reaction of the photosensitive resin composition layer can be suppressed. Therefore, the decrease in the pattern line width due to the passage of time after exposure can be suppressed.

The glass transition temperature of the acid-decomposable resin is preferably 110 ℃ or lower, more preferably 100 ℃ or lower, and still more preferably 90 ℃ or lower. Particularly preferably 85 ℃ or lower, most preferably 80 ℃ or lower. When the glass transition temperature of the acid-decomposable resin is 110 ℃ or lower, the lamination suitability can be improved under high temperature conditions.

Among the above, the glass transition temperature of the acid-decomposable resin is preferably 50 to 90 ℃, more preferably 55 to 90 ℃, still more preferably 55 to 85 ℃, particularly preferably 60 to 85 ℃, and most preferably 60 to 80 ℃. When the glass transition temperature of the decomposable resin is within the above numerical range, the reduction in the line width of the pattern due to the passage of time after exposure can be suppressed, and the lamination suitability can be improved under high temperature conditions.

The glass transition temperature of the acid-decomposable resin is determined by the following method based on JIS K7121: 1987, by the method described therein. The glass transition temperature in the present invention uses an extrapolated glass transition start temperature (hereinafter, also referred to as "Tig").

When the glass transition temperature is measured, the measurement apparatus is held to be stable at a temperature lower by about 50 ℃ than the glass transition temperature of the intended acid-decomposable resin, and then heated at a heating rate of 20 ℃/min to a temperature higher by about 30 ℃ than the temperature at which the glass transition is completed, thereby drawing a Differential Thermal Analysis (DTA) curve or a Differential Scanning Calorimetry (DSC) curve. The extrapolated glass transition start temperature (Tig), that is, the glass transition temperature in the present invention, is obtained as the temperature of the intersection of a straight line extending from a base line on the low temperature side to the high temperature side in the DTA curve or the DSC curve and a tangent drawn from the point where the gradient of the curve in the stepwise change portion of the glass transition becomes maximum.

In the present invention, as a method for adjusting the glass transition temperature of the acid-decomposable resin, for example, a method for adjusting the glass transition temperature using FOX formula as a pointer is given. According to the FOX formula, the glass transition temperature of the acid-decomposable resin can be adjusted based on the glass transition temperature of the homopolymer of each structural unit constituting the target acid-decomposable resin and the mass ratio of each structural unit.

The following description will be given of the formula FOX, taking as an example a copolymer containing the 1 st structural unit and the 2 nd structural unit.

When Tg of the homopolymer of the 1 st structural unit is represented by Tg1, the mass fraction of the 1 st structural unit in the copolymer is represented by W1, Tg of the homopolymer of the 2 nd structural unit is represented by Tg2, and the mass fraction of the 2 nd structural unit in the copolymer is represented by W2, TgO (K: Kelvin) of the copolymer comprising the 1 st structural unit and the 2 nd structural unit can be estimated from the following formula.

FOX formula: 1/TgO ═ W1/Tg1) + (W2/Tg2)

By adjusting the type and mass fraction of each structural unit constituting the copolymer using the above FOX formula, a copolymer having a desired glass transition temperature can be obtained.

Further, the glass transition temperature of the acid-decomposable resin can also be adjusted by adjusting the weight average molecular weight of the acid-decomposable resin.

Acid value-

The acid value of the acid-decomposable resin (preferably the polymer X) is preferably from 0mgKOH/g to 50mgKOH/g, more preferably from 0mgKOH/g to 20mgKOH/g, and particularly preferably from 0mgKOH/g to 10 mgKOH/g. When the acid value of the acid-decomposable resin is within the above numerical range, water hardly enters the photosensitive resin composition layer, and hence an excessive hydrolysis reaction of the unexposed photosensitive resin composition layer can be suppressed. Therefore, the pattern line width can be suppressed from decreasing.

In the present invention, the acid value represents the mass of potassium hydroxide required for neutralizing the acid component of each 1g of the measurement sample. Specifically, after a measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water (volume ratio) of 9/1, the resulting solution was neutralized and titrated with a 0.1mol/L aqueous sodium hydroxide solution AT 25 ℃ using a potential difference titration apparatus (for example, AT-510, manufactured by KYOTO electroluminescen corporation co., ltd.). The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated by the following formula.

Formula (II): a is 56.11 XVs 0.1 Xf/w

A: acid value (mgKOH/g)

Vs: amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration

f: titre of 0.1mol/L aqueous sodium hydroxide solution

w: measurement of the sample Mass (g) (conversion of solid content)

Molecular weight-

The molecular weight of the acid-decomposable resin (preferably the polymer X) is preferably 60,000 or less in terms of weight average molecular weight in terms of polystyrene. Since the weight average molecular weight of the acid-decomposable resin is 60,000 or less, when the photosensitive transfer material is bonded to a polyimide substrate, the photosensitive transfer material can be bonded within a temperature range (for example, 150 ℃ or less) in which deterioration of the film quality of the polyimide substrate can be suppressed.

The weight average molecular weight of the acid-decomposable resin is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

In the present invention, the weight average molecular weight of the acid-decomposable resin is measured by GPC (gel permeation chromatography). Various commercially available devices can be used as the measuring device, and the contents of the device and the measuring technique are well known to those skilled in the art.

In the measurement of the weight average molecular weight by Gel Permeation Chromatography (GPC), as a measurement apparatus, HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used. As the columns, 1 column was used in which TSKgel (registered trademark) Super HZM-M (4.6mmID × 15cm, manufactured by Tosoh Corporation), Super HZ4000(4.6mmID × 15cm, manufactured by Tosoh Corporation), Super HZ3000(4.6mmID × 15cm, manufactured by Tosoh Corporation), and Super HZ2000(4.6mmID × 15cm, manufactured by Tosoh Corporation) were connected in series, respectively. As eluent, THF (tetrahydrofuran) was used.

As the measurement conditions, the sample concentration was set to 0.2 mass%, the flow rate was set to 0.35 mL/min, the sample injection amount was set to 10 μ L, and the measurement temperature was set to 40 ℃. As the detector, a differential Refractive Index (RI) detector is used.

The calibration curve may use a "standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: any of 7 samples of "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" was prepared.

(content)

The photosensitive resin composition layer may contain 1 kind of the acid-decomposable resin alone, or may contain 2 or more kinds of the acid-decomposable resins. From the viewpoint of adhesion, the content of the acid-decomposable resin is preferably 50 to 99.9 mass%, and preferably 70 to 98 mass%, based on the total mass of the photosensitive resin composition layer.

(other Polymer)

The photosensitive resin composition layer may contain, in addition to the acid-decomposable resin, a polymer (hereinafter, also referred to as "other polymer") that does not contain a structural unit having an acid group protected by an acid-decomposable group. In the present invention, the acid-decomposable resin and the other polymer are collectively referred to as "polymer component". Further, even if the compound corresponding to a crosslinking agent, a dispersant and a surfactant described later is a polymer compound, it is not included in the polymer component.

Examples of the other polymer include polyhydroxystyrene. Examples of commercially available polyhydroxystyrenes include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P and SMA 3840F (manufactured by Sartomer Co., Ltd.), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (manufactured by TOAGOSEI CO., LTD., Ltd.), and Joneryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (manufactured by BASF Co., Ltd.).

The photosensitive resin composition layer may contain 1 kind of other polymer alone, or may contain 2 or more kinds 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, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, relative to the total mass of the polymer components.

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

(photoacid generators)

The photosensitive resin composition layer preferably contains a photoacid generator.

The photoacid generator used in the present invention is a compound capable of generating an acid by irradiation with active light such as ultraviolet light, far ultraviolet light, X-rays, and electron beams.

The photoacid generator is preferably a compound that generates an acid by being induced by active light having a wavelength of 300nm or longer (preferably, a wavelength of 300nm to 450nm), but the chemical structure thereof is not limited. The photoacid generator which does not directly sense active light having a wavelength of 300nm or more may be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by sensing active light having a wavelength of 300nm or more with the sensitizer.

The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited. The pKa is preferably at least-10.0, 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 salt compounds or triarylsulfonium salt compounds are particularly preferable.

The ionic photoacid generator described in paragraphs 0114 to 0133 of Japanese patent application laid-open No. 2014-85643 can also be preferably used.

Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among the above, oxime sulfonate compounds are preferable from the viewpoint of sensitivity, resolution and adhesion. Specific examples of the trichloromethyl s-triazine compound, diazomethane compound and imide sulfonate compound include those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

As the oxime sulfonate compound, the oxime sulfonate compounds 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 1 compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably contains an oxime sulfonate compound.

Further, examples of a preferable photoacid generator include those having the following structures.

[ chemical formula 3]

The photosensitive resin composition layer may contain 1 kind of the photoacid generator alone, or may contain 2 or more kinds of the photoacid generator.

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

(other additives)

The photosensitive resin composition layer may contain other additives as necessary.

As the other additives, known additives can be used, and examples thereof include a plasticizer, a sensitizer, a heterocyclic compound, an alkoxysilane compound, a basic compound, a rust inhibitor, and a surfactant.

Examples of the plasticizer, sensitizer, heterocyclic compound, and alkoxysilane compound include plasticizers, sensitizers, heterocyclic compounds, and alkoxysilane compounds described in paragraphs 0097 to 0119 of international publication No. 2018/179640.

The photosensitive resin composition layer may contain a solvent. When the photosensitive resin composition layer is formed from a 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 further preferably 1% by mass or less, relative to the total mass of the photosensitive resin composition layer.

Basic compounds-

The photosensitive resin composition layer preferably contains a basic compound.

The basic compound may be arbitrarily selected from basic compounds used for chemically amplified resists. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium carboxylates. Specific examples of the basic compound include compounds described in paragraphs 0204 to 0207 of Japanese patent application laid-open publication No. 2011-221494, and the contents of these are incorporated in the present specification.

Further, as the basic compound, N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea (CMTU) can be preferably used. Further, as a commercial product of CMTU, there is exemplified CMTU manufactured by Toyo Kasei kogyo.

As the basic compound, a benzotriazole compound is preferable from the viewpoint of being suitable for the linearity of the conductive wiring at the time of forming the conductive pattern.

The benzotriazole compound is not limited as long as it has a benzotriazole skeleton, and a known benzotriazole compound 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-benzotriazol-1-ylmethyl) -9H-carbazole, 1-chloro-1H-benzotriazole, 1- (2-pyridyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1' -hydroxyethyl) benzotriazole, 1- (2-pyridyl) benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, and the like, 1-propylbenzotriazole, 1- (1 ' -hydroxypropyl) benzotriazole, 1- (2 ' -hydroxypropyl) benzotriazole, 1- (3 ' -hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzotriazole, 5-methyl-1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethyl benzotriazole-5-carboxylate, tert-butyl benzotriazole-5-carboxylate, cyclopentylethyl benzotriazole-5-carboxylate, 1H-benzotriazole-1-acetonitrile, 1H-benzotriazole-1-carboxyaldehyde, 2-methyl-2H-benzotriazole, 2-ethyl-2H-benzotriazole and the like.

The photosensitive resin composition layer may contain 1 kind of the basic compound alone, or may contain 2 or more kinds of the basic compounds.

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

Surfactants-

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. Preferably, the surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include a polyoxyethylene higher alkyl ether surfactant, a polyoxyethylene higher alkyl phenyl ether surfactant, a higher fatty acid diester surfactant of polyoxyethylene glycol, a silicone surfactant, and a fluorine surfactant.

Examples of the surfactant include surfactants described in paragraphs 0120 to 0125 of International publication No. 2018/179640.

Further, as a commercially available surfactant, for example, Megaface (registered trademark) F-552 or F-554 (manufactured by DIC CORPORATION, supra) can be used.

The surfactant described in paragraph 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 1 kind of surfactant alone, or may contain 2 or more kinds of surfactants.

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

The photosensitive resin composition layer of the present invention may contain, as additives other than the above, known additives such as metal oxide particles, antioxidants, dispersants, acid growth promoters, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents.

Preferred embodiments of these components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-85643, the contents of which 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 to 20 μm. When the thickness of the photosensitive resin composition layer is 20 μm or less, the pattern resolution 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 to 15 μm, and particularly preferably 1.0 to 10 μm.

The average thickness of the photosensitive resin composition layer is measured by a method based on the above-described method for measuring the average thickness of the polyimide substrate.

(method for Forming photosensitive resin composition layer)

The photosensitive resin composition layer can be formed by using a photosensitive resin composition containing a component for forming the photosensitive resin composition layer and a solvent. The composition may be prepared by dissolving each component in a solvent in advance to prepare a solution, and then mixing the obtained solutions 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 to 30 μm.

In the present invention, the photosensitive resin composition layer in the present invention can be formed, for example, by applying the photosensitive resin composition on a temporary support or a protective film and drying it.

The coating method is not limited, and slit coating, spin coating, curtain coating, and inkjet coating can be mentioned.

Further, an intermediate layer or another layer described later may be formed on the temporary support or the protective film, and then the photosensitive resin composition layer may be formed.

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

Furthermore, a solvent having a vapor pressure of 1kPa or more and 16kPa or less at 20 ℃ as described in paragraph 0014 of Japanese patent application laid-open No. 2018-177889 can be preferably used.

The solvent that can be used in the present invention may be used alone in 1 kind or in combination in 2 kinds.

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

[ intermediate layer ]

The photosensitive transfer material according to the present invention 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. Further, when the polymer contained in the intermediate layer is a water-soluble resin, the water-soluble resin may also have alkali solubility. When the polymer contained in the intermediate layer is an alkali-soluble resin, the alkali-soluble resin may also have water solubility.

In the present invention, "water-soluble" means that the solubility in 100g of water having a pH of 7.0 at 22 ℃ is 0.1g or more, and "alkali-soluble" means that the solubility in 100g of a1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more.

The solubility of the polymer in 100g of water having a pH of 7.0 at 22 ℃ is preferably 1g or more, more preferably 5g or more.

Examples of the water-soluble resin include a cellophane resin, a polyvinyl alcohol resin, a polyvinyl pyrrolidone resin, an acrylamide resin, (meth) acrylate resin, a polyethylene oxide resin, gelatin, a vinyl ether resin, a polyamide resin, and a copolymer thereof. Among the above, the water-soluble resin is preferably a cellulose resin, and more preferably at least 1 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 which can form a salt is more preferable.

The intermediate layer may contain 1 kind of single polymer or 2 or more kinds of polymers.

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

(pH sensitive pigment)

From the viewpoint of ease of confirmation of an exposure pattern, the intermediate layer preferably contains a pH-sensitive dye having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and a maximum absorption wavelength that changes depending on pH.

Here, the "change in maximum absorption wavelength" may mean any of a mode in which a dye in a colored state is decolored, a mode in which a dye in a decolored state is colored, and a mode in which a dye in a colored state is changed to a colored state of another color.

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

Confirmation of pH-sensitive pigments can be carried out by the following method.

0.1g of a dye was dissolved in 100mL of a mixed solution of ethanol and water (ethanol/water: 1/2[ mass ratio), and 0.1mol/L (1N) of a hydrochloric acid aqueous solution was added to adjust the pH to 1. Titration was carried out with 0.01mol/L (0.01N) aqueous sodium hydroxide solution, and a color change and pH at which the color change occurred were confirmed. In addition, the pH was a value measured at 25 ℃ using a pH meter (model: HM-31, manufactured by DKK-TOA CORPORATION).

The method for measuring the maximum absorption wavelength in the present invention is to use a spectrophotometer at 25 ℃ in an atmospheric environment: UV3100 (manufactured by SHIMADZU CORPORATION) measures a transmission spectrum in a range of 400nm to 780nm, and measures a wavelength at which the intensity of light becomes extremely small (maximum absorption wavelength).

Examples of the coloring matter decolorized by exposure to light include a leuco compound, a diphenylmethane coloring matter, an oxazine coloring matter, a xanthene coloring matter, an iminonaphthoquinone coloring matter, an azomethine coloring matter, and an anthraquinone coloring matter.

Among the above, as the coloring matter, a colorless compound is preferable from the viewpoint of visibility.

Examples of the colorless compound include colorless compounds such as triarylmethane-based (e.g., triphenylmethane-based), spiropyran-based, fluorane-based, diphenylmethane-based, rhodamine lactam-based, indolylphthalide-based, and leucoauramine-based compounds. Among these, colorless compounds having a triarylmethane skeleton (i.e., triarylmethane-based dyes) are preferable, and triphenylmethane-based dyes are more preferable.

The colorless compound is preferably a colorless compound having a lactone ring, a sulfintone (sulfene) ring, or a sultone ring, and having a lactone ring, a sulfintone ring, or a sultone ring opened or closed, and more preferably a colorless compound having a sultone ring, and having a sultone ring closed and decolored, from the viewpoint of visibility.

The dye is preferably a water-soluble compound for the purpose of preventing defects caused by precipitation of the dye.

The solubility of the dye in 100g of water having a pH of 7.0 at 22 ℃ is preferably 1g or more, more preferably 5g or more.

The intermediate layer may contain 1 kind of single dye or 2 or more kinds of dyes.

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

(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 no silicon atom can be used. Among the above, the surfactant is preferably a surfactant having a fluorine atom, and more preferably a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group, from the viewpoint of suppressing the occurrence of streaks in the photosensitive resin composition layer and the intermediate layer and the adhesion.

As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic (nonionic surfactant) and an amphoteric surfactant can be used, but the surfactant is preferably a nonionic surfactant.

From the viewpoint of suppressing precipitation of the surfactant, the surfactant preferably has a solubility of 1g or more in 100g of water at 25 ℃.

The intermediate layer may contain 1 kind of surfactant alone, or may contain 2 or more kinds of surfactants.

From the viewpoint of suppressing the occurrence of streaks in the photosensitive resin composition layer and the intermediate layer and the adhesion, the content of the surfactant in the intermediate layer is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and particularly preferably 0.2 to 0.5% by mass, based on the total mass of the intermediate layer.

(inorganic Filler)

The intermediate layer may contain an inorganic filler. Examples of the inorganic filler include silica particles, alumina particles, and zirconia particles, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle diameter are preferable, and an inorganic filler having an average particle diameter of 100nm or less is more preferable. For example, SNOWTEX (registered trademark) is preferably used if it is a commercially available product.

From the viewpoint of adhesion between the intermediate layer and the photosensitive layer, the volume fraction of the particles in the intermediate layer (the volume ratio of the particles in the intermediate layer) is preferably 5% to 90%, more preferably 10% to 80%, and particularly preferably 20% to 60%, relative to the total volume of the intermediate layer.

(pH adjuster)

The intermediate layer may contain a pH adjuster. By containing the pH adjuster in the intermediate layer, the colored state or decolored state of the coloring matter in the intermediate layer can be maintained more stably, and the adhesion between the photosensitive resin composition layer and the intermediate layer can be further improved.

Examples of the pH adjuster include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, and organic ammonium salts. From the viewpoint of water solubility, the pH adjuster is preferably sodium hydroxide. 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)

From the viewpoint of adhesion between the photosensitive resin composition layer and the intermediate layer and pattern formability, the average thickness of the intermediate layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 2 μm.

The average thickness of the intermediate layer is preferably smaller than the average thickness of the photosensitive resin composition layer.

The average thickness of the intermediate layer is measured by a method based on the above-described method for measuring the average thickness of the polyimide substrate.

The intermediate layer may have 2 or more layers.

When the intermediate layer has 2 or more layers, the average thickness of each layer is not limited as long as it is within the above range, but in the 2 or more layers of the intermediate layer, the average thickness of the layer closest to the photosensitive resin composition layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 2 μm, from the viewpoint of the adhesion between the intermediate layer and the photosensitive resin composition layer and the pattern formability.

(method of Forming intermediate layer)

The intermediate layer can be formed by using an intermediate layer-forming composition containing a component for forming the intermediate layer and a water-soluble solvent. The composition may be prepared by preliminarily dissolving each component in a solvent and then mixing the resulting solutions at a predetermined ratio. The composition prepared as described above may be filtered using a filter having a pore size of 3.0. mu.m.

In the present invention, for example, the intermediate layer can be formed on the temporary support by applying the intermediate layer forming composition on 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 water is preferably contained. Examples of the alcohol 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 a 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 1 μm to 2mm, for example. The average thickness of the protective film is measured by a method based on the above-described 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 "other layer"). Examples of the other layer include a contrast-enhancing layer and a thermoplastic resin layer.

Preferable modes for the contrast enhancement layer are described in paragraph 0134 of international publication No. 2018/179640, preferable modes for the thermoplastic resin layer are described in paragraphs 0189 to 0193 of japanese patent application laid-open No. 2014-85643, and preferable modes for the other layers are described in paragraphs 0194 to 0196 of japanese patent application laid-open No. 2014-85643, the contents of which are incorporated in the present specification.

Here, referring to fig. 1, an example of the layer structure of the photosensitive transfer material is schematically shown.

The photosensitive transfer material 100 shown in FIG. 1 is formed by laminating 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 in this order. The transfer layer 14 is a layer transferred (i.e., laminated) onto the polyimide substrate by the above-described bonding step.

[ method for producing 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 the photosensitive transfer material, a method including a step of applying a photosensitive resin composition onto a temporary support and drying the applied photosensitive resin composition to form a photosensitive resin composition layer is preferably used. When the photosensitive transfer material has an intermediate layer, a method including a step of applying and drying the intermediate layer-forming composition on the temporary support to form the intermediate layer and a step of applying and drying the photosensitive resin composition on the intermediate layer to form the photosensitive resin composition layer is preferable.

The method for producing a photosensitive transfer material according to the present invention 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.

< method for manufacturing circuit substrate >

The method for manufacturing a circuit board according to the present invention is not limited as long as the method for manufacturing a circuit board is a method for manufacturing a circuit board by applying the method for manufacturing a substrate with a pattern described above using a polyimide substrate having a conductive layer. The method for manufacturing a circuit board according to the present invention preferably includes, in order: a step of manufacturing a patterned substrate by the method for manufacturing a patterned substrate (hereinafter, also referred to as a "substrate manufacturing step"); a step of etching the conductive layer exposed in a region of the patterned substrate where the pattern of the photosensitive resin composition 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 a "removal step"). The method for manufacturing a circuit board according to the present invention, which includes the above steps, can suppress a decrease in line width of circuit wiring due to the passage of time after exposure, and has excellent lamination suitability under high temperature conditions.

In a preferred embodiment of the method for manufacturing a circuit board according to the present invention, after the removing step, the bonding step, the exposing step, the developing step, and the etching step are repeated a plurality of times while 4 steps are set as 1 group. By the above method, for example, 2 or more different conductive patterns can be formed.

A preferred embodiment of the method for manufacturing a circuit board according to the present invention is a method in which the pattern of the photosensitive resin composition layer is subjected to the exposure step and then the development step before the etching step and the removal step. By the above method, for example, 2 or more different conductive patterns can be formed.

Further, the polyimide substrate can be reused (reworked). In the photosensitive resin composition layer, since the solubility of the exposed portion is improved by using a photosensitizer or the like which generates an acid by irradiation with active light, for example, irradiation with active light, neither the exposed portion nor the unexposed portion is cured at the time of pattern exposure, and the substrate can be reused (reworked) by full-surface exposure or the like in the case where the shape of the obtained pattern is defective.

As an embodiment of the method for manufacturing a circuit board according to the present invention, international publication No. 2006/190405, the contents of which are incorporated herein, can be referred to.

[ Process for producing substrate ]

The method for manufacturing a circuit board according to the present invention preferably includes a step of manufacturing a patterned substrate by the method for manufacturing a patterned substrate. In the above step, the polyimide substrate included in the patterned substrate preferably has a conductive layer, and at least one surface thereof has a conductive layer. The preferred embodiments of the method for manufacturing a patterned substrate and the materials used in the method are the same as those described in the above "method for manufacturing a patterned substrate".

[ etching Process ]

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

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

The method of the etching treatment is not limited, and a known method can be applied. Examples of the etching treatment include the methods described in, for example, paragraphs 0048 to 0054 of jp 2010-152155 a and a known dry etching method using plasma etching or the like.

As a method of the etching treatment, for example, a wet etching method in which the substrate is immersed in an etching solution is generally performed. The etching solution used for wet etching may be an acid type or an alkali type etching solution, as appropriate, depending on the etching target.

Examples of the acidic etching solution include an aqueous solution of a single acidic component such as hydrochloric acid, sulfuric acid, hydrofluoric acid, or phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, or potassium permanganate. The acidic component may be a combination of a plurality of acidic components.

Examples of the alkaline etching solution include an aqueous solution of a single alkali component such as a salt of an organic amine such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or tetramethylammonium hydroxide, and a mixed aqueous solution of an alkali component and a salt such as potassium permanganate. The alkali component may be a combination of a plurality of alkali components.

The temperature of the etching solution is not limited, but is preferably 45 ℃ or lower. The resin pattern used as an etching mask (etching pattern) in the present invention preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature region of 45 ℃ or lower. Therefore, the photosensitive resin composition layer can be prevented from peeling off in the etching step, and a portion where the photosensitive resin composition layer is not present can be selectively etched.

After the etching step, in order to prevent contamination of the process line, a cleaning step of cleaning the substrate subjected to the etching treatment and a drying step of drying the cleaned substrate may be performed as necessary.

[ removal Process ]

The method for manufacturing a circuit board according to the present invention preferably includes a step of removing the pattern of the photosensitive resin composition layer.

The removal step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.

The method for removing the residual photosensitive resin composition layer is not particularly limited, and a method for removing by a chemical treatment may be mentioned, and a removing liquid may be particularly preferably used.

The method for removing the photosensitive resin composition layer includes a method in which a substrate having the photosensitive resin composition layer and the like is immersed in a removing solution under stirring at preferably 30 to 80 ℃ (more preferably 50 to 80 ℃) for 1 to 30 minutes.

Examples of the removal solution include a solution obtained by dissolving an inorganic base component such as sodium hydroxide or potassium hydroxide, or an organic base component such as a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.

The removal liquid may be used, and the removal liquid may be removed by a spraying method, a shower method, a spin coating immersion method, or the like.

[ Whole surface Exposure Process ]

The method for manufacturing a circuit board according to the present invention preferably includes a step of exposing the photosensitive resin composition layer to full-surface light (hereinafter, also referred to as "full-surface exposure step") between the step of performing etching (etching step) and the step of removing (removing step).

The method for manufacturing a circuit board according to the present invention may further include a step of heating the photosensitive resin composition layer exposed on the entire surface (hereinafter, also referred to as "heating step") as necessary. The entire surface exposure step and the heating step are preferably performed after the etching step and before the removal step.

After the etching step, the photosensitive resin composition layer used as an etching mask is exposed over the entire surface thereof, whereby the solubility in the removing solution and the permeability of the removing solution are improved, and the removing solution is excellent in the removability even when the removing solution is used for a long time. When the heating step is included, the reaction rate of the photoacid generator and the reaction rate of the generated acid with the photosensitive resin can be further increased by the heating step, and as a result, the removal performance can be improved.

The light source used for exposure in the entire surface 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.

The exposure amount in the whole exposure step is preferably 5mJ/cm from the viewpoint of removability²～1,000mJ/cm²More preferably 10mJ/cm²～800mJ/cm²Particularly preferably 100mJ/cm²～500mJ/cm²。

From the viewpoint of removability, the exposure amount in the whole area exposure step is preferably equal to or greater than the exposure amount in the exposure step, and more preferably greater than the exposure amount in the exposure step.

[ other Processes ]

The method of manufacturing a circuit board according to the present invention may include steps other than the above steps (hereinafter, also referred to as "other steps"). Examples of the other steps include, but are not limited to, the following steps.

Further, as examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of Japanese patent application laid-open No. 2006-23696 can also be preferably used in the present invention.

(protective film peeling step)

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

(step of reducing reflectance of visible ray)

The method for manufacturing a circuit board according to the present invention may include a step of performing a treatment for reducing the visible light reflectance of a part or all of the conductive layer on the polyimide substrate.

As the treatment for reducing the visible light reflectance, for example, oxidation treatment may be mentioned. For example, the visible light reflectance can be reduced by making copper into copper oxide by oxidation treatment and blackening it.

Preferable modes of the treatment for reducing the reflectance of visible rays are described in paragraphs 0017 to 0025 of Japanese patent laid-open publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese patent laid-open publication No. 2013-206315, the contents of which are incorporated in the present specification.

(step of Forming insulating film and step of Forming New conductive layer on insulating film)

The method for manufacturing a circuit board according to the present invention preferably further includes: forming an insulating film on a conductive pattern formed on a polyimide substrate; and forming a new conductive layer on the insulating film.

With the above configuration, a new conductive layer can be formed while insulating from a previously formed conductive pattern.

The step of forming the insulating film is not limited, and a known method of forming a permanent film may be used. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.

The step of forming a new conductive layer on the insulating film is not limited, and a photosensitive material having conductivity may be used to form a new conductive layer having a desired pattern by photolithography.

In the method for manufacturing a circuit board according to the present invention, it is preferable to use a polyimide substrate having a plurality of conductive layers on both surfaces thereof, and to form a circuit on the conductive layers formed on both surfaces of the polyimide substrate sequentially or simultaneously. With the above configuration, the circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the polyimide substrate and the second conductive pattern is formed on the other surface can be formed. Further, it is also preferable that the circuit wiring for a touch panel having the above-described structure is formed on both surfaces of the polyimide substrate by roll-to-roll.

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

< method for manufacturing touch panel >

One embodiment of a method for manufacturing a touch panel according to the present invention includes the method for manufacturing the circuit board.

Another embodiment of the method for manufacturing a touch panel according to the present invention includes a step of preparing a circuit board manufactured by the method for manufacturing a circuit board. In the above embodiments, the touch panel is manufactured using the circuit substrate according to the present invention.

In the above embodiments, the preferred embodiments of the method for manufacturing a circuit board are the same as those described in the above "method for manufacturing a circuit board".

In addition to the above, a known method for manufacturing a touch panel can be used for the method for manufacturing a touch panel according to the present invention.

The method for manufacturing a touch panel according to the present invention may have any process (other process) other than the above-described process.

Fig. 2 and 3 show an example of a mask pattern used in the method for manufacturing a touch panel according to the present invention.

In the pattern shown in fig. 2 and the pattern shown in fig. 3, SL and G are non-image portions (light-shielding portions), and DL virtually shows an alignment frame. In the method for manufacturing a touch panel according to the present invention, for example, a touch panel in which circuit wirings having patterns corresponding to SL and G are formed can be manufactured by exposing the photosensitive resin composition layer through a mask having the pattern shown in fig. 2. Specifically, the gene can be produced by the method described in fig. 1 of international publication No. 2016/0190405. In an example of the touch panel to be manufactured, G is a portion where a transparent electrode (electrode for touch panel) is formed, and SL is a portion where a wiring of a peripheral extraction portion is formed.

The touch panel according to the present invention is a touch panel including at least a circuit board manufactured by the method for manufacturing a circuit board according to the present invention. The touch panel according to the present invention preferably includes at least a transparent substrate, an electrode, an insulating layer, or a protective layer.

The detection method in the touch panel according to the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among the above, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include so-called In-cell (e.g., the contents described In fig. 5, 6, 7, and 8 of jp 2012-517051 a), so-called On-cell (e.g., the contents described In fig. 19 of jp 2013-168125 a, the contents described In fig. 1 and 5 of jp 2012-89102 a), OGS (One Glass Solution), TOL (Touch-On-Lens) (e.g., the contents described In fig. 2 of jp 2013-54727 a), other structures (e.g., the contents described In fig. 6 of jp 2013-164871 a), and various Out-cell (e.g., so-called GG, G1-G2, GFF, GF2, GF1, G1F).

< laminate >

The laminate according to the present invention comprises: a polyimide substrate; and a photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher. By having the above-described structure, the laminate according to the present invention can suppress excessive diffusion of an acid in the photosensitive resin composition layer after exposure when the laminate according to the present invention is exposed to light, and thus can suppress excessive acid decomposition reaction of the photosensitive resin composition layer. Therefore, the decrease in the pattern line width due to the passage of time after exposure can be suppressed.

In the laminate according to the present invention, the preferred embodiments of the polyimide substrate and the photosensitive resin composition layer are the same as those described in the above "method for producing a patterned substrate".

In the laminate according to the present invention, 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 (i.e., a method of bonding a photosensitive transfer material and a polyimide substrate).

When the polyimide substrate has conductivity, the laminate of the present invention preferably comprises, in order, the polyimide substrate, the conductive layer, and the photosensitive resin composition layer containing an acid-decomposable resin having a glass transition temperature of 50 ℃ or higher.

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

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In addition, "part" and "%" are based on mass unless otherwise specified.

< abbreviation >

The following abbreviations used in the examples represent the following compounds, respectively.

"MATHF": 2-tetrahydrofurfuryl methacrylate (synthetic product, methacrylate compound having a cyclic ether group at the ester position)

"THFHS": 4- (2-tetrahydrofuryloxy) styrene (synthetic product)

"ATHF": 2-tetrahydrofurfuryl acrylate (synthetic product, acrylate compound having a cyclic ether group at the ester position)

"MAA": methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.; Ltd.)

"MMA": methyl methacrylate (a methacrylate compound having a linear alkyl group at the ester position, manufactured by Tokyo Chemical Industry Co., Ltd.)

"CHMA": cyclohexyl methacrylate (a methacrylate compound having a cyclic alkyl group at the ester position, manufactured by Tokyo Chemical Industry Co., Ltd.)

"EA": ethyl acrylate (an acrylate compound having a linear alkyl group at the ester position, manufactured by Tokyo Chemical Industry Co., Ltd.)

"EHMA": 2-ethylhexyl methacrylate (a methacrylate compound having a branched alkyl group at the ester position, manufactured by Tokyo Chemical Industry Co., Ltd.)

"MPMP": 1, 2, 2, 6, 6-Pentamethyl-4-piperidinylmethacrylate (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 ester (2, 2' -azobis (2-methylpropionate)) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

< Synthesis of MATHF >

Methacrylic acid (86.1 parts by mass, 1.0 molar equivalent) and hexane (86.1 parts by mass) were added to a three-necked flask, and cooled to 20 ℃. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass and 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass and 1.0 mol equivalent), the mixture was stirred at 20 ℃. + -. 2 ℃ for 1.5 hours. Subsequently, the liquid temperature was raised to 35 ℃ and stirred for 2 hours. KYOWAAD200 and KYOWAAD1000 (both manufactured by Kyowa Chemical Industry co., ltd.) were sequentially laid on a suction filter, and then the reaction solution was filtered to obtain a filtrate. To the resulting filtrate, MEHQ (4-methoxyphenol (manufactured by Tokyo Chemical Industry co., ltd.) and 0.0012 parts by mass) were added, and then concentrated under reduced pressure at 40 ℃ to obtain 156.2 parts by mass of 2-tetrahydrofurfuryl methacrylate (MATHF, tetrahydro-2H-furan-2-yl methacrylate) 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 ℃. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass and 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass and 1.0 mol equivalent), the temperature was raised to 80 ℃ and the mixture was stirred for 5 hours. KYOWAAD200 and KYOWAAD1000 (both manufactured by Kyowa chemical industry co., ltd.) were sequentially laid on a suction filter, and then the reaction solution was filtered to obtain a filtrate. MEHQ (0.0019 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ℃ to obtain 185.0 parts by mass of 4- (2-tetrahydrofuryloxy) styrene (THFHS, 4- (2-tetrahydrofuryloxy) styrene) 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 a three-necked flask, and cooled to 20 ℃. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass and 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass and 1.0 mol equivalent), the mixture was stirred at 20 ℃. + -. 2 ℃ for 1.5 hours. Subsequently, the liquid temperature was raised to 35 ℃ and stirred for 2 hours. KYOWAAD200 and KYOWAAD1000 (both manufactured by Kyowa Chemical Industry co., ltd.) were sequentially laid on a suction filter, and then the reaction solution was filtered to obtain a filtrate. To the resulting filtrate, MEHQ (0.0012 parts by mass) was added, and then concentrated under reduced pressure at 40 ℃ to obtain 140.8 parts by mass of 2-tetrahydrofurfuryl acrylate (ath f, tetrahydro-2H-furan-2-yl acrylate) as a colorless oil (yield 99.0%).

< Synthesis of Polymer A-1 >

Propyl acetate (75.0 parts by mass, manufactured by SHOWA DENKO k.k.) was added to a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution containing 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) was added dropwise to the solution in the above three-necked flask maintained at a temperature in the range of 90 ℃. + -. 2 ℃ over a period of 2 hours. After completion of the dropwise addition, the mixture was stirred at a temperature of 90 ℃. + -. 2 ℃ for 2 hours, thereby obtaining a solution containing the polymer A-1 (solid content concentration: 40.0%).

< Synthesis examples of polymers A-2 to A-11

Solutions containing each of polymers A-2 to A-11 were obtained in the same manner as for polymer A-1 except that the kinds and amounts of monomers used were changed as shown in Table 1 below. The solid content concentration in the solution was set to 40.0 mass%.

[ Table 1]

In table 1, "monomer a" represents a monomer forming a structural unit having an acid group protected by an acid-decomposable group. In table 1, "monomer B" represents a monomer that forms a structural unit other than a structural unit having an acid group protected by an acid-decomposable group. In Table 1, "-" indicates that the corresponding monomer was not used. The glass transition temperature (Tg), acid value, and weight average molecular weight (Mw) shown in table 1 were measured by the methods described above.

< examples 1 to 12 and comparative examples 1 to 2 >

[ production of photosensitive transfer Material ]

After weighing the solutions containing the polymers (a-1 to a-11), the photoacid generator, the basic compound, and the surfactant so as to have the solid content mass ratios shown in table 2 below, the above components were dissolved and mixed with propyl acetate to obtain a mixed solution having a solid content concentration of 10 mass%. The mixture was filtered through a filter made of polytetrafluoroethylene having a diameter of 0.2 μm to obtain a photosensitive resin composition (composition for photosensitive transfer material). The photosensitive resin composition was applied to a 30 μm thick polyethylene terephthalate film as a temporary support using a slit nozzle so that the dry film thickness became 4.0 μm. Thereafter, the resultant was passed through a drying zone having an average temperature of 85 ℃ for 50 seconds, thereby forming a photosensitive resin composition layer on the temporary support. Finally, a polyethylene film (OSM-N, manufactured by Tredegar Corporation) as a protective film was pressure-bonded to the photosensitive resin composition layer, thereby producing photosensitive transfer materials of examples 1 to 12 and comparative examples 1 to 2, respectively.

[ production of substrate ]

Copper layers having a thickness of 500nm were stacked on the respective substrates shown in table 2 below by sputtering, thereby producing substrates with copper layers.

[ evaluation of sensitivity (Exposure sensitivity) ]

The photosensitive transfer materials thus produced were bonded to a substrate having a copper layer under lamination conditions of a roll temperature of 130 ℃, a line pressure of 0.8MPa and a line speed of 3.0 m/min. The photosensitive resin composition layer was exposed using an ultra-high pressure mercury lamp without peeling off the temporary support and with a line-to-space pattern (Duty ratio of 1: 1) mask having a line width of 20 μm, and then left to stand for 1 hour, after which the temporary support was peeled off and developed. Development was carried out for 40 seconds by shower development using a 0.9% aqueous sodium carbonate solution at 22 ℃. When a line and space pattern having a line width of 20 μm was formed by the above method, the residue in the space of 20 μm was observed by using a Scanning Electron Microscope (SEM), and the exposure amount at which the residue completely disappeared was determined. The exposure amount was set to an exposure amount applied for the following evaluation (resolution evaluation, pattern width change rate).

[ evaluation ]

(lamination adaptability (roll-to-roll mode))

After the protective film was peeled off from each of the produced photosensitive transfer materials, the photosensitive transfer materials were bonded to the substrate with the copper layer in a roll-to-roll manner under lamination conditions of a roll temperature of 130 ℃, a line pressure of 0.8MPa, and a line speed (conveyance speed) of 3.0 m/min. A 50cm square test piece was cut out from the roll after the bonding, and the adhesion state of the photosensitive resin composition and the copper layer was visually confirmed. The area ratio (%) of the photosensitive resin composition layer to the copper layer in the state where no foam or floating was present in the test piece was determined by the following formula, and the lamination suitability under high temperature and high speed conditions was evaluated according to the following criteria. The evaluation results are shown in table 2. The larger the adhesion area (%) of the photosensitive resin composition layer, the more excellent the lamination suitability under high-temperature and high-speed conditions.

Formula (II): area (%) ([ (area of adhesion of photosensitive resin composition layer)/(area of test piece) ] × 100

-benchmark-

The area (%) was 95% or more, and the photosensitive resin composition layer was not cracked: 5

The area (%) was 95% or more, but the photosensitive resin composition layer had cracks: 4

Area (%) is 85% or more and less than 95%: 3

Area (%) less than 85%: 2

(resolution)

The photosensitive transfer materials thus produced were bonded to a substrate having a copper layer under lamination conditions of a roll temperature of 130 ℃, a line pressure of 0.8MPa and a line speed of 3.0 m/min.

The photosensitive resin composition layer was exposed to light using an ultra-high pressure mercury lamp with an exposure amount determined by the sensitivity evaluation described above through a line-and-space pattern (duty ratio of 1: 1) mask having a line width of 3 to 20 μm without peeling the temporary support, and then left to stand for 3 hours, and then the temporary support was peeled off and developed. Development was carried out for 40 seconds by shower development using a 1.0% aqueous solution of sodium carbonate at 22 ℃. Among the line and space patterns obtained in this way, the pattern having the smallest line width is set as the arrival resolution. When the resolution is determined to be reached, the pattern is observed using a Scanning Electron Microscope (SEM), and when the sidewall portion of the pattern is largely roughened, it is assumed that no image analysis is performed. From the obtained arrival 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 resolution achieved, the more a pattern with excellent resolution can be obtained even when left after exposure.

-benchmark-

The arrival resolution is less than 6 μm: 5

The arrival resolution is less than 8 μm and 6 μm or more: 4.5

The arrival resolution is less than 10 μm and 8 μm or more: 4

The arrival resolution is less than 15 μm and 10 μm or more: 3

The arrival resolution is less than 20 μm and 15 μm or more: 2

The arrival resolution is 20 μm or more: 1

(Pattern Width Change Rate)

The photosensitive transfer materials thus produced were bonded to a substrate having a copper layer under lamination conditions of a roll temperature of 130 ℃, a line pressure of 0.8MPa and a line speed of 3.0 m/min.

The photosensitive resin composition layer was exposed to light using an ultra-high pressure mercury lamp with an exposure amount determined by sensitivity evaluation, without peeling off the temporary support and with a line-and-space pattern (duty ratio of 1: 1) mask having a line width of 6 μm, and then the temporary support was peeled off after leaving for 3 hours and 24 hours, followed by development. Development was carried out for 40 seconds by shower development using a 1.0% aqueous solution of sodium carbonate at 22 ℃. The substrate with the line and space pattern thus obtained was obtained. The pattern width after 3 hours and the pattern width after 24 hours of the 6 μm pattern (resin pattern) on the substrate were obtained. The rate of change of the pattern width after 24 hours with respect to the pattern width after 3 hours was determined according to the following equation. From the obtained change rate of the pattern width, 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, the more suppressed the decrease in line width due to the passage of time after exposure, and the more stable the performance.

Formula (II): pattern width change rate (%) { [ pattern width after 24 hours (μm) ]/[ pattern width after 3 hours (μm) ] } × 100

-benchmark-

Less than 2%: 3

Less than 5%, and 2% or more: 2

5 percent or more: 1

(copper line width Change ratio)

The photosensitive transfer materials thus produced were bonded to a substrate having a copper layer under lamination conditions of a roll temperature of 130 ℃, a line pressure of 0.8MPa and a line speed of 3.0 m/min.

The photosensitive resin composition layer was exposed to light using an ultra-high pressure mercury lamp with an exposure amount determined by sensitivity evaluation, without peeling off the temporary support and with a line-and-space pattern (duty ratio of 1: 1) mask having a line width of 6 μm, and then the temporary support was peeled off after leaving for 3 hours and 24 hours, followed by development. Development was carried out for 40 seconds by shower development using a 1.0% aqueous solution of sodium carbonate at 22 ℃. The line and space pattern thus obtained is obtained. Next, the copper layer was etched using a copper etching solution (Cu-02 manufactured by KANTO CHEMICAL co., inc.) to obtain a substrate drawn with copper (solid line portion SL). The copper line width after 3 hours and the copper line width after 24 hours were obtained for the 6 μm pattern (copper pattern) on the substrate. The rate of change of the copper wire width after 24 hours with respect to the copper wire width after 3 hours was determined according to the following equation. From the change rate of the obtained copper wire width, the change rate of the 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, the more suppressed the decrease in line width due to the passage of time after exposure, and the more stable the performance.

Formula (II): copper line width change rate (%) { [ copper line width after 24 hours (μm) ]/[ copper line width after 3 hours (μm) ] } × 100

-benchmark-

Less than 5%: 3

Less than 10%, and 5% or more: 2

More than 10 percent: 1

[ display characteristics (luminance) ]

As one index of the display characteristics, the luminance was evaluated.

An Indium Tin Oxide (ITO) layer (having a thickness of 150nm) was formed as a conductive layer of the 2 nd layer on each of the polyimide substrate and the polyethylene terephthalate substrate by sputtering, and then a copper layer (having a thickness of 200nm) was formed as a conductive layer of the 1 st layer on the ITO layer by vacuum deposition, thereby producing substrates.

Each of the photosensitive transfer materials thus produced was bonded to a copper layer (line pressure: 0.8MPa, line speed: 3.0 m/min, roll temperature: 130 ℃ C.). The contact pattern exposure was performed using a photomask provided with the pattern shown in fig. 2, which had a structure in which the conductive layer pad was 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 dashed line portion DL virtually shows an alignment frame.

After that, the temporary support was peeled off, and development and water washing were performed to obtain the pattern shown in fig. 2. Next, after etching the copper layer using a copper etching liquid (Cu-02 manufactured by KANTO CHEMICAL co., inc.), the ITO layer was etched using an ITO etching liquid (ITO-02 manufactured by KANTO CHEMICAL co., inc.), thereby obtaining a substrate in which copper (solid line portion SL) and ITO (gray portion G) were both depicted in the pattern shown in fig. 2.

Next, in the aligned state, pattern exposure was performed using a photomask provided with openings of the pattern shown in fig. 3, and development and water washing were performed.

In the pattern shown in fig. 3, the gray portion G is a light shielding portion, and the dashed portion DL virtually shows an alignment frame.

Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin composition layer was peeled off using a peeling liquid (KP-301 manufactured by KANTO CHEMICAL co., inc.).

The resulting circuit board was irradiated from the back side with a fluorescent lamp (wavelength range of 380 to 780nm), and the transmitted light intensity was measured with a luminance meter LS-100 (manufactured by MINOLTA).

The luminance maintenance ratio was obtained from the following equation, assuming that the light intensity a when the circuit board was not sandwiched (i.e., the intensity of light emitted from the fluorescent lamp) was the light intensity B when the circuit board was sandwiched (i.e., the intensity of light transmitted through the circuit board). From the obtained luminance maintenance ratios, 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 ratio, the more excellent the display characteristics of the display device when the obtained circuit board is provided in the display device.

Formula (II): luminance maintenance ratio (%) [ light intensity B/light intensity a ] × 100

-benchmark-

More than 60 percent: 2

60 percent of the following: 1

[ Table 2]

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

< photoacid generators >

"B-1": a compound having a structure shown below (synthesized according to the method described in paragraph 0227 of Japanese patent laid-open publication No. 2013-47765.)

[ chemical formula 4]

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

[ chemical formula 5]

< surfactant >

"C-1": a compound having the structure shown below

[ chemical formula 6]

< basic Compound >

"D-1": a compound having the structure (CMTU)

[ chemical formula 7]

< substrate >

"polyimide 1": TORMED (registered trademark) type X (manufactured by I.S.T Corporation, haze 0.4%, total light transmittance 90%, thickness 50 μm)

"polyimide 2": TORMED type S (manufactured by I.S.T Corporation, haze 3.0%, total light transmittance 88%, thickness 25 μm)

"polyimide 3": kapton (registered trademark) 100H (manufactured by DU PONT-TORAY CO., LTD., total light transmittance of 85% or less, thickness of 25 μm)

"polyethylene terephthalate": lumiror (registered trademark) 16QS60 (manufactured by TORAY INDUSTRIES, INC. having haze of 0.4%, total light transmittance of 90%, thickness of 16 μm)

As is clear from Table 2, examples 1 to 12 have a smaller pattern width and a smaller rate of change in copper wire width than comparative examples 1 to 2, and are excellent in lamination suitability under high-temperature and high-speed conditions. Further, it is found that examples 1 to 10 using the polyimide 1 having a small haze and a high total light transmittance are superior to examples 11 to 12 in display characteristics.

The disclosure of japanese patent application No. 2019-036429, filed on 28/2/2019, the contents of which are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.