JPWO2018155192A1 - Photosensitive transfer material, circuit wiring manufacturing method, and touch panel manufacturing method - Google Patents

Abstract

A polymer including a temporary support and a polymer having a structural unit having an acid group protected in the form of an acetal, and the content of the structural unit having a group in which the acid group is protected in the form of an acetal is a polymer. The average value of the I / O values obtained by dividing the inorganic value I based on the organic conceptual diagram of the polymer component by the organic value O is 10% by mass or more and 30% by mass or less with respect to the total mass of the components. A photosensitive transfer material having a polymer component having a glass transition temperature of 5 to 0.7 and an average value of glass transition temperature of 90 ° C. or less, and a photosensitive resin layer containing a photoacid generator, the photosensitive transfer A method for manufacturing circuit wiring using a material and a method for manufacturing a touch panel.

Description

  The present disclosure relates to a photosensitive transfer material, a circuit wiring manufacturing method, and a touch panel manufacturing method.

In a display device (such as an organic EL display device and a liquid crystal display device) having a touch panel such as a capacitive input device, a conductive layer such as an electrode pattern corresponding to a sensor of a visual recognition portion, a peripheral wiring portion, and a wiring of a lead-out wiring portion A pattern is provided inside the touch panel.
In general, a patterned layer is formed by a photosensitive resin composition layer provided on an arbitrary substrate using a photosensitive transfer material because the number of steps for obtaining a required pattern shape is small. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

For example, JP-A-2015-194715 discloses (A) an acid generator that generates acid upon irradiation with actinic rays or radiation, (B) a resin whose solubility in alkali is increased by the action of acid, and (S And (C) a resin having increased solubility in alkali due to the action of acid (B-3) -SO _2. A resin component contained in the chemically amplified positive photosensitive resin composition for thick film, comprising an acrylic resin containing a structural unit derived from an acrylic ester containing a cyclic group or a lactone-containing cyclic group Thick film chemically amplified positive photosensitive resin used for forming a thick film resist pattern having a thickness ratio of 70% by mass or more with respect to the total mass of the above (B-3) acrylic resin. composition Things are disclosed.

The problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material that has excellent laminating properties, high exposure sensitivity, and can provide a pattern with excellent resolution even when left after exposure. It is to be.
Another problem to be solved by another embodiment of the present invention is to provide a circuit wiring manufacturing method or a touch panel manufacturing method using the photosensitive transfer material.

Means for solving the above problems include the following aspects.
<1> A polymer containing a temporary support and a structural unit having a group in which an acid group is protected in the form of an acetal, and the content of the structural unit having a group in which the acid group is protected in the form of an acetal The average value of the I / O values obtained by dividing the inorganic value I based on the organic conceptual diagram of the polymer component by the organic value O is 10% by mass or more and 30% by mass or less with respect to the total mass of the polymer component. A photosensitive transfer material comprising a polymer component having a glass transition temperature of 90 ° C. or lower, and a photosensitive resin layer containing a photoacid generator.
<2> The photosensitive transfer material according to <1>, wherein the structural unit having a group in which the acid group is protected in the form of an acetal is a structural unit represented by the following formula A.

In formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or Represents an aryl group, and R ³¹ or R ³² and R ³³ may combine to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group. Represents.
<3> The content of the structural unit having a group in which the acid group is protected in the form of an acetal is 15% by mass or more and 25% by mass or less with respect to the total mass of the polymer component, <1> or <2 > Photosensitive transfer material.
<4> The photosensitive transfer material according to any one of <1> to <3>, wherein an average value of the I / O values is 0.55 or more and 0.7 or less.
<5> The polymer according to any one of <1> to <4>, wherein the polymer including a structural unit having a group in which the acid group is protected in the form of an acetal further includes a structural unit having an acid group. Photosensitive transfer material.
<6> The photosensitive transfer material according to any one of <1> to <5>, wherein the polymer component further includes a polymer having an acid group.
<7> The content of the structural unit having an acid group contained in the polymer component is 0.5% by mass or more and 20% by mass or less with respect to the total mass of the polymer component, <5> or <6 > Photosensitive transfer material.
<8> The photosensitive transfer material according to any one of <1> to <7>, wherein the polymer component has a weight average molecular weight of 60,000 or less.
<9> A step of bonding the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <8> to the substrate and bonding the substrate to the substrate, and after the bonding step A step of pattern exposing the photosensitive resin layer of the photosensitive transfer material, a step of developing the photosensitive resin layer after the exposing step to form a pattern, and a substrate in an area where the pattern is not disposed A method of manufacturing circuit wiring, comprising: an etching process in this order.
<10> A touch panel manufacturing method including the circuit wiring manufacturing method according to <9>.

According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material that has excellent laminating properties, high exposure sensitivity, and can obtain a pattern with excellent resolution even when left after exposure. .
In addition, according to another embodiment of the present invention, a circuit wiring manufacturing method or a touch panel manufacturing method using the photosensitive transfer material can be provided.

It is the schematic which shows an example of the laminated constitution of the photosensitive transfer material which concerns on this indication. It is the schematic which shows an example of the manufacturing method of the circuit wiring for touchscreens using the photosensitive transfer material which concerns on this indication. FIG. 6 is a schematic diagram showing a pattern A. FIG. 6 is a schematic diagram showing a pattern B.

Hereinafter, the contents of the present disclosure will be described. In addition, although it demonstrates referring an accompanying drawing, a code | symbol may be abbreviate | omitted.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” represents both and / or acrylate and methacrylate.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
In this specification, the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

(Photosensitive transfer material)
The photosensitive transfer material according to the present embodiment includes a temporary support and a polymer including a structural unit having a group in which an acid group is protected in the form of an acetal, and the acid group is protected in the form of an acetal. The content of the structural unit having a ratio of 10% by mass to 30% by mass with respect to the total mass of the polymer component is obtained by dividing the inorganic value I based on the organic conceptual diagram of the polymer component by the organic value O. A photosensitive resin layer containing a polymer component having an average I / O value of 0.5 or more and 0.7 or less and an average value of a glass transition temperature of 90 ° C. or less, and a photoacid generator; Have

In circuit wiring for touch panels, etc.
From the standpoint of improving productivity, the substrate for forming circuit wiring and the photosensitive transfer material are bonded together while being conveyed, for example, by roll-to-roll, and exposure, development, and the like are performed. preferable.
As the photosensitive transfer material, one having a high resolution of circuit wiring to be patterned is preferable from the viewpoint of manufacturing a finer pattern with high accuracy.
In addition, as the photosensitive transfer material, a material that can be bonded at a low temperature is preferable from the viewpoint of energy saving and high-speed process. In particular, when a substrate such as a heat-sensitive resin film is used as the substrate, one that can be bonded at a low temperature is more preferable.

In the case of adopting the above roll-to-roll process, for example, the transfer, exposure, and development processes are arranged independently, unwinding before and after each process, and a process incorporating winding. May be. As described above, when winding and unwinding are incorporated between the exposure and development steps, the time from exposure to development in the photosensitive transfer material may be long.
Thus, when pattern formation is performed using a photosensitive transfer material, the photosensitive transfer material may be left for a long time (for example, several hours to several days) after exposure and then developed.
The present inventors have found that the chemically amplified positive photosensitive resin composition according to JP-A-2015-194715 has a sufficient resolution of the resist pattern shape obtained by subsequent development when left for a long time after exposure. I found it not.

Therefore, as a result of intensive studies by the present inventors, the photosensitive transfer material according to the present embodiment has excellent laminating properties, high exposure sensitivity, and excellent resolution even when left after exposure. It has been found that a photosensitive transfer material can be provided from which a pattern can be obtained.
Although the detailed mechanism by which the above effect is obtained is unknown, it is estimated as follows.
In the photosensitive transfer material according to the present embodiment, the content of the structural unit having a group in which the acid group is protected in the form of an acetal is limited. Therefore, the elimination reaction of the group and the subsequent deprotection generation By suppressing the diffusion of the object, it is presumed that a pattern with excellent resolution can be obtained even when left after exposure.
In addition, in order to prevent diffusion of the deprotected product, the sensitivity may decrease when the content of the structural unit having a group in which the acid group is protected in the form of an acetal is simply reduced. Conceivable. However, in the photosensitive transfer material according to this embodiment, by further setting the average value of the I / O values of the polymer components to an appropriate value, the resolution and exposure sensitivity of the pattern when left after exposure is set. It is presumed that
Furthermore, in the photosensitive transfer material according to the present embodiment, it is presumed that a photosensitive transfer material having excellent laminating properties can be obtained by setting the average value of Tg of the polymer component to an appropriate value. In the photosensitive transfer material according to the present embodiment, it is considered that a photosensitive transfer material excellent in laminating ability can be easily obtained even when lamination is performed at a low temperature.
The “low temperature” in the laminate is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and particularly preferably 90 ° C. or lower. Although the minimum of the temperature at the time of lamination is not specifically limited, It is preferable that it is 40 degreeC or more, and it is more preferable that it is 60 degreeC or more.
Hereinafter, the photosensitive transfer material according to this embodiment will be described in detail.

FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material according to this embodiment. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 12, a photosensitive resin layer 14, and a cover film 16 are laminated in this order. The photosensitive resin layer 14 includes a polymer containing a structural unit having a group in which an acid group is protected in the form of an acetal, and the content of the structural unit having a group in which the acid group is protected in the form of an acetal, The average value of I / O values obtained by dividing the inorganic value I based on the organic conceptual diagram of the polymer component by the organic value O is 10% by mass or more and 30% by mass or less with respect to the total mass of the polymer component. The polymer component which is 0.5 or more and 0.7 or less and whose average value of glass transition temperature is 90 ° C. or less and a photoacid generator are included.
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present embodiment will be described. Note that the above configuration in the present embodiment may be referred to as follows in this specification.
A polymer containing a structural unit having a group in which an acid group is protected in the form of an acetal may be referred to as a “specific polymer”.
The photosensitive resin layer is a positive photosensitive resin layer and may be referred to as a “positive photosensitive resin layer”.

<Temporary support>
The temporary support is a support that supports the photosensitive resin layer and is peelable from the photosensitive resin layer.
The temporary support used in the present embodiment preferably has light transparency from the viewpoint that the photosensitive resin layer can be exposed via the temporary support when the photosensitive resin layer is subjected to pattern exposure.
Having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is from the viewpoint of improving sensitivity. 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, more preferably in the range of 8 μm to 150 μm, and most preferably in the range of 8 μm to 40 μm in terms of ease of handling and versatility.
The temporary support may be selected according to the material in terms of strength as a support, flexibility required for bonding with a circuit wiring formation substrate, light transmittance required in the first exposure process, and the like. Good.

  Preferred embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, and the contents of this publication are incorporated herein.

<Photosensitive resin layer>
The photosensitive transfer material according to this embodiment has a photosensitive resin layer disposed on a temporary support. The photosensitive resin layer in this embodiment includes a polymer containing a structural unit having a group in which an acid group is protected in the form of an acetal, and contains the structural unit in which the acid group has a group protected in the form of an acetal The amount is 10% by mass to 30% by mass with respect to the total mass of the polymer component, and the average of the I / O values obtained by dividing the inorganic value I based on the organic conceptual diagram of the polymer component by the organic value O A polymer component having a value of 0.5 or more and 0.7 or less and an average value of glass transition temperature of 90 ° C. or less and a photoacid generator are included.
Further, the photosensitive resin layer in the present embodiment is a positive photosensitive resin layer, and is preferably a chemically amplified positive photosensitive resin layer.
Photo acid generators such as onium salts and oxime sulfonate compounds described below are produced by reacting with actinic radiation (actinic rays), and catalyzing the deprotection of protected acid groups in the specific polymer. Therefore, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a so-called chemical amplification. As a result, high sensitivity is obtained.
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic radiation, a carboxy group is generated by a sequential photochemical reaction, but its quantum yield is always 1 or less and does not correspond to a chemical amplification type.

(Polymer component)
-Specific polymer-
The polymer component according to the present embodiment includes a polymer (specific polymer) including a structural unit (hereinafter, also referred to as “structural unit a1”) having a group in which an acid group is protected in the form of an acetal, and the acid The content of the structural unit having a group protected in the form of an acetal is 10% by mass or more and 30% by mass or less with respect to the total mass of the polymer component, and is based on an organic conceptual diagram of the polymer component The average value of I / O values obtained by dividing the value I by the organic value O is 0.5 or more and 0.7 or less, and the average value of the glass transition temperature is 90 ° C. or less.
The specific polymer contained in the photosensitive resin layer may be only one type or two or more types.
In the specific polymer, a group in which the acid group in the specific polymer is protected in the form of acetal is subjected to a deprotection reaction to be an acid group by the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables development.

The polymer component may further contain a polymer other than the specific polymer.
Moreover, it is preferable that all the polymers contained in the polymer component are polymers each containing at least a structural unit having an acid group.
The polymer component may further contain a polymer other than these. Unless otherwise stated, the polymer component in the present embodiment means one including other polymers added as necessary. In addition, even if it is a high molecular compound, the compound applicable to the plasticizer mentioned later, a heterocyclic compound, and surfactant shall not be contained in the said polymer component.

The specific polymer is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
Hereinafter, preferred embodiments of the structural unit a1 will be described.

<< Structural Unit a1 >>
The polymer component includes a polymer including a structural unit a1 having a group in which an acid group is protected in the form of an acetal. When the polymer component contains a polymer containing the structural unit a1, an extremely sensitive photosensitive resin layer can be obtained.
As the acid group in the “group in which the acid group is protected in the form of an acetal” in the present embodiment, known ones can be used and are not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group. These acid groups are in an acetal form that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, a tetrahydrofuranyl ester group, etc. protected in the form of an acetal as described in Formula A, etc. Acetal-based functional groups) can be used.

  As the structural unit a1, a structural unit (a) represented by the following formula A is preferable from the viewpoints of sensitivity during pattern formation and resolution of the pattern to be obtained.

In formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or Represents an aryl group, R ³¹ or R ³² and R ³³ may combine to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group. Represents.

In Formula A, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferred. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula A, R ³³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group and aryl group in R ³³ may have a substituent.
In Formula A, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and R ³¹ or R ³² and R ³³ are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula A, X ⁰ represents a single bond or a divalent linking group, preferably a single bond or an arylene group, and more preferably a single bond. The arylene group may have a substituent.

In Formula A, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the specific polymer can be further lowered.
More specifically, the structural unit in which R ³⁴ in Formula A is a hydrogen atom is preferably 20% by mass or more based on the total content of the structural unit (a) contained in the polymer.
In addition, the content (content ratio: mass ratio) of the structural unit in which R ³⁴ in formula A in the structural unit (a) is a hydrogen atom is calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.

  Among the structural units (a) represented by the formula A, a structural unit represented by the following formula A1 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In Formula A1, R ³⁴ represents a hydrogen atom or a methyl group, and R ^{35 to} R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A1, R ³⁴ is preferably a hydrogen atom.
In the formula ^A1, R 35 ^{to R 41} is preferably a hydrogen atom.

Preferable specific examples of the structural unit (a) represented by Formula A include the following structural units. R ³⁴ represents a hydrogen atom or a methyl group.

  Moreover, as said structural unit a1, the structural unit (b) represented by the following formula B is preferable from the viewpoint of the storage stability of the photosensitive resin composition.

In Formula B, R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^B1 and R ^B2 is an alkyl group or an aryl group, and R ^B3 is an alkyl group or Represents an aryl group, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, and X ^B represents a single bond or a divalent linking group; , R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In Formula B, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ^B1 or R ^B2 is an aryl group, a phenyl group is preferable. R ^B1 and R ^B2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula B, R ^B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group and aryl group in R ^B3 may have a substituent.
In Formula B, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, and R ^B1 or R ^B2 and R ^B3 are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula B, X ^B represents a single bond or a divalent linking group, and is a single bond or an alkylene group, —C (═O) O—, —C (═O) NR ^N —, —O—, or a combination thereof. Are preferable, and a single bond or —C (═O) O— is more preferable. The alkylene group may be linear, branched or cyclic, and may have a substituent. 1-10 are preferable and, as for carbon number of an alkylene group, 1-4 are more preferable. If X ^B -C where (= O) containing O- a, -C (= O) and carbon atoms contained in the ^O-, embodiments the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. When ^{containing, -C (= O) NR N} - - is ^{X B -C (= O) NR} N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In Formula B, the group containing R ^{B1 to} R ^B3 and X ^B are preferably bonded to each other at the para position.
In Formula B, R ^B12 represents a substituent, and is preferably an alkyl group or a halogen atom. 1-10 are preferable and, as for carbon number of an alkyl group, 1-4 are more preferable.
In Formula B, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In Formula B, R ^B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the specific polymer.
More specifically, the structural unit in which R ^B4 in Formula B is a hydrogen atom is preferably 20% by mass or more with respect to the total content of the structural unit (a) contained in the specific polymer.
In the structural unit (a), the content (content ratio: mass ratio) of the structural unit in which R ^B4 in formula B is a hydrogen atom is calculated from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement by a conventional method. It can be confirmed by the intensity ratio of the peak intensity.

  Among the structural units (b) represented by the formula B, a structural unit represented by the following formula B1 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In Formula B1, R ^B4 represents a hydrogen atom or a methyl group, R ^{B5 to} R ^B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and X ^B represents A single bond or a divalent linking group is represented, and n represents an integer of 0 to 4.
In the formula B1, X ^B have the same meanings as X ^B in the formula B, and also the same preferred embodiment.
In formula B1, R ^B4 is preferably a hydrogen atom.
In formula B1, R ^{B5 to} R ^B11 are preferably hydrogen atoms.
In Formula B1, R ^B12 represents a substituent, and is preferably an alkyl group or a halogen atom. 1-10 are preferable and, as for carbon number of an alkyl group, 1-4 are more preferable.
In Formula B1, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

Preferable specific examples of the structural unit (b) represented by the formula B include the following structural units. R ^B4 represents a hydrogen atom or a methyl group.

The structural unit a1 contained in the specific polymer may be one type or two or more types.
The content of the structural unit a1 in the specific polymer is 10% by mass or more and 30% by mass or less with respect to the total mass of the specific polymer from the viewpoint of excellent pattern resolution when left after exposure. Is more preferable, it is more preferable that it is 12 to 28 mass%, and it is still more preferable that it is 15 to 25 mass%.
Content (content ratio: mass ratio) of the structural unit a1 in a specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.
In addition, the content of the structural unit represented by the above formula A in the specific polymer is 10% by mass with respect to the total mass of the specific polymer from the viewpoint of sensitivity during pattern formation and resolution of the pattern to be obtained. It is preferably 30% by mass or less, more preferably 12% by mass or more and 28% by mass or less, and further preferably 15% by mass or more and 25% by mass or less.
Furthermore, after decomposing all the polymer components into structural units (monomer units), the proportion of the structural unit a1 is 10% by mass or more and 30% by mass or less, and 12% by mass with respect to the total mass of the polymer component. % To 28% by mass, more preferably 15% to 25% by mass.

<< Structural Unit a2 >>
The specific polymer used in the present embodiment preferably further includes a structural unit a2 having an acid group. The structural unit a2 is a structural unit containing an acid group that is not protected in the form of an acetal, that is, an acid group that does not have a group in the form of an acetal. By including the structural unit a2 in the specific polymer, the specific polymer has good sensitivity at the time of pattern formation, becomes easily soluble in an alkaline developer in the development process after pattern exposure, and shortens the development time. Can do.
The acid group in this specification means a proton dissociable group having a pKa of 12 or less. The acid group is usually incorporated into the specific polymer as a structural unit [structural unit a2] having an acid group using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. The pKa of the acid group is preferably −5 or more.

As the acid group that the structural unit a2 has, an acid group derived from a carboxy group, an acid group derived from a sulfonamide group, an acid group derived from a sulfonylimide group, an acid group derived from a phosphonic acid group, or derived from a sulfonic acid group And acid groups derived from phenolic hydroxyl groups, and the like. Of these, at least one selected from an acid group derived from a carboxy group and an acid group derived from a phenolic hydroxyl group is preferred.
Introduction of the structural unit having an acid group into the specific polymer can be carried out by copolymerizing a monomer having an acid group.
The structural unit having an acid group as the structural unit a2 includes a structural unit derived from styrene or a structural unit obtained by substituting an acid group for a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid, and the like. preferable.

As the structural unit a2 contained in the specific polymer, a structural unit having a carboxy group and a structural unit having a phenolic hydroxyl group are preferable from the viewpoint that sensitivity at the time of pattern formation becomes better.
The monomer having an acid group that can form the structural unit a2 is not limited to the examples described above.

The structural unit a2 contained in the specific polymer may be only one type or two or more types.
The content of the structural unit having an acid group (structural unit a2) is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to the total mass of the specific polymer from the viewpoint of pattern formation. 15 mass% is more preferable, and 1 mass%-10 mass% is still more preferable.
In addition, the content of the structural unit having an acid group (structural unit a2) is preferably 0.1% by mass to 20% by mass, and 0.5% by mass with respect to the total mass of the polymer component, from the viewpoint of pattern formation. % To 15% by mass is more preferable, and 1% to 10% by mass is even more preferable.
Content (content ratio: mass ratio) of the structural unit a2 in a specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

<< Structural Unit a3 >>
The specific polymer may be referred to as other structural unit (“structural unit a3”) other than the structural unit having a group in which the above-described acid group is protected in the form of an acetal and the structural unit having an acid group. ) May be included.
There is no restriction | limiting in particular as a monomer which forms another structural unit, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having an aliphatic cyclic skeleton, etc. Mention may be made of unsaturated compounds.
Various characteristics of the specific polymer can be adjusted by adjusting at least one of the type and the content using other structural units. In particular, the Tg of the specific polymer can be easily adjusted to 90 ° C. or lower by appropriately using other structural units.
The said specific polymer may contain only 1 type of other structural units, and may contain 2 or more types.

  Other structural units are specifically styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate. , 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or Echile It can be mentioned a structural unit derived from such a glycol mono-acetoacetate mono (meth) acrylate. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  Further, as another structural unit, a group having an aromatic ring or a group having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specific examples include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentani (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Is mentioned. Especially, as another structural unit, the structural unit derived from cyclohexyl methacrylate is mentioned preferably.

  Moreover, as a monomer which forms another structural unit, (meth) acrylic-acid alkylester is preferable from a viewpoint of lamination suitability and resolution, Acrylic acid alkylester is more preferable, Acrylic acid which has a C4-C12 alkyl group Alkyl esters are particularly preferred. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  Furthermore, it is preferable that the said specific polymer has a structural unit represented by following formula 2 as another structural unit.

In Formula 2, R ^b represents a hydrogen atom or a methyl group, and R ^c represents an alkyl group.

R ^b in Formula 2 is preferably a hydrogen atom from the viewpoint of laminate suitability and resolution.
R ^c in Formula 2 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 2 to 12 carbon atoms, and more preferably an alkyl group having 2 to 12 carbon atoms from the viewpoint of laminating suitability and resolution. An alkyl group is more preferable, and an alkyl group having 5 to 9 carbon atoms is particularly preferable.
The alkyl group in R ^c is, may be a straight chain, it may have a branch or may have a cyclic structure.

85 mass% or less is preferable with respect to the total mass of the said specific polymer, content of the structural unit a3 has more preferable 80 mass% or less, and 75 mass% or less is still more preferable. The lower limit may be 0% by mass, but is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more.
In addition, the content of the structural unit represented by the above formula 2 is preferably 10% by mass to 85% by mass, and preferably 15% by mass to 80% by mass with respect to the total mass of the specific polymer, from the viewpoints of laminate suitability and resolution. % Is more preferable, and 20% by mass to 75% by mass is still more preferable.

  Preferable examples of the specific polymer in the present embodiment include A-1 to A-21 used in the examples, but it goes without saying that the specific polymer is not limited thereto.

<< Method for Producing Specific Polymer >>
Although the production method (synthesis method) of the specific polymer is not particularly limited, for example, a polymerizable monomer for forming the structural unit a1 having a group in which an acid group is protected in the form of an acetal, If necessary, using a polymerization initiator in an organic solvent containing a polymerizable monomer for forming the structural unit a2 having an acid group and a polymerizable monomer for forming the other structural unit a3. It can be synthesized by polymerization. It can also be synthesized by a so-called polymer reaction.

-Other polymers-
The photosensitive resin layer contains, as a polymer component, a polymer not containing the structural unit a1 having a group in which an acid group is protected in the form of an acetal in addition to the specific polymer (referred to as “other polymer”). May further be included. When the photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the total polymer component, More preferably, it is 20 mass% or less.
Another polymer may contain only 1 type and may contain 2 or more types.

It is preferable that the polymer component according to the present embodiment further includes a polymer having an acid group as another polymer.
Preferred examples of the acid group include a carboxy group.
There is no restriction | limiting in particular as a polymer which has an acid group, Although a well-known thing can be used, It is preferable to use the polymer (linear organic polymer) which has a linear acid group. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film-forming agent but also as a developer for water, weak alkaline water or an organic solvent. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxy group alone or Resin copolymerized, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half-esterified or half-amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride. It is done.
Similarly, there are acidic cellulose derivatives having a carboxy group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

The polymer having an acid group may be contained singly or in combination of two or more.
When the photosensitive resin layer according to the present embodiment contains a polymer having an acid group, the content of the polymer having an acid group is not particularly limited, but with respect to the total solid content of the photosensitive resin layer, The content is preferably 1% by mass to 70% by mass, more preferably 2% by mass to 50% by mass, and still more preferably 5% by mass to 30% by mass.

  In addition, as other polymers, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, Sartomer Company) ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), and Joncry 690, Joncryl 678, Joncryl 67, Joncryl 586 (manufactured by BASF) or the like can also be used.

-Average value of I / O value of polymer component-
From the viewpoint of exposure sensitivity, the polymer component used in the present embodiment has an average I / O value obtained by dividing the inorganic value I based on the organic conceptual diagram by the organic value O, from 0.5 to 0.7. Or less, preferably 0.55 or more and 0.7 or less, and more preferably 0.55 or more and 0.65 or less.
Further, the I / O value of the specific polymer used in the present embodiment may be appropriately set so that the average value of the I / O values is included in the above range, but it is 0.5 or more and 0.7 or less. It is preferable that it is 0.55 or more and 0.65 or less.
Regarding the above I / O values, organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); 10, 719-725 (1957); Fragrance Journal, 34, 97-111 (1979); Fragrance Journal, 50, 79-82 (1981); There is a detailed explanation. The concept of the I / O value is that the properties of a compound are divided into an organic group that represents covalent bonding and an inorganic group that represents ionic bonding, and all the organic compounds are orthogonal coordinates named organic axes and inorganic axes. Each of the above points is shown.

The I / O value when the polymer component contains two or more kinds of polymers can be considered as follows. For example, when the polymer component contains three kinds of polymers (polymer 1 to polymer 3), the I / O value of polymer 1 is A1, the mass fraction is M1, and the I / O value of polymer 2 is Is A2, the mass fraction is M2, the I / O value of the polymer 3 is A3, and the mass fraction is M3, the I / O value Am of the mixed component can be estimated as follows.
Am = A1 * M1 + A2 * M2 + A3 * M3
In addition, when a polymer component contains only 1 type of polymer independently, the I / O value of only 1 type of polymer contained becomes an average value of the I / O value in a polymer component.

-Average value of glass transition temperature of polymer component-
The average value of the glass transition temperature (Tg) of the polymer component used in the present embodiment is 90 ° C. or less, preferably −20 ° C. to 90 ° C., and preferably 20 ° C. to 90 ° C. from the viewpoint of laminate suitability. More preferably, it is 20 to 60 degreeC, and it is especially preferable that it is 25 to 45 degreeC.
The Tg of the specific polymer used in the present embodiment may be appropriately set so that the average value of the Tg is included in the above range, but is preferably 0 ° C. or higher and 90 ° C. or lower, and preferably 20 ° C. or higher. It is more preferably 70 ° C. or lower, and further preferably 20 ° C. or higher and 50 ° C. or lower.
The glass transition temperature of a resin such as a polymer in the present embodiment is measured using differential scanning calorimetry (DSC).
The specific measurement method is performed in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011). As the glass transition temperature in the present specification, an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after maintaining the apparatus at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus is stabilized, the heating rate is about 30 ° C./minute at a heating rate of 20 ° C./min. Heat to a higher temperature and draw a DTA or DSC curve.
The extrapolated glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line obtained by extending the low-temperature base line in the DTA curve or DSC curve to the high-temperature side, and the stepwise change portion of the glass transition. Calculated as the temperature of the intersection with the tangent drawn at the point where the slope of the curve is maximum.

As a method for adjusting the Tg of the polymer to the above-described preferable range, for example, from the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit, the FOX formula is used as a guideline. It is possible to control the Tg of the target polymer.
Regarding FOX Formula For example, in the case of a binary copolymer, Tg of the homopolymer of the first structural unit contained in the polymer is Tg1, and the mass fraction of the copolymer of the first structural unit is W1, Copolymer containing the first structural unit and the second structural unit when Tg of the homopolymer of the structural unit of 2 is Tg2 and the mass fraction in the copolymer of the second structural unit is W2. The combined Tg0 (K) can be estimated according to the following equation.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
In the case of a ternary or more n-element copolymer, the Tg of the homopolymer of the nth structural unit contained in the polymer is Tgn, and the mass fraction in the copolymer of the nth structural unit is Wn. Then, as described above, it is possible to estimate according to the following formula.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2) + (W3 / Tg3) ... + (Wn / Tgn)
A copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the FOX formula described above.
It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.

  Further, as a method for separating the specific polymer and the like from the photosensitive resin layer for measuring Tg and the like, a method in which the photosensitive resin layer is dissolved in an organic solvent and then separated by a reprecipitation method is preferable. It is mentioned in.

The glass transition temperature in the case where the polymer component contains two or more kinds of polymers can be considered as follows. For example, when the polymer component contains three kinds of polymers (polymer 1 to polymer 3), the glass transition temperature of polymer 1 is Tg1 (K), the mass fraction is M1, and the glass transition of polymer 2 When the temperature is Tg2 (K), the mass fraction is M2, the glass transition temperature of the polymer 3 is Tg3 (K), and the mass fraction is M3, the average value Tgm (K) of the glass transition temperature of the mixed components. Can be estimated as follows.
1 / Tgm = (M1 / Tg1) + (M2 / Tg2) + (M3 / Tg3)
In addition, when a polymer component contains only 1 type of polymer independently, Tg of only 1 type of polymer contained becomes an average value of Tg in a polymer component.

-Weight average molecular weight of polymer component-
The molecular weight of the polymer component is preferably a weight average molecular weight (Mw) in terms of polystyrene of 60,000 or less. When the weight average molecular weight of the polymer is 60,000 or less, the melt viscosity of the photosensitive resin layer is suppressed to be low, and bonding at a low temperature (for example, 130 ° C. or less) is realized when bonding to the substrate. Can do.
Moreover, it is preferable that the weight average molecular weights of the said polymer component are 2,000-60,000, and it is more preferable that it is 3,000-50,000.
What is necessary is just to set suitably the weight average molecular weight of the specific polymer used in this embodiment so that the weight average molecular weight of the said polymer component may be contained in the said range, but it is 6,000 or more and 40,000 or less. Preferably, it is 10,000 or more and 30,000 or less.
In addition, the weight average molecular weight of resin, such as a polymer in this embodiment, is measured by GPC (gel permeation chromatography).
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) was used as a column. .6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, manufactured by Tosoh Corp.), each connected in series, and THF (tetrahydrofuran) can be used as an eluent.
Measurement conditions are 0.2% by mass, flow rate is 0.35 ml / min, sample injection amount is 10 μl, measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
The calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using any one of 7 samples of “A-2500” and “A-1000”.
The ratio (dispersity) between the number average molecular weight and the weight average molecular weight of the specific polymer component is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

-Amount of acid group of polymer component-
The content of the structural unit having an acid group with respect to the total mass of the polymer component is preferably 0.5% by mass or more and 20% by mass or less with respect to the total mass of the polymer component, from the viewpoint of pattern formation. 0.5 mass% or more and 15 mass% or less are more preferable, and 1 mass% or more and 10 mass% or less are still more preferable.
The content of the structural unit having an acid group is a structural unit having an acid group when all polymers contained in the polymer component are decomposed into structural units (monomer units) with respect to the total mass of the polymer component. It is the ratio of the containing mass of.

The photosensitive resin layer in this embodiment preferably contains the polymer component in a proportion of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of suitability for lamination. More preferably, it is contained in a proportion of mass% to 98 mass%.
Moreover, the said photosensitive resin layer is a ratio of 50 mass%-99.9 mass% of the said specific polymer with respect to the total mass of the photosensitive resin layer from a viewpoint of expressing favorable adhesiveness with respect to the said board | substrate. It is preferable to contain in the ratio of 70 mass%-98 mass%.

[Photoacid generator]
The photosensitive resin layer contains a photoacid generator.
The photoacid generator used in the present embodiment is a compound capable of generating an acid by irradiation with active radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present embodiment is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
The photoacid generator used in this embodiment 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 a pKa of 2 Photo acid generators that generate the following acids are particularly preferred. The lower limit value of pKa is not particularly defined, but is preferably −10.0 or more, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
The photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound. It is more preferable to contain.

  Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A.

  As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following formula (B1) is preferable.

In formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site with another atom or another group.

As for the compound containing the oxime sulfonate structure represented by the formula (B1), any group may be substituted, and the alkyl group in R ²¹ may be linear or have a branched structure. And may have a ring structure. Acceptable substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group). , Preferably a bicycloalkyl group or the like), or a halogen atom.
As the aryl group for R ^21, an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.

  The compound containing an oxime sulfonate structure represented by the formula (B1) is also preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP 2014-85643 A.

  Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.

  As the ionic photoacid generator, ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

A photo-acid generator may be used individually by 1 type, or may use 2 or more types together.
The content of the photoacid generator in the photosensitive resin layer is preferably 0.5% by mass to 20% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution. It is more preferably from 15% by mass to 15% by mass, and further preferably from 1% by mass to 10% by mass.

〔solvent〕
When forming the said photosensitive resin layer, it is preferable to apply and dry the photosensitive resin composition containing a polymer component, a photo-acid generator, and a solvent.
More specifically, in order to easily form the photosensitive resin layer, the viscosity of the photosensitive resin composition is adjusted by adding a solvent, and the photosensitive resin composition containing the solvent is applied and dried, A photosensitive resin layer can be suitably formed.
A known solvent can be used as the solvent. Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, the contents of which are incorporated herein.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate can also be added.
Only 1 type may be used for a solvent and 2 or more types may be used for it.
A solvent may be used individually by 1 type and it is more preferable to use 2 types together. When two or more solvents are used, for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates Use in combination with the other is preferred.

The solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and An example is propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butylene glycol diacetate (boiling point 232 ° C) There can be exemplified.

The content of the solvent in applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is -900 mass parts.
The content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass with respect to the total mass of the photosensitive resin layer. % Or less is more preferable.

[Other additives]
In addition to the specific polymer and the photoacid generator, the photosensitive resin layer in the present embodiment can contain a known additive as necessary.

-Plasticizer-
The photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a weight average molecular weight smaller than that of the specific polymer.
The weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the specific polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

  In the above formula, R represents an alkylene group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding site with another atom.

  For example, even if the compound has an alkyleneoxy group (referred to as “Compound X”), the photosensitive resin layer obtained by mixing Compound X, the specific polymer, and the photoacid generator is a compound. When plasticity does not improve compared with the photosensitive resin layer formed without X, it does not correspond to the plasticizer in this embodiment. For example, an optionally added surfactant is generally not used in an amount that brings plasticity to the photosensitive resin layer, and thus does not correspond to a plasticizer in the present specification.

  Examples of the plasticizer include compounds having the following structure, but are not limited thereto.

In the case of using a plasticizer, the content of the plasticizer is preferably 1% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer, from the viewpoint of suitability for lamination. More preferably, it is -20 mass%.
The said photosensitive resin layer may contain only 1 type of plasticizers, and may contain 2 or more types.

-Sensitizer-
The photosensitive resin layer can further contain a sensitizer.
The sensitizer absorbs active radiation (active light) and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
Exposure sensitivity can be improved by containing a sensitizer.

As the sensitizer, a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene or 9,10-dimethoxyanthracene is preferred.

  Examples of the sensitizer include the compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.

  The content of the sensitizer is preferably 0% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer.

-Basic compounds-
The photosensitive resin layer preferably further contains a basic compound.
As the basic compound, any basic compound used in a resist can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP2011-221494A, the contents of which are incorporated herein.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] And -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The said basic compound may be used individually by 1 type, or may use 2 or more types together.
The content of the basic compound is preferably 0.001% by mass to 5% by mass and more preferably 0.005% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer. .

-Heterocyclic compound-
The said photosensitive resin layer in this embodiment can contain the compound containing a heterocyclic compound.
There is no restriction | limiting in particular in the heterocyclic compound in this embodiment. For example, compounds having an epoxy group or oxetanyl group in the molecule described below, alkoxymethyl group-containing heterocyclic compounds, other oxygen-containing monomers such as various cyclic ethers and cyclic esters (lactones), nitrogen-containing monomers such as cyclic amines and oxazolines Furthermore, heterocyclic monomers having d electrons such as silicon, sulfur, and phosphorus can be added.

  The addition amount of the heterocyclic compound in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer when the heterocyclic compound is added, More preferably, it is 0.1 mass%-10 mass%, and it is still more preferable that it is 1 mass%-5 mass%. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together. When using 2 or more types together, the said preferable content points out the total content of 2 or more types of heterocyclic compounds.

  Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.

A compound having an epoxy group in the molecule can be obtained as a commercial product. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like, commercially available products described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212 , EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX -121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (above, manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel & Sumitomo Chemical) Etc.
The compound which has an epoxy group in a molecule | numerator may be used individually by 1 type, and may use 2 or more types together.

  Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.

  Specific examples of the compound having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd.) Can be used.

  Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

  The photosensitive resin layer in the present embodiment preferably includes a compound having an epoxy group as a heterocyclic compound from the viewpoint of etching resistance and line width stability.

-Alkoxysilane compounds-
The photosensitive resin layer may contain an alkoxysilane compound. Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.

-Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFuck (manufactured by DIC Corporation), and Florard (Sumitomo 3M). Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (Toray Dow Corning Silicone).
Moreover, the weight average of polystyrene conversion measured by the gel permeation chromatography in case tetrahydrofuran (THF) is used as a surfactant contains the structural unit A and the structural unit B represented by the following formula I-1. A preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.

In formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon. Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and * represents a bonding position with another structure. To express.

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

  The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

  In addition, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP 2009-237362 A can also be used.

Surfactant may be used individually by 1 type and may use 2 or more types together.
The content of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. It is still more preferable that it is% -3 mass%.

-Other ingredients-
The photosensitive resin layer in the present embodiment includes an antioxidant, an acid proliferation agent, a development accelerator, a colorant, a thermal acid generator, an ultraviolet absorber, a thickener, a crosslinking agent, and organic or inorganic precipitation prevention. A known additive such as an agent can be further added.
Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP 2014-85643 A, and the contents of this publication are incorporated in this specification.

[Thickness of photosensitive resin layer]
The thickness of the photosensitive resin layer is preferably 0.5 μm to 20 μm. When the thickness of the photosensitive resin layer is 20 μm or less, the pattern resolution is good, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
As thickness of the photosensitive resin layer, 0.8 micrometer-15 micrometers are more preferable, and 1.0 micrometer-10 micrometers are especially preferable.

[Method for forming photosensitive resin layer]
A photosensitive resin composition for forming a photosensitive resin layer can be prepared by mixing each component and a solvent at a predetermined ratio and by any method, stirring and dissolving. For example, it is possible to prepare a composition by preparing each solution of each component in advance in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

The photosensitive transfer material according to this embodiment having a photosensitive resin layer on the temporary support can be obtained by applying the photosensitive resin composition to the temporary support and drying it.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, the photosensitive resin layer can also be apply | coated on the laminated body of the temporary support body which has the other layer mentioned later on a temporary support body, and another layer.

<Other layers>
The photosensitive transfer material according to the present embodiment may have a layer other than the photosensitive resin layer (hereinafter sometimes referred to as “other layer”). Examples of other layers include a contrast enhancement layer, an intermediate layer, a cover film, and a thermoplastic resin layer.

<Contrast enhancement layer>
The photosensitive transfer material according to the present embodiment can have a contrast enhancement layer in addition to the photosensitive resin layer.
A contrast enhancement layer (CEL) is a material (photo-decoloring) that has a large absorption with respect to an exposure wavelength before exposure, but gradually decreases with exposure, that is, has a higher light transmittance. It is a layer containing a coloring pigment component). Known photodecolorable dye components include diazonium salts, stilbazolium salts, arylnitroso salts, and the like. A phenolic resin or the like is used as the film forming component.
In addition, as contrast enhancement layers, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to 0055 of JP-A-6-332167, photopolymer handbook, photopolymer social gathering, industrial research group ( 1989), photopolymer technology, Yamaoka, edited by Nagamatsu, Nikkan Kogyo Shimbun (1988) can be used.

<Intermediate layer>
An intermediate layer can be provided on the photosensitive resin layer for the purpose of preventing the mixing of components during application of a plurality of layers and storage after application.
As the intermediate layer, the intermediate layer described in paragraphs [0084] to [0087] of JP-A-2005-259138 can be used. The intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution.
Examples of the material used for the intermediate layer include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Resin. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

<Thermoplastic resin layer, cover film, etc.>
The photosensitive transfer material according to the present embodiment can also include, for example, a temporary support, a thermoplastic resin layer, and a positive photosensitive resin layer in this order. Furthermore, you may have a cover film in order to protect the photosensitive resin layer.
About the preferable aspect of a thermoplastic resin layer, Paragraph 0189-paragraph 0193 of Unexamined-Japanese-Patent No. 2014-85643, About the preferable aspect of another layer, it describes in Paragraph 0194-paragraph 0196 of Unexamined-Japanese-Patent No. 2014-85643, respectively. The contents of this publication are incorporated herein.

In the case where the photosensitive transfer material according to the present embodiment has other layers such as a thermoplastic resin layer, in accordance with the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. Can be produced.
For example, when producing a photosensitive transfer material according to the present embodiment having a thermoplastic resin layer and an intermediate layer, a solution (thermal) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support. The coating liquid for the plastic resin layer) was applied and dried to provide a thermoplastic resin layer, and then the resin and additives were added to a solvent that did not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer. The preparation liquid (intermediate layer coating liquid) is applied and dried to laminate the intermediate layer. On the formed intermediate layer, a photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer is further applied and dried to laminate the photosensitive resin layer, whereby the photosensitive transfer according to this embodiment is performed. A material can be suitably produced.

(Method for manufacturing circuit wiring)
A first embodiment of a method for manufacturing circuit wiring using the photosensitive transfer material according to the present embodiment will be described.
The first embodiment of the circuit wiring manufacturing method is as follows:
A step of bonding the outermost layer on the side opposite to the temporary support of the photosensitive transfer material according to the present embodiment to the substrate to be in contact with the substrate (bonding step);
A step of exposing the photosensitive resin layer of the photosensitive transfer material after the bonding step (exposure step);
Developing the photosensitive resin layer after the exposing step to form a pattern (developing step);
And a step of etching the substrate in a region where the pattern is not disposed (etching step).
The substrate in the first embodiment of the method for producing circuit wiring may be a substrate itself such as glass, silicon, or film, and may be a conductive layer or the like on the substrate such as glass, silicon, or film, if necessary. The board | substrate with which arbitrary layers of were provided may be sufficient.
According to the first embodiment of the circuit wiring manufacturing method, a fine pattern can be formed on the substrate surface.

The second embodiment of the circuit wiring manufacturing method is:
And a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials from each other, and on the surface of the base material, the outermost surface layer in order from the surface of the base material The outermost layer opposite to the temporary support of the photosensitive transfer material according to this embodiment is brought into contact with the first conductive layer with respect to the substrate on which the first conductive layer and the second conductive layer are stacked. Bonding process,
A first exposure step of pattern exposing the photosensitive resin layer through the temporary support of the photosensitive transfer material after the bonding step;
A first developing step of developing the photosensitive resin layer after the first exposure step to form a first pattern after peeling the temporary support from the photosensitive resin layer after the first exposure step;
A first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in a region where the first pattern is not disposed;
A second exposure step of pattern exposing the first pattern after the first etching step with a pattern different from the first pattern;
A second development step of developing the first pattern after the second exposure step to form a second pattern;
A second etching step of etching at least the first conductive layer among the plurality of conductive layers in the region where the second pattern is not disposed. As the second embodiment, International Publication No. 2006/190405 can be referred to, the contents of which are incorporated herein.

The circuit wiring manufacturing method according to the present embodiment can be used as a circuit wiring manufacturing method for a touch panel or a touch panel display device.
Hereinafter, details of each step will be described based on the second embodiment.

<Lamination process>
An example of the bonding process is schematically shown in FIG.
First, in the bonding step, the substrate 22 has a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 having different constituent materials, and the substrate 22 is formed on the surface of the substrate 22. The photosensitive transfer according to this embodiment described above is applied to the substrate (circuit wiring forming substrate) 20 on which the first conductive layer 24 and the second conductive layer 26 which are the outermost surface layers are laminated in order from the surface of the substrate. The positive photosensitive resin layer 14 of the material 100 is brought into contact with the first conductive layer 24 and bonded. Such a bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as “transfer” or “laminate”.
The outermost layer on the side opposite to the temporary support of the photosensitive transfer material may be a photosensitive resin layer, or may be another layer such as an ultraviolet absorbing layer or an adhesion layer.

As shown in FIG. 1, when the cover film 16 is provided on the positive photosensitive resin layer 14 of the photosensitive transfer material 100, the cover film 16 is removed from the photosensitive transfer material 100 (positive photosensitive resin layer 14). After that, the positive photosensitive resin layer 14 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and bonded thereto.
Bonding (transferring) the photosensitive transfer material onto the first conductive layer is performed by stacking the positive photosensitive resin layer side of the photosensitive transfer material on the first conductive layer, and applying pressure and heating with a roll or the like. It is preferable to be performed. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
When the base material of the circuit wiring forming substrate is a resin film, roll-to-roll bonding can also be performed.

〔Base material〕
As for the board | substrate with which the some electroconductive layer was laminated | stacked on the base material, it is preferable that a base material is a glass base material or a film base material, and it is more preferable that it is a film base material. When the circuit wiring manufacturing method according to the present embodiment is a circuit wiring for a touch panel, the substrate is particularly preferably a sheet-shaped resin composition.
The substrate is preferably transparent.
The refractive index of the substrate is preferably 1.50 to 1.52.
The base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by Corning gorilla glass can be used. Moreover, as the above-mentioned transparent substrate, the materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency. Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[Conductive layer]
Examples of the plurality of conductive layers formed on the substrate include arbitrary conductive layers used for general circuit wiring or touch panel wiring.
Examples of the material for the conductive layer include metals and metal oxides.
Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.

In the circuit wiring manufacturing method according to this embodiment, it is preferable that at least one of the plurality of conductive layers includes a metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor for a visual recognition part used in a capacitive touch panel or a wiring for a peripheral extraction part.

[Circuit wiring formation board]
It is a board | substrate which has a conductive layer on the surface of a base material. Circuit wiring is formed by patterning the conductive layer. In this example, a film substrate such as PET is preferably provided with a plurality of conductive layers such as a metal oxide or a metal.

<Exposure process (first exposure process)>
The exposure process is performed in the first embodiment, and the first exposure process is performed in the second embodiment. An example of the exposure process (first exposure process) is schematically shown in FIG.
In the exposure process (first exposure process), the positive photosensitive resin layer 14 is subjected to pattern exposure via the temporary support 12 of the photosensitive transfer material after the bonding process.

  As examples of the exposure step, the development step, and other steps in the present embodiment, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can also be suitably used in this embodiment.

For example, a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (on the side opposite to the side in contact with the first conductive layer 24), and then the mask 30 And a method of exposing with ultraviolet rays from above the mask.
In the present embodiment, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wiring manufactured according to the present embodiment and to reduce the area occupied by the extraction wiring as much as possible, at least a part of the pattern (particularly the touch panel) The electrode pattern and the lead-out wiring portion) are preferably fine wires of 100 μm or less, and more preferably 70 μm or less.
Here, the light source used for exposure can be appropriately selected and used as long as it can irradiate light (for example, 365 nm, 405 nm, etc.) in a wavelength region where the exposed portion of the photosensitive transfer material can be dissolved in the developer. . Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
Energy of exposure generally ^5mJ / cm ^{2 ~200mJ} / cm 2 mm, preferably 10mJ ^/ cm ² ~100mJ ^/ cm 2 approximately.
It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called PEB (Post Exposure Bake), pattern edge roughness due to standing waves generated in the photosensitive resin layer during exposure can be reduced.

  In addition, even if pattern exposure is performed after peeling the temporary support from the positive photosensitive resin layer, it is exposed through the temporary support before peeling the temporary support, and then the temporary support is peeled off. May be. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask, and to avoid the influence on the exposure due to the foreign matter adhering to the mask, it is preferable to perform the exposure without peeling off the temporary support. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Development process (first development process)>
In the first embodiment, the developing step is performed, and in the second embodiment, the first developing step is performed. An example of the development process (first development process) is schematically shown in FIG.
In the development step (first development step), the temporary support 12 is peeled from the positive photosensitive resin layer 14 after the exposure step (first exposure step), and then the positive type photosensitive after the exposure step (first exposure step). The first resin layer 14 is developed to form the first pattern 14A.

The development step (first development step) is a step of forming a pattern (first pattern) by developing the pattern-exposed positive photosensitive resin layer.
Development of the pattern-exposed positive photosensitive resin layer can be performed using a developer.
The developer is not particularly limited as long as the exposed portion of the positive photosensitive resin layer can be removed. For example, a known developer such as a developer described in JP-A-5-72724 can be used. it can. The developer is preferably a developer in which the exposed portion of the positive photosensitive resin layer exhibits a dissolution type development behavior. For example, an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present embodiment include a developer described in paragraph 0194 of International Publication No. 2015/092731.

  The development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used. Here, the shower development will be described. The exposed portion can be removed by spraying a developer onto the positive photosensitive resin layer after exposure. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C to 40 ° C.

Furthermore, you may have the post-baking process which heat-processes the pattern containing the positive photosensitive resin layer obtained by image development.
The post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 506.6 kPa or more. On the other hand, it is more preferable to perform in an environment of 114.6 kPa or less, and it is particularly preferable to perform in an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
The post-bake may be performed in an air environment or a nitrogen substitution environment.

  You may have other processes, such as a post-exposure process.

<Etching step (first etching step)>
The etching process is performed in the first embodiment, and the first etching process is performed in the second embodiment. An example of the etching process (first etching process) is schematically shown in FIG.
In the etching step (first etching step), at least the first conductive layer 24 and the second conductive layer 26 are etched among the plurality of conductive layers in the region where the first pattern 14A is not disposed. The first conductive layer 24A and the second conductive layer 26A having the same pattern are formed by etching.

  Etching of the conductive layer can be performed by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A or a dry etching method such as a known plasma etching.

For example, as an etching method, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used. As an etchant used for wet etching, an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched.
Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
Examples of alkaline type etchants include aqueous solutions of alkali components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. Examples thereof include a mixed aqueous solution of salt. As the alkali component, a component obtained by combining a plurality of alkali components may be used.

  The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The first pattern used as an etching mask (etching pattern) in the present embodiment preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the positive photosensitive resin layer is prevented from peeling off during the etching process, and the portion where the positive photosensitive resin layer does not exist is selectively etched.

After the etching process, in order to prevent contamination of the process line, a cleaning process and a drying process may be performed as necessary. For the washing step, for example, performed by washing 10 seconds to 300 seconds substrate with pure water at room temperature, the drying step, for example using air blow, air blow pressure ^{(0.1kg / cm 2 ~5kg / cm} 2 or so) The drying may be performed by appropriately adjusting.

<Second exposure step>
In the second embodiment, the second exposure step is performed. An example of the second exposure step is schematically shown in FIG.
After the first etching step, the first pattern 14A after the first etching step is subjected to pattern exposure with a pattern different from the first pattern.

In the second exposure step, the first pattern remaining on the first conductive layer is exposed to at least a portion corresponding to a portion to be removed in the second development step described later.
For the pattern exposure in the second exposure step, the same method as the pattern exposure in the first exposure step can be applied except that the mask 40 having a pattern different from that of the mask 30 used in the first exposure step is used.

<Second development process>
In the second embodiment, the second development step is performed. An example of the second developing process is schematically shown in FIG.
In the second development step, the first pattern 14A after the second exposure step is developed to form a second pattern 14B.
By the development, the exposed portion of the first pattern in the second exposure step is removed.
In the second development step, the same method as the development in the first development step can be applied.

<Second etching process>
In the second embodiment, the second exposure step is performed. An example of the second etching step is schematically shown in FIG.
In the second etching step, at least the first conductive layer 24A is etched among the plurality of conductive layers in the region where the second pattern 14B is not disposed.

For the etching in the second etching step, the same method as the etching in the first etching step can be applied except that an etching solution corresponding to the conductive layer to be removed by etching is selected.
In the second etching step, it is preferable to selectively etch fewer conductive layers than in the first etching step, depending on the desired pattern. For example, as shown in FIG. 2, the first conductive layer is etched by using an etchant that selectively etches only the first conductive layer 24 </ b> B in a region where the positive photosensitive resin layer is not disposed. The pattern can be different from the pattern of the second conductive layer.
After the second etching step is completed, circuit wiring including conductive layers 24B and 26A having at least two types of patterns is formed.

<Positive photosensitive resin layer removal step>
An example of the positive photosensitive resin layer removing step is schematically shown in FIG.
After the second etching step, the second pattern 14B remains on a part of the first conductive layer 24B. If the positive photosensitive resin layer is unnecessary, all the remaining positive photosensitive resin layer 14B may be removed.

Although there is no restriction | limiting in particular as a method of removing the remaining positive type photosensitive resin layer, The method of removing by chemical processing can be mentioned.
As a method for removing the positive type photosensitive resin layer, for example, a substrate having a positive type photosensitive resin layer or the like in a stripping solution being stirred at 30 ° C. to 80 ° C., preferably 50 ° C. to 80 ° C. for 1 minute to The method of immersing for 30 minutes is mentioned.

  Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkali components such as primary amine, secondary amine, tertiary amine, and quaternary ammonium salt. , A stripping solution dissolved in dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof. A stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.

  The circuit wiring manufacturing method according to the present embodiment may include other optional steps. For example, although the following processes are mentioned, it is not limited to these processes.

<Process for attaching protective film>
The second embodiment may further include a step of attaching a light-transmitting protective film (not shown) on the first pattern after the first etching step and before the second exposure step. Good.
In this case, it is preferable that in the second exposure step, the first pattern is subjected to pattern exposure via the protective film, and after the second exposure step, the protective film is peeled from the first pattern, and then the second development step is performed.

<Step of reducing visible light reflectance>
The circuit wiring manufacturing method according to the present embodiment can include a step of performing a process of reducing the visible light reflectance of some or all of the plurality of conductive layers on the substrate.
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, the visible light reflectance can be reduced by blackening by oxidizing copper to copper oxide.
Regarding preferred embodiments of the processing for reducing the visible light reflectance, paragraphs 0017 to 0025 of JP2014-150118A, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The contents of this publication are incorporated herein.

<Step of forming a new conductive layer on the insulating film>
The circuit wiring manufacturing method according to the present embodiment preferably includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.
With such a configuration, the second electrode pattern described above can be formed while being insulated from the first electrode pattern.
There is no restriction | limiting in particular about the process of forming an insulating film, The method of forming a well-known permanent film can be mentioned. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
There is no particular limitation on the process of forming a new conductive layer on the insulating film. A new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

  In the description with reference to FIG. 2, a case has been described in which circuit wirings having two different patterns are formed on a circuit wiring forming substrate having two conductive layers. The number of conductive layers of the substrate to which the manufacturing method of the present invention is applied is not limited to two, but a combination of the above-described exposure process, development process, and etching process using a circuit wiring forming substrate in which three or more conductive layers are laminated By performing the above three times or more, three or more conductive layers can be formed in different circuit wiring patterns.

  In addition, although not shown in FIG. 2, the circuit wiring manufacturing method according to the present embodiment is such that the base material has a plurality of conductive layers on both surfaces, and the conductive material formed on both surfaces of the base material. It is also preferable to form circuits sequentially or simultaneously on the layers. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material by roll-to-roll.

(Circuit wiring and circuit board)
The circuit wiring according to the present embodiment is a circuit wiring manufactured by the circuit wiring manufacturing method according to the present embodiment.
The circuit board according to the present embodiment is a substrate having circuit wiring manufactured by the circuit wiring manufacturing method according to the present embodiment.
Although the use of the circuit board according to the present embodiment is not limited, for example, a circuit board for a touch panel is preferable.

(Input device and display device)
An input device is an example of a device provided with circuit wiring manufactured by the circuit wiring manufacturing method according to the present embodiment.
The input device in the present embodiment is preferably a capacitive touch panel.
The display device in the present embodiment preferably includes the input device in the present embodiment. The display device in the present embodiment is preferably an image display device such as an organic EL display device and a liquid crystal display device.

(Touch panel, touch panel display device and manufacturing method thereof)
The touch panel according to the present embodiment is a touch panel having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present embodiment. Moreover, it is preferable that the touch panel which concerns on this embodiment has a transparent substrate, an electrode, and an insulating layer or a protective layer at least.
The touch panel display device according to the present embodiment is a touch panel display device having at least a circuit wiring manufactured by the circuit wiring manufacturing method according to the present embodiment, and is a touch panel display device having the touch panel according to the present embodiment. preferable.
The manufacturing method of the touch panel or the touch panel display device according to the present embodiment preferably includes the manufacturing method of the circuit wiring according to the present embodiment.
The manufacturing method of the touch panel or the touch panel display device according to the present embodiment is a process in which the outermost layer on the side opposite to the temporary support of the photosensitive transfer material obtained by the photosensitive transfer material manufacturing method is brought into contact with the substrate and bonded together. And a step of pattern exposing the photosensitive layer of the photosensitive transfer material after the bonding step, a step of developing the photosensitive layer after the exposing step to form a pattern, and the pattern It is preferable to include a step of etching the substrate in the unexposed region in this order. The details of each process are synonymous with the details of each process in the above-described method for manufacturing circuit wiring, and the preferred embodiments are also the same.
As a detection method in the touch panel according to the present embodiment and the touch panel display device according to the present embodiment, any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. . Among these, the electrostatic capacity method is preferable.
As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of the gazette, those described in FIG. 1 and FIG. 5 of JP 2012-89102 A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP No. 2013-54727 shown in FIG. 2), other configurations (for example, those shown in FIG. 6 of JP2013-164471A), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).
As the touch panel of this embodiment and the touch panel display device of this embodiment, "latest touch panel technology" (July 6, 2009, issued by Techno Times Co., Ltd.), supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress
Semiconductor Corporation The configuration disclosed in application note AN2292 or the like can be applied.

  The embodiment of the present invention will be described more specifically with reference to the following examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis of polymer components)
In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
ATHP: Tetrahydro-2H-pyran-2-yl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
MATHP: Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
ATB: tert-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
THFHS: 4- (2-tetrahydrofuranyloxy) styrene (synthetic product)
THFCS: 4- (2-tetrahydrofuranyloxycarbonyl) styrene (synthetic product)
THFMS: 2-tetrahydrofuranyl protected form of 1- [2- (methacryloyloxy) ethyl] succinate (synthetic product)
AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHMA: cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
BMA: n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<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 ° C. After adding camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. Then, the temperature was raised to 35 ° C. and stirred for 2 hours. After spreading Nyche in the order of Kyoward 200 and Kyoward 1000 (aluminum hydroxide adsorbent, both manufactured by Kyowa Chemical Industry Co., Ltd.), the reaction solution was filtered to obtain a filtrate. MEHQ (0.0012 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C., thereby obtaining 156.2 parts by mass of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oil. (Yield 98.0%).

<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 ° C. After adding camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 molar equivalent), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. Then, the temperature was raised to 35 ° C. and stirred for 2 hours. After spreading Kyodo 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) in order in Nutsche, the reaction solution was filtered to obtain a filtrate. MEHQ (0.0012 parts by mass) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 140.8 parts by mass of tetrahydro-2H-furan-2-yl acrylate (ATHF) was obtained as a colorless oil. (Yield 99.0%).

<Synthesis of THFHS>
4-hydroxystyrene (120.2 parts by mass, 1.0 molar equivalent) and hexane (120.2 parts by mass) were added to a three-necked flask and cooled to 20 ° C. After adding camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mol equivalent), the mixture was heated to 80 ° C. and stirred for 5 hours. . After spreading Kyodo 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) in order in Nutsche, the reaction solution was filtered to obtain a filtrate. MEHQ (0.0019 parts by mass) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 185.0 parts by mass of 4- (2-tetrahydrofuranyloxy) styrene (THFHS) was obtained as a colorless oil. (Yield 97.3%).

<Synthesis of THFCS>
4-Carboxystyrene (148.2 mass parts, 1.0 molar equivalent) and hexane (148.2 mass parts) were added to the 3 necked flask, and it cooled at 20 degreeC. After adding camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. Then, the temperature was raised to 35 ° C. and stirred for 2 hours. After spreading Kyodo 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) in order in Nutsche, the reaction solution was filtered to obtain a filtrate. MEHQ (0.0021 parts by mass) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 122.3 parts by mass of 4- (2-tetrahydrofuranyloxycarbonyl) styrene (THFCS) was a colorless oil. (Yield 97.3%).

<Synthesis of THFMS>
To a three-necked flask was added 2-methacryloyloxyethyl succinate (230.2 parts by mass, 1.0 molar equivalent) and hexane (230.2 parts by mass) at 20 ° C. Cooled to. After adding camphorsulfonic acid (0.00070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. Then, the temperature was raised to 35 ° C. and stirred for 2 hours. After spreading Kyodo 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.) in order in Nutsche, the reaction solution was filtered to obtain a filtrate. MEHQ (0.0030 parts by mass) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., thereby protecting 2-tetrahydrofuranyl of 1- [2- (methacryloyloxy) ethyl succinate (THFMS). , 299.0 parts by mass of a compound having the following structure) was obtained as a colorless oil (yield 99.6%).

<Synthesis of Polymer A-1>
PGMEA (75.0 parts by mass) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. ATHF (10.0 mass parts), AA (2.0 mass parts), EA (38.0 mass parts), MMA (5.0 mass parts), CHMA (45.0 mass parts), V-601 (3 0.1 parts by weight) and PGMEA (75.0 parts by weight) were added dropwise to a three-necked flask solution maintained in a temperature range of 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropping, the mixture was stirred for 2 hours in a temperature range of 90 ° C. ± 2 ° C. to obtain a polymer A-1 (solid content concentration 40.0%).

<Synthesis Example of Polymers A-2 to A-31>
The monomer type and amount used were changed as shown in Table 1 below, and the other conditions were synthesized in the same manner as in A-1. The solid content concentration of the polymer was 40% by mass. In Table 1, the amount of monomer used is indicated by mass%.

In Table 1, “-” indicates that the corresponding monomer is not used.
In Table 1, the I / O value, Tg, and Mw were measured by the methods described above. The unit of Tg is ° C.

  Below, it uses for preparation of the photosensitive resin composition mentioned later, and shows the detail of each component described in Table 2 mentioned later.

<Photo acid generator>
B-1: Structure shown below (a compound described in paragraph 0227 of JP 2013-47765 A, synthesized according to the method described in paragraph 0227)

  B-2: PAG-103 (trade name, the following compound, manufactured by BASF)

  B-3: The structure shown below (synthesized according to the method described in paragraph 0160 of International Publication No. 2014/020984. Ts represents a p-toluenesulfonyl group).

  B-4: GSID-26-1, triarylsulfonium salt (manufactured by BASF)

<Surfactant>
C-1: Compound having the structure shown below

<Basic compound>
D-1: Compound (CMTU) having the structure shown below
D-2: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Sensitizer>
DBA: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

(Examples 1 to 23 and Comparative Examples 1 to 10)
<Preparation of photosensitive transfer material>
In Examples 1 to 23 and Comparative Examples 1 to 10, the polymer component, the photoacid generator, the basic compound, the surfactant, and other components were added to PGMEA so as to have the solid content ratio shown in Table 2 below. It was dissolved and mixed in (propylene glycol monomethyl ether acetate) so as to have a solid content concentration of 10% by mass, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain a photosensitive resin composition.
This photosensitive resin composition is formed on a polyethylene terephthalate film (hereinafter referred to as “PET (A)”) having a thickness of 50 μm serving as a temporary support, with a dry film thickness of 3.0 μm using a slit nozzle. It applied so that it might become. Thereafter, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (manufactured by Tredegar, OSM-N) was pressure bonded as a cover film to prepare a photosensitive transfer material.
The total light haze of PET (A) was 0.19%. Film haze measured the total light haze value (%) of the base piece based on JIS-K-7136 using Suga Test Instruments Co., Ltd. haze meter HZ-2.

<Performance evaluation>
A PET substrate with a copper layer was used in which a copper layer was formed by sputtering at a thickness of 500 nm on a 188 μm thick PET film.

<Laminate suitability evaluation>
The produced photosensitive transfer material was cut into a 50 cm square, the cover film was peeled off, a roll temperature of 90 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min. It laminated on the PET board | substrate with a copper layer on the lamination conditions of these. The area where the photosensitive resin layer was in close contact with the copper layer without bubbles or floats was visually evaluated, and the area ratio where the photosensitive resin layer was in close contact / the area (%) of the cut transfer material was determined. It can be said that the larger the area (%), the better the laminate suitability.
〔Evaluation criteria〕
Area (%) is 95% or more: 5
Area (%) is 90% or more and less than 95%: 4
Area (%) is 85% or more and less than 90%: 3
Area (%) is 80% or more and less than 85%: 2
Area (%) is less than 80%: 1

<Sensitivity (exposure sensitivity) evaluation>
The produced photosensitive transfer material was subjected to a linear pressure of 0.8 MPa and a linear velocity of 3.0 m / min. It laminated on the PET board | substrate with a copper layer on the lamination conditions of these. When the laminating suitability was 4 or less when the roll temperature was 90 ° C., the sample was prepared by raising the lami roll temperature until the laminating suitability was judged to be 5. The laminate suitability was evaluated by the method described above.
Without exposing the temporary support, the photosensitive resin layer was exposed with an ultra-high pressure mercury lamp through a line and space pattern mask (Duty ratio 1: 1) having a line width of 3 to 20 μm, and left for 1 hour, and then the temporary support was removed. It peeled and developed. Development was carried out using a 1.0% sodium carbonate aqueous solution at 28 ° C. for 30 seconds by shower development. When a 20 μm line and space pattern was formed by the above method, the residue in the space was observed and evaluated with a scanning electron microscope (SEM), and the exposure amount at which the residue was completely eliminated was determined. An exposure amount of 200 mJ / cm ² or less is a practical level. It can be said that the smaller the exposure amount, the better the exposure sensitivity.
〔Evaluation criteria〕
Less than 80 mJ / cm ² : 5
80 mJ / cm ² or more and less than 100 mJ / cm ² : 4.5
100 mJ / cm ² or more and less than 120 mJ / cm ² : 4
120mJ / cm ² or more 150mJ / cm less than ^2: 3.5
150 mJ / cm ² or more and less than 200 mJ / cm ² : 3
200 mJ / cm ² or more and less than 300 mJ / cm ² : 2
300 mJ / cm ² or more: 1

<Resolution evaluation>
The produced photosensitive transfer material was subjected to a linear pressure of 0.8 MPa and a linear velocity of 3.0 m / min. It laminated on the PET board | substrate with a copper layer on the lamination conditions of these. In addition, when the above-mentioned evaluation result of laminating suitability was 4 or less at a roll temperature of 90 ° C., a sample was prepared by raising the lamiroll temperature until the laminating suitability evaluation result was 5 (area (%) was 95% or more).
After exposing the photosensitive resin layer with an ultrahigh pressure mercury lamp with an exposure amount determined by sensitivity evaluation through a line and space pattern (Duty ratio 1: 1) mask having a line width of 3 μm to 20 μm without peeling off the temporary support, After standing for 24 hours, the temporary support was peeled off and developed. Development was carried out using a 1.0% sodium carbonate aqueous solution at 28 ° C. for 30 seconds by shower development. In the line and space pattern thus obtained, the resolution at which the pattern with the smallest line width could be formed was defined as the ultimate resolution. Further, when determining the ultimate resolution, the pattern was observed with a scanning electron microscope (SEM), and it was determined that the pattern could not be resolved if the pattern side wall portion was greatly roughened. It can be said that the smaller the arrival resolution, the more excellent the resolution even when left after exposure.
〔Evaluation criteria〕
<6 μm: 5
6 μm or more and less than 8 μm: 4.5
8 μm or more and less than 10 μm: 4
10 μm or more and less than 12 μm: 3.5
12 μm or more and less than 15 μm: 3
15 μm or more and less than 20 μm: 2
No resolution: 1

The results are shown in Table 2 below.
As shown in Table 2, the photosensitive transfer material according to this embodiment was excellent in laminate suitability, high exposure sensitivity, and a pattern with excellent resolution even when left after exposure.

In Table 2, the description of “-” indicates that the corresponding compound is not contained.
In Table 2, the I / O value, Tg, and Mw were measured by the methods described above. The unit of Tg is ° C.
Further, for example, “A-16 / A-17” in the type column and “40/60” in the added amount column indicate that A-1 is 60 parts by mass and A-4 is 40 parts by mass. It shows that each was used in quantity.

(Example 101)
Indium tin oxide (ITO) was deposited as a second conductive layer on a 100 μm thick PET substrate by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum deposition. A film was formed with a thickness of 200 nm to obtain a circuit formation substrate.
The photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.). Contact pattern exposure was performed using a photomask provided with a pattern shown in FIG. 3 (hereinafter also referred to as “pattern A”) having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support. .
In the pattern A shown in FIG. 3, the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etchant (Kanto Chemical Co., Ltd. Cu-02), the ITO layer is etched using an ITO etchant (Kanto Chemical Co., Ltd. ITO-02), A substrate on which copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.

Next, pattern alignment was performed using a photomask provided with openings of the pattern shown in FIG. 4 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
In the pattern B shown in FIG. 4, the gray portion G is a light shielding portion, and the dotted line portion DL is a virtual alignment alignment frame.
Thereafter, the copper layer is etched using Cu-02, and the remaining photosensitive resin layer is peeled off using a stripping solution (dimethyl sulfoxide: monoethanolamine = 7: 3 (mass ratio) solution). Obtained.
As a result, a circuit wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and the pattern was clean.

(Example 102)
On a 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum deposition at a thickness of 200 nm. The film was formed into a circuit forming substrate.
The photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.).
The photosensitive resin layer was subjected to pattern exposure using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etchant (Kanto Chemical Co., Ltd. Cu-02), the ITO layer is etched using an ITO etchant (Kanto Chemical Co., Ltd. ITO-02), A substrate on which copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.
Next, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern alignment was performed using a photomask provided with an opening of the pattern B shown in FIG. 4 in the aligned state, and after developing the PET (A), development and washing were performed.
Thereafter, the copper wiring is etched using Cu-02, and the remaining photosensitive resin layer is peeled off using a stripping solution (dimethyl sulfoxide: monoethanolamine = 7: 3 (mass ratio) solution), and the circuit wiring board is peeled off. Obtained.
When observed with a microscope, there was no peeling or chipping, and the pattern was clean.

12 Temporary Support 14 Photosensitive Resin Layer 14A First Pattern 14B Second Pattern 16 Cover Film 20 Circuit Forming Substrate 22 Base Material 24 First Conductive Layer 24A First Conductive Layer (After First Etching Step)
24B 1st conductive layer (after 2nd etching process)
26 2nd conductive layer 26A 2nd conductive layer (after 1st etching process and 2nd etching process)
30 Mask 40 Mask 100 Photosensitive transfer material SL Solid line part G Gray part DL Dotted line part

Claims (10)

A temporary support;
A polymer containing a structural unit having a group in which the acid group is protected in the form of an acetal, and the content of the structural unit in which the acid group has a group protected in the form of an acetal is based on the total mass of the polymer component The average value of I / O values obtained by dividing the inorganic value I based on the organic conceptual diagram of the polymer component by the organic value O is 0.5 to 0.7. A photosensitive transfer material, comprising: a polymer component having an average glass transition temperature of 90 ° C. or less and a photosensitive resin layer containing a photoacid generator. The photosensitive transfer material according to claim 1, wherein the structural unit having a group in which the acid group is protected in the form of an acetal is a structural unit represented by the following formula A.

In formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or Represents an aryl group, and R ³¹ or R ³² and R ³³ may combine to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group. Represents.   The content of the structural unit having a group in which the acid group is protected in the form of an acetal is 15% by mass or more and 25% by mass or less with respect to the total mass of the polymer component. Photosensitive transfer material.   The photosensitive transfer material according to claim 1, wherein an average value of the I / O values is 0.55 or more and 0.7 or less.   The photosensitive transfer according to any one of claims 1 to 4, wherein the polymer containing a structural unit having a group in which the acid group is protected in the form of an acetal further comprises a structural unit having an acid group. material.   The photosensitive transfer material according to claim 1, wherein the polymer component further comprises a polymer having an acid group.   The content of the structural unit having an acid group contained in the polymer component is 0.5% by mass or more and 20% by mass or less with respect to the total mass of the polymer component. Photosensitive transfer material.   The photosensitive transfer material of any one of Claims 1-7 whose weight average molecular weights of the said polymer component are 60,000 or less. A step of bringing the outermost layer opposite to the temporary support of the photosensitive transfer material according to any one of claims 1 to 8 into contact with the substrate and bonding the substrate to the substrate;
Pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the bonding step;
Developing the photosensitive resin layer after the exposing step to form a pattern;
Etching the substrate in the region where the pattern is not disposed, in this order,
Circuit wiring manufacturing method. A step of bringing the outermost layer opposite to the temporary support of the photosensitive transfer material according to any one of claims 1 to 8 into contact with the substrate and bonding the substrate to the substrate;
Pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the bonding step;
Developing the photosensitive resin layer after the exposing step to form a pattern;
Etching the substrate in the region where the pattern is not disposed, in this order,
A method for manufacturing a touch panel.