JP2018177889A - Manufacturing method of polymer solution for photosensitive transfer material, manufacturing method of composition for photosensitive transfer material, manufacturing method of photosensitive transfer material, manufacturing method of circuit wiring, and manufacturing method of touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a polymer solution for a photosensitive transfer material which can provide a pattern superior in resolution, manufacturing method of a composition for the photosensitive transfer material, a manufacturing method of the photosensitive transfer material, a manufacturing method of circuit wiring, or a manufacturing method of a touch panel.SOLUTION: There is provided a manufacturing method of a polymer solution for a photosensitive transfer material, including a step of performing polymerization reaction of a composition containing a polymerization solvent component which contains a polymerization initiator and polymerization solvent where steam pressure in 20°C is 1-16 kPa, and a monomer component containing at least one kind of monomer having acid radical protected with acidic cleavage group. There are also provided manufacturing method of a composition for the photosensitive transfer material, a manufacturing method of the photosensitive transfer material, a manufacturing method of circuit wiring, or a manufacturing method of a touch panel.SELECTED DRAWING: Figure 2

Description

  The present disclosure relates to a method for producing a polymer solution for photosensitive transfer material, a method for producing a composition for photosensitive transfer material, a method for producing a photosensitive transfer material, a method for producing a circuit wiring, and a method for producing a touch panel.

In a display device (such as an organic EL display device and a liquid crystal display device) provided with a touch panel such as a capacitance type input device, a conductive layer such as an electrode pattern corresponding to a sensor of a visible portion, and wiring of peripheral wiring portions and extraction wiring portions A pattern is provided inside the touch panel.
In general, for forming a patterned layer, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material since 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.
The layer of such a photosensitive resin composition is formed, for example, by including a polymer compound containing a structural unit derived from at least one monomer having an acid group protected with an acid-degradable group. .

  In Patent Document 1, (A) a vinyl polymer having a monomer unit having an alkali-soluble group blocked by an alkyl vinyl ether, (B) a photothermal conversion material generating heat by active energy rays, and (C) heat A positive resist composition for a circuit board is described, which comprises an acid generator which generates an acid according to the above.

JP 2007-163767 A

The problem to be solved by one embodiment of the present invention is to provide a method for producing a polymer solution for a photosensitive transfer material from which a pattern with excellent resolution can be obtained.
The problem to be solved by another embodiment of the present invention is a method of producing a composition for photosensitive transfer material from which a pattern excellent in resolution is obtained, a method of producing a photosensitive transfer material, and the method of using the same It is providing a manufacturing method of circuit wiring, or a manufacturing method of a touch panel using the same.

Means for solving the above problems include the following aspects.
<1> A polymerization solvent component containing a polymerization initiator and a polymerization solvent, and having a vapor pressure at 20 ° C. of 1 kPa or more and 16 kPa or less, and at least one kind of unitary group having an acid degradable group-protected acid group The manufacturing method of the polymer solution for photosensitive transfer materials which has the process of performing the polymerization reaction in the composition containing the monomer component which contains a body.
The manufacturing method of the polymer solution for photosensitive transfer materials as described in <1> whose vapor pressure in 20 degreeC of the <2> above-mentioned superposition | polymerization solvent component is 1 kPa or more and 10 kPa or less.
<3> The polymerization solvent component includes at least one polymerization solvent selected from an ester group, an ether group and a carbonyl group, and including a polymerization solvent having 4 to 6 carbon atoms, <1> or <2> The manufacturing method of the polymer solution for photosensitive transfer materials as described in 4 ..
<4> The polymerization solvent component does not contain a polymerization solvent containing a hydroxy group, or the content of the polymerization solvent containing a hydroxy group is more than 0% by mass and 5% by mass with respect to the total mass of the polymerization solvent component The manufacturing method of the polymer solution for photosensitive transfer materials as described in any one of <1>-<3> which is less than.
The manufacturing method of the polymer solution for photosensitive transfer materials as described in any one of <1>-<4> in which the <5> above-mentioned monomer component contains the monomer which has an acidic radical.
<6> Any one of <1> to <5>, wherein the monomer containing an acid group protected by an acid decomposable group is a monomer containing a carboxy group protected by an acid decomposable group A method for producing a polymer solution for a photosensitive transfer material as described in 1).
The polymer solution for photosensitive transfer materials manufactured by the manufacturing method of the polymer solution for photosensitive transfer materials as described in any one of <7><1>-<6>, a photo-acid generator, and 20 degreeC The manufacturing method of the composition for photosensitive transfer materials including the process of mixing the dilution solvent whose vapor pressure in 1 is 1 kPa or more and 16 kPa or less.
<8> The content of the structural unit having an acid group is 0.5% by mass to 10% by mass, based on the total mass of the polymer component contained in the composition for photosensitive transfer material to be obtained. The manufacturing method of the composition for photosensitive transfer materials as described.
<9> The average value of I / O values obtained by dividing the inorganicity value I based on the organic conceptual diagram of the polymer component contained in the composition for photosensitive transfer material obtained by the organicity value O is 0.52 or more The manufacturing method of the composition for photosensitive transfer materials as described in <7> or <8> which exists.
The photosensitive property as described in any one of <7>-<9> whose average value of the glass transition temperature of all the polymer components contained in the composition for <10> photosensitive transfer materials obtained is 90 degrees C or less. Method of a composition for a flexible transfer material.
The photosensitive transfer as described in any one of <7>-<10> whose weight average molecular weight of the polymer component contained in the composition for photosensitive transfer materials obtained <11> is 60,000 or less. Method for producing a composition for materials.
<12> Photosensitivity on a temporary support using the composition for photosensitive transfer material obtained by the method for producing a composition for photosensitive transfer material according to any one of <7> to <11> A method of producing a photosensitive transfer material comprising the step of forming a layer.
<13> A step of bringing the photosensitive layer of the photosensitive transfer material obtained by the method of producing a photosensitive transfer material according to <12> into contact with a substrate for bonding, and the photosensitive transfer after the step of laminating A step of pattern exposing the photosensitive layer of the material, a step of developing the photosensitive layer after the exposing step to form a pattern, and a step of etching the substrate in a region where the pattern is not disposed A method of manufacturing a circuit wiring, including in this order.
<14> A step of bringing the photosensitive layer of the photosensitive transfer material obtained by the method of producing a photosensitive transfer material according to <12> into contact with a substrate for bonding, and the photosensitive transfer after the step of laminating A step of pattern exposing the photosensitive layer of the material, a step of developing the photosensitive layer after the exposing step to form a pattern, and a step of etching the substrate in a region where the pattern is not disposed; A method of manufacturing a touch panel, comprising:

According to one embodiment of the present invention, it is possible to provide a method for producing a polymer solution for a photosensitive transfer material which can obtain a pattern excellent in resolution.
In addition, according to another embodiment of the present invention, a method of producing a photosensitive transfer material capable of obtaining a pattern excellent in resolution, a method of producing a circuit wiring using the same, or a touch panel using the same We can provide a way.

It is the schematic which shows an example of the laminated constitution of the photosensitive transfer material which concerns on this embodiment. It is the schematic which shows an example of the manufacturing method of the circuit wiring for touch panels using the photosensitive transfer material which concerns on this embodiment. FIG. 6 is a schematic view showing a pattern A. FIG. 7 is a schematic view showing a pattern B.

The contents of this embodiment will be described below.
Moreover, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
Moreover, in this specification, "(meth) acryl" represents both or any of acrylic and methacryl, and "(meth) acrylate" represents both or any of acrylate and a methacrylate.
Furthermore, in the present specification, the amount of each component in the composition is the total of a plurality of corresponding substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term "process" is included in the term if the intended purpose of the process is achieved, even if it can not be clearly distinguished from other processes, as well as independent processes.
In the notation of groups (atomic groups) in the present specification, notations not describing substitution and non-substitution include those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Moreover, the chemical structural formula in this specification may be described by the simplified structural formula which abbreviate | omitted the hydrogen atom.
In the present embodiment, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
Further, in the present embodiment, a combination of two or more preferable aspects is a more preferable aspect.

(Method of producing polymer solution for photosensitive transfer material)
The method for producing a polymer solution for a photosensitive transfer material according to the present embodiment includes a polymerization initiator, a polymerization solvent component, and a polymerization solvent component having a vapor pressure of 1 kPa to 16 kPa at 20 ° C., and an acid decomposable And (ii) a step of conducting a polymerization reaction in a composition containing a monomer component containing at least one monomer having an acid group protected by a group (hereinafter, also simply referred to as a “polymerization step”).

Conventionally, for the formation of a resist pattern in the formation of a circuit wiring or the like, for example, a photosensitive transfer material or the like described in Patent Document 1 is used, but there is a problem that the resolution of the obtained resist pattern is low. there were.
As a result of intensive investigations, the inventors of the present invention obtained a polymer solution for photosensitive transfer material (hereinafter, also simply referred to as a polymer solution) obtained by the method for producing a polymer solution for photosensitive transfer material according to the present embodiment. It has been found that the resolution of the obtained resist pattern is improved by using the photosensitive transfer material formed by using.
The detailed mechanism is unknown, but is presumed as follows.

The photosensitive layer in the photosensitive transfer material is formed, for example, by applying a composition containing a polymer having an acid-degradable group-protected acid group to a substrate (temporary support).
Here, the above-mentioned polymer is manufactured as a solution (polymerization solvent component solution) of the polymerization solvent component used at the time of polymerization of the polymer, but from the viewpoint of production efficiency and cost, the obtained polymer is purified Things are not common. Therefore, the composition is produced by mixing the polymerization solvent component solution of the polymer and other components without removing the polymerization solvent component, and the composition includes the polymerization solvent component. There is a case.
The photosensitive layer is formed, for example, by applying the composition to a base material, but it is preferable to apply the composition while conveying the base material having a wide application width at a high speed at the time of its production. It is difficult to dry at a high temperature for a long time, since each component of the film is likely to be nonuniform (hereinafter, also referred to as "in-plane nonuniformity") and a film that is easily deformed as a substrate.
Therefore, in the photosensitive layer obtained when the solvent having a vapor pressure of more than 16 kPa at 20 ° C. is used as the polymerization solvent component, the drying of the polymerization solvent component is fast, and the control of the drying is difficult. It is believed that the uniformity is increased. It is presumed that the increase in the in-plane non-uniformity reduces the resolution by disturbing the transmission of light during exposure.
In the photosensitive layer obtained when the solvent having a vapor pressure of less than 1 kPa at 20 ° C. is used as the polymerization solvent component, the polymerization solvent component is difficult to be removed by the above-described drying, and the polymerization solvent component is contained in the photosensitive layer. It is believed to be included as a residual solvent. It is assumed that this residual solvent causes the degradation of resolution to be caused by the diffusion of the deprotected product generated by the deprotection of the acid-degradable group-protected acid group.
According to the method for producing a polymer solution for a photosensitive transfer material according to the present embodiment, a polymer solution containing a polymerization solvent component having a vapor pressure of 1 kPa or more and 16 kPa or less at 20 ° C. can be obtained. Since in-plane nonuniformity is reduced and the polymerization solvent component hardly remains, diffusion of the above-mentioned deprotected product is suppressed, and it is considered that a pattern with excellent resolution can be obtained.
Hereinafter, the method for producing the polymer solution for a photosensitive transfer material according to the present embodiment will be described in detail.

<Polymerization process>
The polymerization step includes a polymerization solvent component containing a polymerization initiator and a polymerization solvent, and a polymerization solvent component having a vapor pressure of 1 kPa or more and 16 kPa or less at 20 ° C., and at least one single type having an acid-degradable group-protected acid group. A step of conducting a polymerization reaction in a composition containing a monomer component containing a monomer (also referred to as a "monomer").
The polymerization reaction may be any reaction in which the monomers contained in the monomer component are polymerized, but is preferably an addition polymerization reaction of the monomers, and more preferably a radical polymerization reaction. In order to perform a radical polymerization reaction, it is preferable that a polymerization initiator is a radical polymerization initiator and a monomer is a radically polymerizable compound.
The polymerization method is not particularly limited, and a known method may be used. For example, when the polymerization initiator is a thermal polymerization initiator, a monomer component, a polymerization solvent component, and a polymerization initiator are mixed. By heating the mixture, the monomers contained in the monomer component can be polymerized.
Hereinafter, the details of each component used in the polymerization step will be described.

[Polymerization solvent component]
The polymerization solvent component comprises at least one polymerization solvent.
From the viewpoint of improving resolution, as the polymerization solvent, a solvent having at least one group selected from the group consisting of an ester group, an ether group and a carbonyl group is preferable.
Hereinafter, the numerical value in the parenthesis after the solvent name represents the vapor pressure (kPa) at 20 ° C. measured by the method described later.
As a solvent having an ester group, ethyl acetate (8.7), propyl acetate (2.5), isobutyl acetate (2.0), sec-butyl acetate (1.3), isopropyl acetate (6.4), etc. Can be mentioned.
As a solvent having an ether group, diisopropyl ether (16.0), 1,4-dioxane (3.9), 1,2-dimethoxyethane (6.7), 1,3-dioxolane (7.5), Propylene glycol dimethyl ether (7.6), propylene glycol monoethyl ether (1.2) and the like can be mentioned.
As the solvent having a carbonyl group, methyl n-butyl ketone (1.3), methyl ethyl ketone (9.5), methyl isobutyl ketone (2.1), diethyl ketone (2.0), methyl n-propyl ketone (3. 3). 6), methyl isopropyl ketone (5.5) and the like.
The polymerization solvent component may also contain other solvents. Other solvents include toluene (2.9), acetonitrile (9.9), isopropanol (4.3), 2-butanol (1.6), isobutyl alcohol (1.2) and the like.
Among the above solvents, from the viewpoint of resolution, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, isobutyl acetate, diisopropyl ether, propylene glycol monoethyl ether, methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone or toluene is preferable. More preferably, it comprises ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, methyl n-butyl ketone, methyl ethyl ketone or methyl isobutyl ketone.

The solvent contained in the polymerization solvent component preferably has a vapor pressure at 20 ° C. of 1 kPa or more and 16 kPa or less.
As long as the vapor pressure at 20 ° C. of the polymerization solvent component described later is 1 kPa or more and 16 kPa or less, the polymerization solvent component may contain a solvent whose vapor pressure at 20 ° C. is less than 1 kPa or more than 16 kPa, From the viewpoint of improving the resolution, the total content of the solvent having a vapor pressure of 1 kPa or more and 16 kPa or less at 20 ° C. is preferably 95% by mass or more based on the total mass of the polymer component, and 98% by mass The content is more preferably 99% by mass or more, and still more preferably 100% by mass.
In the present embodiment, the vapor pressure of the solvent is measured by the static method described in 5th Edition Experimental Chemistry Lecture 6 “Temperature, Heat, Pressure” Maruzen, page 331-364.

  The polymerization solvent component does not contain a polymerization solvent containing a hydroxy group, or the content of the polymerization solvent containing a hydroxy group relative to the total mass of the above-mentioned polymerization solvent component is 0, from the viewpoint of the resolution of the obtained pattern. The content is preferably more than 5% by mass and no polymerization solvent containing a hydroxy group is contained, or the content is more preferably more than 0% by mass and less than 2% by mass, the hydroxy group More preferably, the polymerization solvent is not contained, or the content is more than 0% by mass and less than 1% by mass, and it is particularly preferable not to contain a polymerization solvent containing a hydroxy group.

-Vapor pressure at 20 ° C of polymerization solvent component-
The polymerization solvent component has a vapor pressure at 20 ° C. of 1 kPa or more and 16 kPa or less, preferably 1 kPa or more and 10 kPa or less, and more preferably 2 kPa or more and 6 kPa or less.
When the polymerization solvent component contains only one type of polymerization solvent, the vapor pressure at 20 ° C. of the polymerization solvent component is the same as the vapor pressure at 20 ° C. of the contained polymerization solvent.
When the polymerization solvent component contains two or more kinds of polymerization solvents, the vapor pressure at 20 ° C. of the polymerization solvent component is represented by the sum of (the vapor pressure of each polymerization solvent at 20 ° C.) × (molar fraction of each component) be able to. For example, the polymerization solvents A, B, and C in which the vapor pressure at 20 ° C. of each polymerization solvent is represented by Pa (kPa), Pb (kPa), and Pc (kPa) are included at molar fractions of na, nb, and nc, respectively. The vapor pressure Pm (kPa) of the polymerization solvent component being calculated is calculated by the following equation (Rawool's equation).
Pm = (Pa × na) + (Pb × nb) + (Pc × nc)

[Monomer component containing at least one monomer having an acid-degradable group-protected acid group]
-Monomer a 1-
The said monomer component contains at least 1 sort (s) of monomer a1 which has an acidic group protected by the acid-degradable group. When the monomer component contains the monomer a1, the photosensitive layer in the resulting photosensitive transfer material can be made into a highly sensitive chemically amplified positive type photosensitive resin composition layer.
The monomer a1 is not particularly limited as long as it is a polymerizable monomer, but is preferably a radical polymerizable compound.
The monomer a1 preferably has an ethylenically unsaturated group, and preferably has a (meth) acryloyl group from the viewpoint of reactivity.
The “acid group protected with an acid degradable group” in the present embodiment may be one known as an acid group and an acid degradable group, and is not particularly limited. As a specific acid group, a carboxy group and a phenolic hydroxyl group are preferably mentioned, and a carboxy group is more preferable. That is, the monomer a1 is preferably a monomer containing a carboxy group protected by an acid-degradable group. Moreover, as the acid-degradable protected acid group, a group which is relatively easy to be decomposed by an acid (for example, an ester group protected by a group represented by the formula A1, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) And the like (acetal functional groups such as, etc.) and groups which are relatively difficult to be decomposed by acid (for example, tertiary alkyl groups such as tert-butyl ester group, tertiary alkyl carbonate groups such as tert-butyl carbonate group) it can.
Among these, as the above-mentioned acid-decomposable group, a group having a structure protected in the form of acetal is preferable.

  As the monomer a1, a monomer (a) represented by the following formula A is preferable from the viewpoint of the sensitivity at the time of pattern formation in the photosensitive transfer material to be obtained and the 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 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 is 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. Each of R ³¹ and R ³² is 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 it is preferable that R ³¹ or R ³² and R ³³ link 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, a single bond or an arylene group is preferable, and a single bond is more preferable. 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 of being able to lower the Tg of the resulting polymer.
More specifically, it is preferable that the monomer whose R ³⁴ in Formula A is a hydrogen atom is 20% by mass or more with respect to the total content of the monomer (a) contained in the monomer component.
In addition, the content (content ratio: mass ratio) of the monomer in which R ³⁴ in the formula A in the monomer (a) is a hydrogen atom is an ordinary method based on ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can confirm by the intensity ratio of the peak intensity calculated by

  Among the monomers (a) represented by the formula A, monomers represented by the following formula A1 are more preferable from the viewpoint of further enhancing the sensitivity at the time of pattern formation in the obtained photosensitive transfer material.

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 formula A1, R ^{35 to} R ⁴¹ are preferably hydrogen atoms.

As a preferable specific example of a monomer (a) represented by Formula A, the following monomer can be illustrated. R ³⁴ represents a hydrogen atom or a methyl group.

  In addition, as the monomer a1, a monomer (b) represented by the following formula B is preferable from the viewpoint of storage stability of a polymer solution to be obtained.

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 R ^B1 or R ^B2 and R ^B3 may combine to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, and X ^B is 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 preferred. Each of R ^B1 and R ^B2 is 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 Is preferred, and a single bond or -C (= O) O- is more preferred. 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 having 1 to 4 carbon atoms or a hydrogen atom, and 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 in the para position.
In formula B, R ^B12 represents a substituent, 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 being able to lower the Tg of the resulting polymer.
More specifically, it is preferable that the monomer whose ^RB4 in Formula B is a hydrogen atom is 20 mass% or more with respect to the total content of the monomer (b) contained in a monomer component.
In addition, the content (content ratio: mass ratio) of the monomer in which R ^B4 in Formula B is a hydrogen atom in the monomer (b) is a conventional method based on ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can confirm by the intensity ratio of the peak intensity calculated by

  Among the monomers (b) represented by the formula B, monomers represented by the following formula B1 are more preferable from the viewpoint of further enhancing the sensitivity at the time of pattern formation.

In formula B1, R ^B4 represents a hydrogen atom or a methyl group, R ^{B5 to} R ^B11 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and X ^B is a group Represents a single bond or a divalent linking group, and n represents an integer of 0 to 4;
In Formula B1, X ^B has the same meaning as X ^{B in} Formula B above, and preferred embodiments are also the same.
In formula B1, R ^B4 is preferably a hydrogen atom.
In formula B1, R ^{B5 to} R ^B11 are preferably a hydrogen atom.
In formula B1, R ^B12 represents a substituent, 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, preferably 0 or 1, and more preferably 0.

The following monomers can be illustrated as a preferable specific example of a monomer (b) represented by Formula B. R ^B4 represents a hydrogen atom or a methyl group.

The monomer a1 contained in the monomer component may be of one type or of two or more types.
The content of the monomer a1 in the monomer component is 10% by mass or more and 60% by mass or less based on the total mass of the monomer component from the viewpoint of excellent resolution of the pattern of the photosensitive transfer material to be obtained Is preferable, 12 to 55 mass% is more preferable, and 15 to 50 mass% is further preferable.
The content (content ratio: mass ratio) of the monomer a1 in the monomer component can be confirmed by the intensity ratio of peak intensities calculated from ¹³ C-NMR measurement by an ordinary method.
Further, the content of the monomer represented by the above-mentioned formula A in the monomer component is relative to the total mass of the monomer component from the viewpoint of the sensitivity at the time of pattern formation and the resolution of the obtained pattern. The content is preferably 10% by mass to 60% by mass, more preferably 12% by mass to 55% by mass, and still more preferably 15% by mass to 50% by mass.

<< Monomer a2 >>
It is preferable that the monomer component used in this embodiment further includes a monomer a2 having an acid group. The monomer a2 is a monomer containing an unprotected acid group in the form of acetal, that is, an acid group having no group in the form of acetal. When the monomer component contains the monomer a2, the sensitivity at the time of pattern formation in the obtained photosensitive transfer material becomes good, and it becomes easily soluble in an alkaline developer in the development step after pattern exposure, and the development time is shortened. Can be implemented.
The term "acid group" as used herein means a proton dissociative group having a pKa of 12 or less. From the viewpoint of sensitivity improvement, 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.

Examples of the acid group possessed by the monomer a2 include 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, and a sulfonic acid group. Examples thereof include acid groups derived from and acid groups derived from phenolic hydroxyl groups. Among them, at least one selected from an acid group derived from a carboxy group and an acid group derived from a phenolic hydroxyl group is preferable, and a carboxy group is more preferable.
When the monomer component contains the monomer a2, an acid group is introduced into the resulting polymer.
The monomer a2 is preferably a styrene compound substituted by an acid group, a vinyl compound or (meth) acrylic acid.

As the monomer a2, a monomer having a carboxy group and a monomer having a phenolic hydroxyl group are preferable from the viewpoint that the sensitivity at the time of pattern formation in the photosensitive transfer material to be obtained becomes better.
The monomer a2 is not limited to the examples described above.

The monomer a2 contained in the monomer component may be only one type or two or more types.
The content of the monomer having an acid group (monomer a2) is 0.1% by mass to 20% with respect to the total mass of the monomer component from the viewpoint of patternability in the photosensitive transfer material to be obtained % Is preferable, 0.5 mass%-15 mass% are more preferable, 1 mass%-10 mass% are still more preferable.
The content (content ratio: mass ratio) of the monomer a2 in the monomer component can be confirmed by the intensity ratio of peak intensities calculated from ¹³ C-NMR measurement by an ordinary method.

-Monomer a3-
The monomer component is a monomer other than the monomer having a group in which the above-mentioned acid group is protected in the form of acetal and the monomer having an acid group (“monomer a3” May be included).
The other monomer is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, and bicyclo Unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds Can be mentioned.
The other properties of the resulting polymer can be adjusted by adjusting the type and / or content of other monomers. In particular, by appropriately using other monomers, the Tg of the resulting polymer can be easily adjusted to 90 ° C. or less.
The monomer component may contain only one other monomer component, or may contain two or more.

  Other monomers are, specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic 2-Hydroxyethyl acid, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ,ethylene Recall mono acetoacetate mono (meth) acrylate, and the like. In addition, the compound as described in stage 0021-stage 0024 of Unexamined-Japanese-Patent No. 2004-264623 can be mentioned.

  Further, as another monomer, a group having an aromatic ring or a group having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical properties of the transfer material to be obtained. Specifically, styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and (meth) acrylic And the like. Among them, as another monomer, preferred is cyclohexyl meta) acrylate.

  Moreover, as another monomer, from the viewpoint of lamination suitability and resolution, (meth) acrylic acid alkyl ester is preferable, acrylic acid alkyl ester is more preferable, acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is preferable. Particularly preferred. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate can be mentioned.

  Furthermore, it is preferable that the said monomer component has a monomer represented by following formula 2 as another monomer.

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 lamination suitability and resolution.
R ^c in the 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 preferably 4 to 12 carbon atoms, from the viewpoint of lamination suitability and resolution. The alkyl group is more preferably an alkyl group, and particularly preferably an alkyl group having 5 to 9 carbon atoms.
In addition, the alkyl group in R ^c may be linear, or may have a branch or a ring structure.

85 mass% or less is preferable with respect to the total mass of the said monomer component, as for content of the monomer a3, 80 mass% or less is more preferable, 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 monomer represented by the above formula 2 is preferably 10% by mass to 85% by mass, and 15% by mass to 15% by mass with respect to the total mass of the monomer component from the viewpoint of lamination suitability and resolution. 80 mass% is more preferable, and 20 mass% to 75 mass% is further preferable.

  Examples of preferable combinations of the monomer components in the present embodiment include A-1 to A-22 and the like used in Examples, but it is needless to say that the present invention is not limited thereto.

[Polymerization initiator]
As the polymerization initiator, known polymerization initiators can be used without particular limitation, and both photopolymerization initiators and thermal polymerization initiators can be used, but since crosslinking can be formed with a simple device, it is possible to use heat. Polymerization initiators are preferred. Hereinafter, although the radical polymerization initiator which is a preferable polymerization initiator is explained in full detail, this embodiment does not receive a restriction | limiting by these descriptions.

Preferred polymerization initiators in the present embodiment are, but not limited to, (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaary. Rubiimidazole compounds, (f) ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, (l) Azo compounds and the like can be mentioned.
As said (a)-(k), the compound mentioned by stage 0074-0118 of Unexamined-Japanese-Patent No. 2008-63554 can be used preferably, for example.

(L) Azo compounds As preferable (l) azo compounds as the polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobispropionitrile, 1,1'-azobis ( Cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-) 2,4-Dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methylpropionamidoxime), 2,2′-azobis [2- (2-) Imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [2 -Methyl N- (2-hydroxyethyl) propionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2 ,, 2'-Azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropio) And the like.
Azo compounds are preferably used in view of low solvent contamination and easy handling during production.

The polymerization initiator may be used alone or in combination of two or more.
The use amount of the polymerization initiator is not particularly limited, but is preferably 0.01 to 30% by mass, and more preferably 0.1 to 20% by mass with respect to the total mass of the monomer component. And 1 to 15%.

[Other ingredients]
In the polymerization reaction, other components such as a sensitizer and a catalyst may be further used, but it is preferable not to use other components from the viewpoint that it is preferable not to perform the purification step described later.

<Other process>
The method for producing a polymer solution for a photosensitive transfer material according to the present embodiment may include a purification step of purifying the obtained polymer, but preferably does not include a purification step.
As an example of a purification process, the aspect which re-precipitates the polymer obtained using a poor solvent, dissolves using a solvent, after performing operations, such as filtration, is mentioned.
By not including such reprecipitation operation, the amount of the organic solvent used is reduced, so that the mass production suitability is excellent and the environmental load is reduced.
In particular, when the glass transition temperature (Tg) of the polymer obtained by the polymerization reaction is 90 ° C. or less in order to improve the laminating property of the photosensitive transfer material obtained, the polymer is soft and solidifies easily. It is preferable not to do it because it can not be done and re-sinking operation is difficult.
As another example of the purification process, for example, there is an aspect of performing a concentration operation of removing the polymerization solvent component by raising the temperature of the polymer solution.
Since the decomposition of the acid-degradable group protecting the acid group derived from the monomer a1 generated at high temperature is preferably suppressed by not performing the concentration operation.
Moreover, by not including the purification step such as the above reprecipitation operation or the above concentration operation, the working time is shortened, and the production efficiency in terms of time and cost is improved.
As described above, the polymer solution obtained by the method for producing a polymer solution for a photosensitive transfer material of the present embodiment is used for the method for producing a composition for a photosensitive transfer material described later without passing through a purification step. Is preferred.

(Method of producing composition for photosensitive transfer material)
The method for producing a composition for photosensitive transfer material (hereinafter, also simply referred to as “composition”) according to the present embodiment is a method for producing a photosensitive transfer material manufactured by a method for producing a polymer solution for photosensitive transfer material. And a step of mixing the combined solution, the photoacid generator, and a dilution solvent having a vapor pressure of 1 kPa or more and 16 kPa or less at 20 ° C. (hereinafter, also referred to as “mixing step”).
Hereinafter, the polymer contained in the polymer solution for photosensitive transfer materials is also referred to as “specific polymer”.

<Mixing process>
In the mixing step, the components contained in the photosensitive transfer material composition are mixed.
It does not specifically limit as method to mix, What is necessary is just to mix by a well-known method. For example, the composition for photosensitive transfer material can be prepared by stirring and dissolving the above-mentioned components.
In the mixing step, each component to be used may be mixed at one time or, for example, after each component is made into a solution previously dissolved in a solvent such as a dilution solvent, the obtained solution is made in a predetermined ratio It may be mixed.
Hereinafter, the details of each component used in the method for producing a polymer solution for a photosensitive transfer material according to the present embodiment will be described.

[Polymer solution for photosensitive transfer material]
The polymer solution for a photosensitive transfer material is a solution obtained by the method for producing a polymer solution for a photosensitive transfer material according to the present embodiment described above.
As described above, by using the polymer solution for photosensitive transfer material without purification, it is excellent in mass production suitability, the environmental load is reduced, and the acid group derived from the monomer a1 is protected. The effects of suppressing the decomposition of the acid-degradable group and improving the production efficiency in terms of time and cost can be obtained.

Further, in the polymer solution for photosensitive transfer material, the content of the specific polymer contained is relative to the total solid content of the polymer solution for photosensitive transfer material, from the viewpoint of excellent adhesion of the photosensitive transfer material to the substrate. It is preferable to use the amount which will be 50 mass%-99.9 mass%, and it is more preferable to use the amount which becomes 70 mass%-98 mass%.
In the present embodiment, the solid content refers to the total mass of components excluding the solvent from the entire composition.

[Dilution solvent whose vapor pressure at 20 ° C is 1 kPa or more and 16 kPa or less]
In the mixing step, a dilution solvent having a vapor pressure of 1 kPa or more and 16 kPa or less at 20 ° C. (hereinafter, also simply referred to as “dilution solvent”) is used.
1 kPa or more and 10 kPa or less are preferable, and, as for the vapor pressure in 20 degreeC of a dilution solvent, 2 kPa or more and 6 kPa or less are more preferable.

The dilution solvent is not particularly limited as long as the vapor pressure at 20 ° C. falls within the above range, and may be selected in consideration of the mixability, solubility, and the like of each component contained.
As said dilution solvent, the solvent similar to the polymerization solvent whose steam | vapor pressure in above-mentioned 20 degreeC is 1 kPa or more and 16 kPa or less is mentioned, for example.
Among the above solvents, from the viewpoint of the solubility of other components used in the mixing step, ethyl acetate, propyl acetate, isopropyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, tert butyl acetate, cyclopentyl methyl ether, diisopropyl ether, propylene glycol mono It preferably contains ethyl ether, methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl isopropyl ketone or toluene, and more preferably contains propyl acetate, isopropyl acetate, isobutyl acetate, methyl ethyl ketone or.
In particular, the dilution solvent is preferably at least one selected from the group consisting of propyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, tert butyl acetate, methyl ethyl ketone and cyclopentyl methyl ether, and as a polymerization solvent, propyl acetate, It is more preferable to combine with at least one selected from the group consisting of isopropyl acetate, isobutyl acetate, butyl acetate and tert butyl acetate.
As the dilution solvent, the same solvent as the polymerization solvent contained in the polymer solution for photosensitive transfer material to be used may be used, or a different solvent may be used.
Moreover, a dilution solvent may be used individually by 1 type, and may use 2 or more types together.

  95 mass% or more is preferable, as for the usage-amount of a dilution solvent with respect to the total mass of the dilution solvent used in a mixing process, and the other solvent mentioned later, 98 mass% or more is preferable, 99 mass% or more is more preferable, 100 % By mass is more preferred.

[Photo acid generator]
The photoacid generator is a compound capable of generating an acid upon irradiation with actinic radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
As a photo-acid generator used by this embodiment, although it is sensitive to the actinic light of wavelength 300 nm or more, preferably a wavelength of 300 nm-450 nm, and generates the acid, it is preferred, but it is not restricted by the chemical structure. In addition, a photoacid generator which does not directly react to actinic light having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that responds to actinic light having a wavelength of 300 nm or more by using it in combination with a sensitizer. It can be preferably used in combination.
As a photo-acid generator used in this embodiment, a photo-acid generator that generates an acid with a pKa of 4 or less is preferable, a photo-acid generator that generates an acid with a pKa of 3 or less is more preferable, and a pKa of 2 Particularly preferred are photoacid generators which generate the following acids. The lower limit value of pKa is not particularly limited, but is preferably, for example, -10.0 or more.

As a photo-acid generator, an ionic photo-acid generator and a nonionic photo-acid generator can be mentioned.
Further, 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 More preferably,

  Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound in terms of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. As a specific example of trichloromethyl-s-triazines and a diazomethane derivative, the compound as described in stage 0083-stage 0088 of Unexamined-Japanese-Patent No. 2011-221494 can be illustrated.

  As the oxime sulfonate compound, that is, the 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 to another atom or another group.

In the compound containing an oxime sulfonate structure represented by the formula (B1), any group may be substituted, and the alkyl group in R ²¹ may be linear or branched. And may have a ring structure. The permissible substituents are described below.
The alkyl group of R ^21, 1 to 10 carbon atoms, straight-chain or branched alkyl group is preferable. The alkyl group of R ²¹ is a bridged alicyclic group such as an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group (7, 7-dimethyl-2-oxonorbornyl group, etc. And preferably a bicycloalkyl group or the like, or a halogen atom.
The aryl group of R ^21, preferably an aryl group having 6 to 18 carbon atoms, a phenyl group or a naphthyl group are 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 the oxime sulfonate compound described in paragraph 0078 to paragraph 0111 of JP-A-2014-85643.

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

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

The photoacid generators may be used alone or in combination of two or more.
The amount of the photoacid generator used in the mixing step is preferably 0.5% by mass to 20% by mass with respect to the total solid content of the composition obtained, from the viewpoint of sensitivity and resolution. It is more preferable to use an amount of 1% by mass to 15% by mass, and even more preferable to use an amount of 1% by mass to 10% by mass.

-Other polymers-
In the mixing step, in addition to the above specific polymer, a polymer containing no structural unit derived from the monomer a1 having a group in which the acid group is protected in the form of acetal may be referred to as "other polymer" ) May also be used.
In the present embodiment, unless otherwise stated, “polymer component” means one including other polymers added as needed in addition to the above-mentioned specific polymer contained in the composition. I assume. In addition, even if it is a high molecular compound, the compound applicable to the plasticizer, the heterocyclic compound, and surfactant which are mentioned later shall not be contained in the said polymer component.
The blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less in the total polymer components.
The other polymer may contain only one type, or may contain two or more types.

  In the mixing step, the other polymer may be used as a solution of the other polymer, but in that case, the solvent component used is the same as the above-mentioned polymerization solvent component, and the preferred embodiments are also the same. .

It is preferable that the polymer component which concerns on this embodiment further contains the polymer which has an acidic radical as another polymer.
As an acid group, a carboxy group is mentioned preferably.
There is no restriction | limiting in particular as a polymer which has an acidic radical, Although a well-known thing can be used, it is preferable to use the polymer (linear organic polymer) which has a linear acidic radical. As such a linear organic polymer, known ones can be optionally used. Preferably, a linear organic polymer which is soluble or swellable in water or weakly alkaline water is selected to enable water development or weakly 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, weakly alkaline water or an organic solvent. For example, water development is possible with water-soluble organic polymers. As such a linear organic polymer, a radical polymer having a carboxylic acid group in a side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a monomer having a carboxy group alone or A copolymerized resin, a monomer having an acid anhydride mono- or copolymerized to hydrolyze or half-esterify or half-amidate an acid anhydride unit, an epoxy resin with unsaturated monocarboxylic acid and acid anhydride The modified epoxy acrylate etc. are mentioned. Examples of monomers having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like, and monomers having an acid anhydride include maleic anhydride and the like Be
There are also acid cellulose derivatives having a carboxy group in the side chain. In addition to this, a polymer having a hydroxyl group to which a cyclic acid anhydride is added is useful.

The polymer having an acid group may be used alone or in combination of two or more.
When a polymer having an acid group is used, the amount of the polymer having an acid group is not particularly limited, but is 1% by mass to 70% by mass with respect to the total solid content of the composition obtained. Is preferable, 2 to 50% by mass is more preferable, and 5 to 30% by mass is even more preferable.

  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 (all, Sartmar, Inc.) ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, made by Toagosei Co., Ltd.), and Joncryl 690, It is also possible to use Joncryl 678, Joncryl 67, and Joncryl 586 (manufactured by BASF).

-Average value of I / O value of polymer component-
The polymer component used in this embodiment has an average value of I / O values obtained by dividing the inorganicity value I based on the organic conceptual diagram by the organicity value O from the viewpoint of exposure sensitivity of the photosensitive transfer material to be obtained. It is preferably 0.52 or more, more preferably 0.55 or more and 0.70 or less, and still more preferably 0.57 or more and 0.68 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 value is included in the above range, but it is preferably 0.52 or more It is preferable that it is 0.55 or more and 0.70 or less, and it is still more preferable that it is 0.57 or more and 0.68 or less.
Regarding the above I / O values, refer to organic conceptual diagram (Yoshida Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, page 1-16 (1954); domain of chemistry, vol. 11, vol. 10, pp. 719-725 (1957); Fragrance Journal, No. 34, pp. 97-111 (1979); Fragrances Journal, No. 50, pp. 79-82 (1981); There is a detailed explanation. The concept of I / O value is a Cartesian coordinate in which the property of a compound is divided into an organic group exhibiting covalent bondability and an inorganic group exhibiting ionic bondability, and all organic compounds are named organic axis and inorganic axis It is positioned and shown one by one above.

The I / O value in the case where the polymer component contains two or more types 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 Where A2 is a mass fraction, M2 is a mass fraction, A3 is a polymer 3 I / O value, and M3 is a mass fraction, the I / O value Am of the mixed component can be estimated as follows.
Am = A1 x M1 + A2 x M2 + A3 x M3
In addition, when a polymer component contains only 1 type of polymer independently, the I / O value of only 1 type of contained polymer turns into 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, and from −20 ° C. to 90 ° C., from the viewpoint of laminate suitability in the photosensitive transfer material obtained. The temperature is preferably 20 ° C. to 90 ° C., more preferably 20 ° C. to 60 ° C., and particularly preferably 25 ° C. to 45 ° C.
Further, the Tg of the specific polymer used in the present embodiment may be appropriately set so that the average value of the above Tg is included in the above range, but it is preferably 0 ° C. or more and 90 ° C. or less, and preferably 20 ° C. or more It is more preferable that it is 70 degrees C or less, and it is still more preferable that it is 20 degrees C or more and 50 degrees C or less.
The glass transition temperature of the resin such as the 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). The glass transition temperature in the present specification uses an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig).
The method of measuring the glass transition temperature will be described more specifically.
When the glass transition temperature is determined, the temperature is kept at about 50 ° C. lower than the expected polymer Tg until the device is stabilized, and then the heating rate: 20 ° C./min, and the temperature is about 30 Heat to a high temperature and draw a differential thermal analysis (DTA) curve or a DSC curve.
Extrapolation glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line extending the baseline on the low temperature side in the DTA curve or DSC curve to the high temperature side, and the step change portion of the glass transition It is determined as the temperature at the point of intersection with the tangent drawn at the point where the slope of the curve is maximum.

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

The glass transition temperature when the polymer component contains two or more polymers can be considered as follows. For example, when the polymer component contains three types of polymers (polymer 1 to polymer 3), the glass transition temperature of the polymer 1 is Tg1 (K), the mass fraction is M1, and the glass transition of the polymer 2 When the temperature is Tg 2 (K), the mass fraction is M 2, the glass transition temperature of the polymer 3 is Tg 3 (K), and the mass fraction is M 3, the average value Tgm (K) of the glass transition temperatures of the mixed components Can be estimated as follows.
1 / Tgm = (M1 / Tg1) + (M2 / Tg2) + (M3 / Tg3)
In addition, when a polymer component contains the polymer of only 1 type independently, Tg of the polymer of only 1 type 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 60,000 or less in terms of weight average molecular weight (Mw) in terms of polystyrene. When the weight-average molecular weight of the above-mentioned polymer is 60,000 or less, the melt viscosity of the photosensitive layer in the photosensitive transfer material is kept low, and bonding at a low temperature (for example, 130 ° C. or less) It can be realized.
The weight average molecular weight of the polymer component is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000.
The weight average molecular weight of the specific polymer used in the present embodiment may be appropriately set so that the weight average molecular weight of the polymer component is included in the above-mentioned range, but it is 6,000 or more and 40,000 or less Preferably, it is more preferably 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).
The measurement of the weight average molecular weight by gel permeation chromatography (GPC) is carried out using HLC (registered trademark) -8220GPC (manufactured by Tosoh Corp.) as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) as a column. .6 mm ID x 15 cm, Tosoh Corp. product, Super HZ 4000 (4.6 mm ID x 15 cm, Tosoh Corp. product), Super HZ 3000 (4.6 mm ID x 15 cm, Tosoh Corp. product), Super HZ 2000 (4.6 mm ID) It is possible to use THF (tetrahydrofuran) as an eluent using one obtained by connecting in series each one x 15 cm, manufactured by Tosoh Corp., in series.
In addition, as measurement conditions, the sample concentration is 0.2% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, and the measurement temperature is 40 ° C., using a differential refractive index (RI) detector be able to.
The standard curve is "standard sample TSK standard, polystyrene" manufactured by Tosoh Corp .: "F-40", "F-20", "F-4", "F-1", "A-5000", " It can produce using any of seven samples of A-2500 "and" A-1000. "
The ratio (dispersion degree) of the number average molecular weight to the weight average molecular weight of the specific polymer component is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

-Amount of acid groups 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 patternability. 0.5 mass% or more and 15 mass% or less are more preferable, and 1 mass% or more and 10 mass% or less are more preferable.
The content of the constituent unit having an acid group is a constituent unit having an acid group when all the polymers contained in the polymer component are decomposed into constituent units (monomer units) with respect to the total mass of the polymer component. The ratio of the content mass of

The composition in the present embodiment preferably contains the above-mentioned polymer component in a proportion of 50% by mass to 99.9% by mass with respect to the total solid content of the composition, from the viewpoint of lamination suitability, 70% by mass to 98%. It is more preferable to include in the ratio of mass%.
In addition, from the viewpoint of expressing good adhesion to the substrate in the photosensitive transfer material to be obtained, the above specific polymer is contained in a ratio of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive layer. Is preferable, and it is more preferable to contain in the ratio of 70 mass%-98 mass%.

[Other solvents]
In the mixing step, other solvents other than the above-mentioned dilution solvents may be used.
The composition in the present embodiment does not use other solvents, or the amount of other solvents used is more than 0% by mass and 5% by mass or less with respect to the total mass of the solvent contained in the composition It is preferable to use any other solvent, or the amount of other solvent used is more than 0% by mass and not more than 2% by mass with respect to the total mass of the solvent contained in the composition. More preferably, no other solvent is used, or the amount of other solvent used is more than 0% by mass and not more than 1% by mass with respect to the total mass of the solvent contained in the composition. It is further preferred to use, and it is particularly preferred not to use other solvents.

  Other 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, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, etc. It is possible to exemplify one that does not correspond to the above-mentioned dilution solvent. Further, specific examples of the solvent include the solvents described in paragraph 0174 to paragraph 0178 of JP-A-2011-221494, which do not correspond to the above-mentioned dilution solvents, and the contents thereof are incorporated in the present specification. Be

  When another solvent is used in the mixing step, the vapor pressure at 20 ° C. of the solvent component contained in the composition, which is determined by the above Raool equation, is preferably 1 kPa or more and 16 kPa or less, more preferably 1 kPa or more and 10 kPa or less Preferably, 2 kPa or more and 6 kPa or less is more preferable.

[Other additives]
In the mixing step, other additives may be further used, as necessary.

-Plasticizer-
In the mixing step, a plasticizer may be used for the purpose of improving the plasticity of the photosensitive layer in the resulting photosensitive transfer material.
It is preferable that the said plasticizer has a smaller weight average molecular weight than the said 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 to develop 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 said formula, R is a C2-C8 alkylene group, n represents the integer of 1-50, and * represents a coupling | bonding site | part with another atom.

  In addition, for example, even if it is a compound (it is set as "the compound X") which has the said alkylene oxy group, the photosensitive layer obtained using the composition which mixed the compound X, the said specific polymer, and a photo-acid generator However, when the plasticity is not improved as compared with the photosensitive layer formed without containing the compound X, it does not correspond to the plasticizer in the present embodiment. For example, surfactants that are optionally added do not fall under the plasticizers herein because they are not generally used in amounts that provide plasticity to the photosensitive layer.

  As said plasticizer, although the compound which has the following structure is mentioned, for example, it is not limited to these.

When a plasticizer is used, the amount of the plasticizer is preferably 1% by mass to 50% by mass, based on the total solid content of the composition obtained, from the viewpoint of lamination suitability, 2% by mass It is more preferable that the amount be 20% by mass.
The photosensitive layer may contain only one type of plasticizer, or may contain two or more types.

-Sensitizer-
A sensitizer can further be used in the mixing step.
The sensitizer absorbs actinic radiation (actinic radiation) to be in an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photoacid generator to produce actions such as electron transfer, energy transfer and heat generation. Thus, the photoacid generator chemically changes and decomposes to generate an acid.
By using a sensitizer, the exposure sensitivity of the resulting photosensitive transfer material can be improved.

As the sensitizer, compounds selected from the group consisting of anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyryl benzene derivatives are preferable, and anthracene derivatives are more preferable.
As the anthracene derivative, 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.

  As said sensitizer, the compound as described in Paragraph 0139-Paragraph 0141 of WO2015 / 093271 can be mentioned.

  The amount of the sensitizer used is preferably an amount of 0% by mass to 10% by mass, based on the total solid content of the composition, and more preferably 0.1% by mass to 10% by mass. preferable.

-Basic compound-
In the mixing step, it is preferable to further use a basic compound.
The basic compound can be arbitrarily selected from basic compounds used in the resist. For example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids can be mentioned. Specific examples thereof include the compounds described in paragraphs [0204] to [0207] of JP-A-2011-221494, the contents of which are incorporated herein.

Specifically, as aliphatic amines, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of aromatic amines include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
As the heterocyclic amine, for example, 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, nicotinic acid amide, 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-undesen.
Examples of quaternary ammonium hydroxides include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, and tetra-n-hexyl ammonium hydroxide.
Examples of quaternary ammonium salts of carboxylic acids include tetramethyl ammonium acetate, tetramethyl ammonium benzoate, tetra-n-butyl ammonium acetate, and tetra-n-butyl ammonium benzoate.

The above basic compounds may be used alone or in combination of two or more.
The amount of the basic compound used is preferably an amount of 0.001% to 5% by mass, preferably 0.005% to 3% by mass, with respect to the total solid content of the composition to be obtained. It is more preferable that

-Heterocyclic compound-
In the mixing step, a compound containing a heterocyclic compound can be used.
There is no particular limitation on the heterocyclic compound in the present embodiment. For example, a compound having an epoxy group or an oxetanyl group in the molecule described below, an alkoxymethyl group-containing heterocyclic compound, various cyclic ethers, oxygen-containing monomers such as 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 amount of the heterocyclic compound used is preferably 0.01% by mass to 50% by mass, and preferably 0.1% by mass to 10% by mass, with respect to the total solid content of the composition to be obtained. More preferably, an amount of 1% by mass to 5% by mass is more preferable. It is preferable in the viewpoint of adhesiveness and etching tolerance as it is the said range. The heterocyclic compound may be used alone or in combination of two or more. When two or more kinds are used in combination, the above-mentioned preferable use amount refers to a total use amount of two or more kinds of heterocyclic compounds.

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

Compounds having an epoxy group in the molecule are commercially available. For example, commercially available products described in paragraph 0189 of JP-A-2011-221494, such as JER 828, JER 1007, JER 157 S70 (manufactured by Mitsubishi Chemical Corporation), JER 157 S 65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc. may be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), 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-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, Nagase ChemteX Co., Ltd. product), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (all available from Nippon Steel & Sumikin Chemical Co., Ltd.), Celoxide 2021 P, 2081, 2000, 3000, EHPE 3150, Epolide GT 400, Celliners B 0134, B 0177 (made by Daicel Co., Ltd.) Etc.
The compound which has an epoxy group in a molecule 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 epoxy resin, bisphenol F epoxy resin, phenol novolac 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 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.

  In the mixing step in the present embodiment, it is preferable to use a compound having an epoxy group as the heterocyclic compound from the viewpoint of etching resistance and line width stability of the photosensitive transfer material to be obtained.

-Alkoxysilane compound-
In the mixing step, an alkoxysilane compound may be used. As an alkoxysilane compound, a trialkoxysilane compound is mentioned preferably.
As the alkoxysilane compound, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxy Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is further preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used singly or in combination of two or more.

-Surfactant-
In the mixing step, it is preferable to use 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 surfactants, and fluorine surfactants. . In addition, KP (made by Shin-Etsu Chemical Co., Ltd.), Polyflow (made by Kyoeisha Chemical Co., Ltd.), F-top (made by JEMCO), Megafac (made by DIC), Florard (Sumitomo 3M) under the following trade names. (Manufactured by Asahi Kasei Corp.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (Toray Dow Corning Silicone).
Moreover, the weight average as polystyrene conversion measured by gel permeation chromatography at the time of using tetrahydrofuran (THF) as a solvent, containing the structural unit A and the structural unit B represented by following formula I-1 as surfactant A copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferred example.

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 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon L represents an alkyl group having 3 to 6 carbon atoms, p and q each represent a polymerization percentage, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18 and s represents an integer of 1 to 10, and * represents a bonding position with another structure Represent.

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in the formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and in view of compatibility and wettability to the coated surface, an alkyl group having 1 to 3 carbon atoms is preferable, and the carbon number Two or three alkyl groups are more preferred. The sum of p and q (p + 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, the surfactant described in paragraph 0017 of Japanese Patent No. 4502784 and paragraph 0060 to paragraph 0071 of JP2009-237362A can also be used.

The surfactant may be used alone or in combination of two or more.
The amount of surfactant used is preferably 10% by mass or less based on the total solid content of the composition to be obtained, and more preferably 0.001% by mass to 10% by mass. The amount is preferably 0.01 to 3% by mass.

-Other ingredients-
In the mixing step, known additions such as antioxidants, acid multipliers, development accelerators, colorants, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic precipitation inhibitors Agents can be used further.
About the preferable aspect of another component, it describes in Unexamined-Japanese-Patent No.2014-85643, Paragraph 0165-Paragraph 0184, respectively, The content of this gazette is integrated in this specification.

<Other process>
The method for producing a composition for a photosensitive transfer material according to the present embodiment may include other steps.
As another process, a filtration process is mentioned, for example.
In the filtration step, each component mixed in the mixing step can be filtered using, for example, a filter with a pore diameter of 0.2 μm to make a composition.

(Method of producing photosensitive transfer material)
The method for producing a photosensitive transfer material according to the present embodiment uses the composition for a photosensitive transfer material obtained by the method for producing a composition for a photosensitive transfer material according to the present embodiment to sensitize on a temporary support Forming a property layer (hereinafter, also referred to as "photosensitive layer forming step").

<Photosensitive layer formation process>
The photosensitive layer forming step is not particularly limited. For example, the photosensitive transfer material composition obtained by the method for producing a photosensitive transfer material composition according to the present embodiment is applied to a temporary support described later. By drying and drying, a photosensitive transfer material having a photosensitive layer on the temporary support can be obtained.
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, or ink jet coating.
The application width is not particularly limited, but when the application width is relatively wide, such as 0.5 m to 10 m, for example, the effect of improving the resolution according to the present embodiment can be easily obtained.
In addition, a photosensitive layer can also be apply | coated on the laminated body of the temporary support body and other layer which have the below-mentioned other layer on a temporary support body.
The method for producing a photosensitive transfer material according to the present embodiment may use a temporary support having another layer as the temporary support, and may further include the step of forming another layer described later.

The drying method is not particularly limited, and a known drying method may be used, for example, a method of transporting the temporary support on which the composition is applied, in a high-temperature drying apparatus, and the like.
Here, the drying is performed at a low temperature (for example, 50 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C.), or the drying time is short (for example, 10 seconds to 5 minutes), 20 seconds In the case where the time of 80 seconds is more preferable), the effect of improving the resolution according to the present embodiment can easily be obtained. Moreover, according to the drying at a low temperature for a short time, the effect of the improvement of the resolution is further easily obtained.

  FIG. 1 schematically shows an example of the layer configuration of a photosensitive transfer material produced by the method for producing a photosensitive transfer material of the present embodiment. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 12, a photosensitive layer 14, and a cover film 16 are laminated in this order. The photosensitive layer 14 is a layer formed using the composition obtained by the production of the composition for a photosensitive transfer material according to the present embodiment described above.

In addition, the photosensitive layer in the present embodiment is a positive photosensitive layer, and is preferably a chemically amplified positive photosensitive layer.
The photoacid generators such as the above-mentioned onium salts and oxime sulfonate compounds are catalysts for the acid generated in response to actinic radiation (actinic radiation) against the deprotection of the protected acid groups in the specific polymer. Since the acid generated by the action of one photon contributes to a large number of deprotection reactions, the quantum yield is greater than 1, for example, a large value such as a power of 10, so-called chemical amplification High sensitivity is obtained as a result of
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic radiation, a carboxy group is produced by successive photochemical reactions, but its quantum yield is necessarily 1 or less and does not fall under the chemical amplification type.

[Temporary support]
The temporary support is a support that supports the photosensitive layer and can be peeled off from the photosensitive layer.
The temporary support used in the present embodiment preferably has light transparency from the viewpoint of being able to expose the photosensitive layer through the temporary support when the photosensitive layer is subjected to pattern exposure.
Having transparency 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 sensitivity improvement. 60% or more is preferable, and 70% or more is more preferable. As a measuring method of the transmittance | permeability, the method of measuring using Otsuka Electronics Co., Ltd. product MCPD Series is mentioned.
As a temporary support body, a glass substrate, a resin film, paper etc. are mentioned, A resin film is especially preferable from a viewpoint of intensity | strength, flexibility, etc. As a resin film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film etc. are mentioned. Among them, biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, and 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.
The temporary support may be selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring formation substrate, light transmittance required in the first exposure step, and the like. Good.

  About the preferable aspect of a temporary support body, it describes in Unexamined-Japanese-Patent No.2014-85643, Paragraph 0017-Paragraph 0018, for example, The content of this gazette is integrated in this specification.

[Other layers]
The photosensitive transfer material obtained may have a layer other than the photosensitive layer (hereinafter, may be referred to as "other layer"). Other layers may include contrast enhancement layers, interlayers, cover films, thermoplastics, and the like.

-Contrast enhancement layer-
The resulting photosensitive transfer material can have a contrast enhancement layer in addition to the photosensitive layer.
A material with a contrast enhancement layer (Contrast Enhancement Layer; CEL) that absorbs significantly to the exposure wavelength before exposure but gradually decreases as it is exposed, that is, the light transmittance increases (photo-decoloring (Referred to as a sex pigment component). As the photobleachable dye component, diazonium salts, stilbazolium salts, aryl nitroso salts and the like are known. A phenolic resin etc. are used as a film formation component.
In addition, as the contrast enhancement layer, paragraph 0004 to paragraph 0051 of JP-A-6-97065, paragraph 0012 to paragraph 0055 of JP-A-6-332167, photopolymer handbook, photopolymer conference, industry research meeting ( 1989), Photopolymer Technology, Yamaoka, Nagamatsu ed., Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

-Middle layer-
An intermediate layer can be provided on the photosensitive layer for the purpose of forming an intermediate layer and preventing mixing of components when applying a plurality of layers and during storage after application.
As an intermediate | middle layer, the intermediate | middle layer as described in stage-of Unexamined-Japanese-Patent No. 2005-259138 can be used. As the intermediate layer, those which are dispersed or dissolved in water or an aqueous alkali solution are preferable.
Materials used for the intermediate layer include, for example, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers of these. Resin is mentioned. Among them, particularly preferred is a combination of polyvinyl alcohol and polyvinyl pyrrolidone.

-Thermoplastic resin layer, cover film etc.-
The photosensitive transfer material obtained can also have, for example, a temporary support, a thermoplastic resin layer, and a photosensitive layer in this order. Furthermore, you may have a cover film in order to protect a photosensitive layer.
The preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-85643, and the preferred embodiments of the other layers are described in paragraphs 0194 to 0-196 of JP-A-2014-85643, respectively. The contents of this publication are incorporated herein.

<Step of forming other layer>
The method for producing a photosensitive transfer material according to the present embodiment may include the step of forming the other layers described above.
Specifically, other layers can be formed according to the method for producing a photosensitive transfer material described in paragraphs [0094] to [0098] of JP-A-2006-259138.
For example, in the case of producing a photosensitive transfer material having a thermoplastic resin layer and an intermediate layer, a solution obtained by dissolving a thermoplastic organic polymer and an additive on a temporary support (application for a thermoplastic resin layer) Solution) is applied and dried to form a thermoplastic resin layer, and then a resin and an additive are added to a solvent which does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer (intermediate layer) Coating solution is applied and dried to laminate an intermediate layer. Further, a composition for a photosensitive transfer material obtained by the method for producing a composition for a photosensitive transfer material according to the present embodiment, which is prepared using a solvent which does not dissolve the intermediate layer, is coated on the formed intermediate layer. The photosensitive transfer material can be suitably produced by drying and laminating the photosensitive layer.

(Method of manufacturing circuit wiring)
A first embodiment of a method for producing a circuit wiring using a photosensitive transfer material obtained by the method for producing a photosensitive transfer material according to the present embodiment will be described.
The first embodiment of the method of manufacturing circuit wiring
A step of bringing the photosensitive layer of the photosensitive transfer material obtained by the method for producing a photosensitive transfer material according to this embodiment into contact with the substrate and bonding the substrate to the substrate (bonding step);
Exposing the photosensitive layer of the photosensitive transfer material after the laminating step to a pattern exposure step (exposure step);
Developing the photosensitive layer after the exposing step to form a pattern (developing step);
Etching the substrate in the region where the pattern is not disposed (etching step) in this order.
The substrate in the first embodiment of the method for producing a circuit wiring may be a substrate such as glass, silicon, or film itself, and may be a conductive layer or the like on the substrate such as glass, silicon, or film. The substrate may be provided with any layer of
According to the first embodiment of the method of manufacturing a circuit wiring, a fine pattern can be formed on the substrate surface.

The second embodiment of the method of manufacturing circuit wiring is:
A substrate, and a plurality of conductive layers including a first conductive layer and a second conductive layer which are different in constituent material from each other, and the outermost surface layer on the surface of the substrate in order from the surface of the substrate The photosensitive layer of the photosensitive transfer material obtained by the method for producing a photosensitive transfer material according to the present embodiment is a substrate on which the first conductive layer and the second conductive layer are laminated. 1 bonding step in contact with the conductive layer for bonding
A first exposure step of pattern exposing the photosensitive layer through the temporary support of the photosensitive transfer material after the laminating step;
After peeling off the temporary support from the photosensitive layer after the first exposure step, developing the photosensitive layer after the first exposure step to form a first pattern;
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 exposing the first pattern after the first etching step to a pattern different from the first pattern;
A second developing step of developing the first pattern after the second exposure step to form a second pattern;
And 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. The second embodiment can be referred to WO 2006/190405, the contents of which are incorporated herein.

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

<Lamination process>
An example of the bonding step is schematically shown in FIG. 2 (a).
First, in the bonding step, the base material 22 and a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 which are different in constituent material from each other are provided. The positive type of the photosensitive transfer material 100 described above with respect to the substrate (substrate for circuit wiring formation) 20 on which the first conductive layer 24 and the second conductive layer 26 as the outermost surface layer are stacked in order from the surface of The photosensitive layer 14 is brought into contact with the first conductive layer 24 and attached. In addition, bonding of such a substrate for circuit wiring formation and photosensitive transfer material may be called "transfer" or "lamination."

When the cover film 16 is provided on the positive photosensitive layer 14 of the photosensitive transfer material 100 as shown in FIG. 1, after the cover film 16 is removed from the photosensitive transfer material 100 (positive photosensitive layer 14) Then, the positive type photosensitive layer 14 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and attached.
Bonding (transfer) of the photosensitive transfer material onto the first conductive layer is performed by overlapping the positive photosensitive layer side of the photosensitive transfer material on the first conductive layer and applying pressure and heat with a roll or the like. It is preferred to be done. For lamination, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further enhancing productivity can be used.
When the base material of the circuit wiring formation substrate is a resin film, bonding by roll-to-roll can also be performed.

〔Base material〕
The substrate in which a plurality of conductive layers are laminated on a substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. In the circuit wiring manufacturing method according to the present embodiment, in the case of a circuit wiring for a touch panel, it is particularly preferable that the substrate is a sheet-like resin composition.
Moreover, it is preferable that a base material is transparent.
The refractive index of the substrate is preferably 1.50 to 1.52.
The substrate may be made of a translucent substrate such as a glass substrate, and for example, tempered glass represented by Gorilla glass of Corning Co., Ltd. can be used. Moreover, as said transparent base material, the material used by Unexamined-Japanese-Patent No. 2010-86684, 2010-152809, and 2010-257492 can be used preferably.
In the case of using a film substrate as the substrate, it is more preferable to use a substrate having no optical distortion and a substrate having high transparency, and for a specific material, polyethylene terephthalate (PET), Examples include polyethylene naphthalate, polycarbonate, triacetyl cellulose and cycloolefin polymers.

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

In the method for manufacturing a circuit wiring according to the present embodiment, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.
As a conductive layer, it is preferable that it is an electrode pattern corresponded to the sensor of the visual recognition part used for an electrostatic capacitance type touch panel, or wiring of a periphery extraction part.

[Substrate for forming circuit wiring]
It is a substrate which has a conductive layer on the surface of a substrate. The conductive layer is patterned to form circuit wiring. In this example, it is preferable that a plurality of conductive layers such as metal oxides and metals be provided on a film substrate such as PET.

<Exposing step (first exposing step)>
In the first embodiment, the exposure step is performed, and in the second embodiment, the first exposure step is performed. An example of the exposure process (first exposure process) is schematically shown in FIG.
In the exposure step (first exposure step), the positive photosensitive layer 14 is pattern-exposed through the temporary support 12 of the photosensitive transfer material after the bonding step.

  As an example of the exposure step, the development step and the other steps in the present embodiment, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present 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 (the side opposite to the side in contact with the first conductive layer 24), and then the mask 30 is formed. And exposure to ultraviolet light from above the mask.
The detailed arrangement and specific size of the pattern in the present embodiment are not particularly limited. Since it is desirable to improve the display quality of a display device (for example, a touch panel) provided with an input device having circuit wiring manufactured according to this embodiment and to minimize the area occupied by the extraction wiring, at least a part of the pattern (especially the touch panel) Preferably, the electrode pattern and the part of the lead-out wiring are thin lines of 100 .mu.m or less, and more preferably 70 .mu.m or less.
Here, as a light source used for exposure, it can be appropriately selected and used as long as it can emit light (for example, 365 nm, 405 nm, etc.) in a wavelength range in which the exposed portion of the photosensitive transfer material can dissolve in the developer. . Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned.
Energy of exposure generally ^5mJ / cm ^{2 ~200mJ} / cm 2 or so, preferably 10mJ ^/ cm ² ~100mJ ^/ cm 2 approximately.
Further, it is also preferable to carry out heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By means of a process called so-called PEB (Post Exposure Bake), it is possible to reduce roughness of the pattern edge due to standing waves generated in the photosensitive layer at the time of exposure.

  In addition, even if pattern exposure is performed after peeling a temporary support from a positive photosensitive layer, it is exposed through a temporary support before peeling a temporary support, and then peels off the temporary support. May be In order to prevent the contamination of the mask due to the contact between the photosensitive layer and the mask and to avoid the influence on the exposure due to the foreign matter attached 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 developing step (first developing step) is schematically shown in FIG. 2 (c).
In the developing step (first developing step), after the temporary support 12 is peeled off from the positive photosensitive layer 14 after the exposing step (first exposing step), the positive photosensitive after the exposing step (first exposing step) The layer 14 is developed to form a 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 layer.
The development of the patternwise exposed positive-working photosensitive layer can be carried out using a developer.
The developer is not particularly limited as long as the exposed portion of the positive photosensitive layer can be removed, and for example, known developers such as the developer described in JP-A-5-72724 can be used. . The developing solution is preferably a developing solution in which the exposed portion of the positive photosensitive layer has a dissolution type developing behavior. For example, a developing solution of an aqueous alkaline solution system containing a compound of pKa = 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. As a developing solution suitably used in this embodiment, the developing solution as described in Paragraph 0194 of WO2015 / 093271 is mentioned, for example.

  The developing method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, dip development and the like. Here, to describe shower development, an exposed portion can be removed by spraying a developer onto the positive photosensitive layer after exposure. In addition, after development, it is preferable to remove a development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The solution 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 type photosensitive layer obtained by developing.
Post-baking heating is preferably performed under an environment of 8.1 kPa to 121.6 kPa, and more preferably performed under an environment of 506.6 kPa or more. On the other hand, it is more preferable to carry out under an environment of 1114.6 kPa or less, and it is particularly preferable to carry out under 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.
Post-baking may be performed in an air environment or in a nitrogen-substituted environment.

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

<Etching Process (First Etching Process)>
In the first embodiment, the etching step is performed, and in the second embodiment, the first etching step is performed. An example of the etching step (first etching step) 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 among the plurality of conductive layers in the region where the first pattern 14A is not disposed are etched. By the etching, the first conductive layer 24A and the second conductive layer 26A having the same pattern are formed.

  The etching of a conductive layer can apply etching by well-known methods, such as the method as described in Unexamined-Japanese-Patent No.2010-152155 Paragraph 0048-paragraph 0054 grade | etc., The method by dry etchings, such as a well-known plasma etching.

For example, as a method of etching, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be mentioned. The etching solution used for wet etching may be appropriately selected from acid type or alkaline type etching solution in accordance with the object of etching.
Examples of the acid type etching solution include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid and phosphoric acid alone, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride and potassium permanganate Be done. An acidic component may use the component which combined the several acidic component.
As an alkaline type etching solution, an aqueous solution of an alkali component alone such as sodium hydroxide, potassium hydroxide, ammonia, organic amine, salt of organic amine such as tetramethyl ammonium hydroxide, alkali component and potassium permanganate etc. A mixed aqueous solution of salts and the like are exemplified. 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 less. It is preferable that the first pattern used as an etching mask (etching pattern) in the present embodiment exhibits particularly excellent resistance to an acidic and alkaline etching solution in a temperature range of 45 ° C. or less. Therefore, peeling of the positive photosensitive layer during the etching process is prevented, and portions where the positive photosensitive layer is not present are selectively etched.

After the etching process, a cleaning process and a drying process may be performed as needed in order to prevent contamination of the process line. 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) Is adjusted appropriately and drying may be performed.

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

<Second developing step>
In the second embodiment, the second development step is performed. An example of the second developing step 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, a portion of the first pattern exposed 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 step>
In the second embodiment, a 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 of the plurality of conductive layers in the region where the second pattern 14B is not disposed is etched.

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, depending on the desired pattern, it is preferable to selectively etch less conductive layers than in the first etching step. For example, as shown in FIG. 2, the first conductive layer is etched by using an etching solution that selectively etches only the first conductive layer 24B in the region where the positive photosensitive layer is not disposed. The pattern of the two conductive layers can be different.
After the completion of the second etching process, a circuit wiring including the conductive layers 24B and 26A of at least two types of patterns is formed.

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

Although there is no restriction | limiting in particular as a method to remove the positive type photosensitive layer which remain | survives, The method to remove by chemical processing can be mentioned.
The method for removing the positive photosensitive layer is, for example, a substrate having a positive photosensitive layer or the like as a peeling solution during stirring at 30 ° C. to 80 ° C., preferably 50 ° C. to 80 ° C. for 1 minute to 30 minutes. The method of immersing is mentioned.

  As the peeling solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide or an organic alkali component such as a primary amine, a secondary amine, a tertiary amine or a quaternary ammonium salt, And dimethylsulfoxide, N-methyl pyrrolidone or a mixed solution thereof. A peeling solution may be used to peel off by a spray method, a shower method, a paddle method or the like.

  The method of manufacturing a circuit wiring 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.

<Step of sticking protective film>
In the second embodiment, even after the first etching step and before the second exposure step, the method further includes the step of sticking a light transmitting protective film (not shown) on the first pattern. Good.
In this case, it is preferable that in the second exposure step, the first pattern is pattern-exposed through the protective film, and after the second exposure step, the second development step is performed after the protective film is peeled off from the first pattern.

<Step of reducing visible light reflectance>
The method of manufacturing a circuit wiring according to the present embodiment can include the step of reducing the visible light reflectance of part or all of the plurality of conductive layers on the substrate.
An oxidation process etc. can be mentioned as a process which reduces the visible light reflectance. For example, by oxidizing copper to form copper oxide, the visible light reflectance can be reduced by blackening.
About the preferable aspect of the process to which the visible light reflectance is reduced, Paragraph 0017-Paragraph 0025 of Unexamined-Japanese-Patent No. 2014-150118, and Paragraph 0041, Paragraph 0042, Paragraph 0048, and paragraph 0058 of Unexamined-Japanese-Patent No. 2013-206315. The contents of this publication are incorporated herein by reference.

<Step of forming a new conductive layer on the insulating film>
The method for manufacturing a circuit wiring according to the present embodiment preferably includes the steps of forming an insulating film on the formed circuit wiring and 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 with a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
There is no particular limitation on the step of forming a new conductive layer on the insulating film. A photosensitive material having conductivity may be used to form a new conductive layer of a desired pattern by photolithography.

  Moreover, although the case where the circuit wiring which has two different patterns was formed with respect to the board | substrate for circuit wiring formation provided with the conductive layer of two layers was demonstrated in the description which referred to FIG. 2, the circuit wiring which concerns on this embodiment. The number of conductive layers of the substrate to which the manufacturing method of the present invention is applied is not limited to two, and a combination of the exposure step, the developing step, and the etching step described above is used using the circuit wiring forming substrate in which three or more conductive layers are stacked. By performing three or more times, three or more conductive layers can be formed in different circuit wiring patterns.

  Further, although not shown in FIG. 2, in the method of manufacturing a circuit wiring according to the present embodiment, the base material has a plurality of conductive layers respectively on both surfaces, and the conductive material formed on both surfaces of the base material It is also preferred that the layers be circuited sequentially or simultaneously. With such a configuration, it is possible to form a touch panel circuit wiring in which the first conductive pattern is formed on one surface of the base and the second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touchscreens 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 method for manufacturing a circuit wiring according to the present embodiment.
The circuit board which concerns on this embodiment is a board | substrate which has the circuit wiring manufactured by the manufacturing method of the circuit wiring which concerns on this embodiment.
Although the use of the circuit board which concerns on this embodiment is not limited, For example, it is preferable that it is a circuit board for touch panels.

(Input device and display device)
As an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring which concerns on this embodiment, an input device is mentioned.
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, and 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 method for manufacturing a circuit wiring 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 method for manufacturing a circuit wiring according to the present embodiment, and is a touch panel display device having a touch panel according to the present embodiment. preferable.
It is preferable that the manufacturing method of the touch panel or touch-panel display apparatus which concerns on this embodiment includes the manufacturing method of the circuit wiring which concerns on this embodiment.
In the method of manufacturing a touch panel or a touch panel display device according to the present embodiment, a step of bringing the photosensitive layer of the photosensitive transfer material obtained by the method of producing a photosensitive transfer material into contact with a substrate and bonding them; Subsequent steps of pattern exposing the photosensitive layer of the photosensitive transfer material, developing the photosensitive layer after the exposing step to form a pattern, and a substrate in a region where the pattern is not disposed It is preferable to include the step of performing the etching process in this order. The details of each step are the same as the details of each step in the method of manufacturing a circuit wiring described above, 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 methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. . Among them, the capacitance method is preferable.
As a touch panel type, a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), a so-called on-cell type (for example, JP-A 2013-168125) 19 described in Japanese Patent Application Laid-Open No. 2012-89102, and those described in FIG. 1 and FIG. 5 of Japanese Patent Application Laid-Open No. 2012-89102, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (e.g. The other structures (for example, the ones described in FIG. 6 of JP-A-2013-164871), various out-cell types (so-called GG, G1 · G2, GFF, GFF, etc.) GF2, GF1, G1F etc. can be mentioned.
As the touch panel of the present embodiment and the touch panel display device of the present embodiment, “latest touch panel technology” (issued on July 6, 2009, published by Techno Times Inc.), supervised by Yuji Mitani, “touch panel technology and development”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress
The configuration disclosed in Semiconductor Corporation Application Note AN2292 and the like can be applied.

  Hereinafter, the embodiment of the present embodiment will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following Examples can be appropriately changed without departing from the spirit of the present embodiment. Therefore, the scope of the present embodiment is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.

(Synthesis of polymer component)
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.)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
THFHS: 4- (2-tetrahydrofuranyloxy) styrene (synthetic product)
THFCS: 4- (2-tetrahydrofuranyloxycarbonyl) styrene (synthetic product)
AA: acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
MAA: methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: Ethyl acrylate (made 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 KH Neochem Co., Ltd.)
Methyl n-butyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Butyl acetate (made by Tokyo Chemical Industry Co., Ltd.)
MEK: methyl ethyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Propyl acetate (manufactured by Showa Denko KK)
Isobutyl acetate (made by Tokyo Chemical Industry Co., Ltd.)
Ethyl acetate (made by Tokyo Chemical Industry Co., Ltd.)
MIBK: methyl isobutyl ethyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Diisopropyl ether (made by Tokyo Chemical Industry Co., Ltd.)
Toluene (manufactured by Tokyo Chemical Industry Co., Ltd.)
MFG: Propylene glycol methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
γ-butyrolactone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
MEDG: diethylene glycol methyl ethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
THF: tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.)
Acetone (made by Tokyo Chemical Industry Co., Ltd.)
MEHQ: 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
V-601: dimethyl 2,2'-azobis (2-methyl propionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: 2,2'-azobis (2,4-dimethyl valeronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-70: 2, 2'-azobis (4-methoxy-2, 4-dimethyl valeronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of MATHF>
In a three-necked flask, methacrylic acid (86.1 parts by mass, 1.0 molar equivalent) and hexane (86.1 parts by mass) were added, and the mixture was cooled to 20 ° C. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.03 milliequivalents) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalents), the reaction was carried out in the temperature range of 20 ° C. ± 2 ° C. After stirring for 5 hours, the temperature was raised to 35 ° C. and stirred for 2 hours. After laying in a Nutche in order of Kyoward 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.), the reaction solution was filtered to obtain a filtrate. MEHQ (4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.0012 parts by mass) is added to the obtained filtrate, and the solution is concentrated under reduced pressure at 40 ° C. to obtain tetrahydro-2H-furan-methacrylic acid. 156.2 parts by mass of 2-yl (MATHF) was obtained 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 dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.03 milliequivalents) and 2-dihydrofuran (77.9 parts by mass, 1.0 molar equivalents), the reaction was carried out in the temperature range of 20 ° C. ± 2 ° C. After stirring for 5 hours, the temperature was raised to 35 ° C. and stirred for 2 hours. After laying in a Nutche in order of Kyoward 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.), the reaction solution was filtered to obtain a filtrate. MEHQ (0.0012 parts by mass) is added to the obtained filtrate, and the solution is concentrated under reduced pressure at 40 ° C. to obtain 140.8 parts by mass of tetrahydro-2H-furan-2-yl acrylate (ATHF) as a colorless oil. The product was obtained as a product (yield 99.0%).

<Synthesis of THFHS>
In a three-necked flask, 4-hydroxystyrene (120.2 parts by mass, 1.0 molar equivalent) and hexane (120.2 parts by mass) were added and cooled to 20 ° C. After dropwise addition of camphor sulfonic acid (0.00070 parts by mass, 0.03 milliequivalents) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalents), the mixture was heated to 80 ° C. and stirred for 5 hours . After laying in a Nutche in order of Kyoward 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.), the reaction solution was filtered to obtain a filtrate. MEHQ (0.0019 parts by mass) is added to the obtained filtrate and concentrated under reduced pressure at 40 ° C. to obtain 185.0 parts by mass of 4- (2-tetrahydrofuranyloxy) styrene (THFHS) as a colorless oil As a 97.3% yield.

<Synthesis of THFCS>
In a three-necked flask, 4-carboxystyrene (148.2 parts by mass, 1.0 molar equivalent) and hexane (148.2 parts by mass) were added and cooled to 20 ° C. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.03 milliequivalents) and 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalents), the reaction was carried out in the temperature range of 20 ° C. ± 2 ° C. After stirring for 5 hours, the temperature was raised to 35 ° C. and stirred for 2 hours. After laying in a Nutche in order of Kyoward 200 and Kyoward 1000 (both manufactured by Kyowa Chemical Industry Co., Ltd.), the reaction solution was filtered to obtain a filtrate. MEHQ (0.0021 parts by mass) is added to the obtained filtrate, and the solution is concentrated under reduced pressure at 40 ° C. to obtain 212.3 parts by mass of 4- (2-tetrahydrofuranyloxycarbonyl) styrene (THFCS) as a colorless oil. The product was obtained as a product (yield 97.3%).

<Synthesis of Polymer A-1>
Methyl n-butyl ketone (75.0 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. MATHF (45.0 parts by mass), AA (2.0 parts by mass), EA (30.0 parts by mass), MMA (7.0 parts by mass), CHA (16.0 parts by mass), V-601 (4 0 parts by mass), a solution to which methyl n-butyl ketone (75.0 parts by mass) was added was added dropwise over 2 hours into a three-necked flask solution maintained at a temperature range of 90 ° C ± 2 ° C. After completion of the dropwise addition, the mixture was stirred at a temperature range of 90 ° C. ± 2 ° C. for 2 hours to obtain a polymer solution for photosensitive transfer material (solid content 40.0%) containing the polymer A-1.

Synthesis Example of Polymer A-2, 4, 5, 8, 10 to 20, 23 to 27
The type and amount of the monomer used and the type of the solvent were changed as shown in the following table, 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.
The numerical values in Table 1 indicate the content (parts by mass) of each component, and the numerical values contained in parentheses next to the solvent name indicate the content of the corresponding solvent with respect to the total mass of the polymerization solvent ( %) Is shown.

Synthesis Example of Polymer A-3, 6, 7
The type and amount of monomer used and the type of solvent are changed as shown in the following table, the polymerization temperature is changed to 75 ° C., the polymerization initiator is changed to V-65, and other conditions are as follows: A It synthesize | combined by the method similar to -1. The solid content concentration of the polymer was 40% by mass.

<Synthesis Example of Polymer A-9, 21, 22>
The type and amount of monomer used, and the type of solvent are changed as shown in the following table, the polymerization temperature is changed to 54 ° C., the polymerization initiator is changed to V-70, and other conditions are as follows: A It synthesize | combined by the method similar to -1. The solid content concentration of the polymer was 40% by mass.

The description of "-" in Table 1 indicates that the corresponding monomer is not used.
Moreover, in Table 1, I / O value, Tg, vapor pressure, and Mw were measured by the above-mentioned method.

  Hereinafter, details of each component used in preparation of a photosensitive resin composition (a composition for photosensitive transfer material) described later and described in Table 2 described later will be shown.

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

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

  B-3: A structure shown below (synthesized according to the method described in paragraph 0210 of JP-A-2014-197155. Ts represents a p-toluenesulfonyl group.)

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

<Surfactant>
C-1: a compound having a structure shown below

<Basic compound>
D-1: Compound of the structure shown below (CMTU)
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 24 and Comparative Examples 1 to 7)
Preparation of Photosensitive Transfer Material
In Examples 1 to 24 and Comparative Examples 1 to 7, the polymer component, the photoacid generator, the basic compound, the surfactant, and the other components are PGMEA such that the solid content ratio shown in Table 2 below is obtained. It is dissolved and mixed in (Propylene glycol monomethyl ether acetate) to a solid content concentration of 10% by mass, and filtered with a 0.2 μm-diameter polytetrafluoroethylene filter to obtain a photosensitive resin composition (composition for photosensitive transfer material Object).
This photosensitive resin composition was dried on a 30 μm thick polyethylene terephthalate film (hereinafter referred to as “PET (A)”) to be a temporary support using a slit nozzle to have a dry film thickness of 4.0 μm. It applied so that it might become. Then, it passed through a drying zone with an average temperature of 85 ° C. for 50 seconds, and finally a polyethylene film (manufactured by Tredegger, OSM-N) was press-bonded as a cover film to prepare a photosensitive transfer material.
The total light haze of PET (A) was 0.19%. The film haze measured the total light haze value (%) of the base piece according to JIS-K-7136 using Suga Test Instruments Co., Ltd. product haze meter HZ-2.

<Performance evaluation>
A copper layer-coated PET substrate was used in which a copper layer was produced by a sputtering method at a thickness of 500 nm on a PET film having a thickness of 188 μm.

<Lamination suitability evaluation>
The prepared photosensitive transfer material is cut into 50 cm squares, the cover film is peeled off, and the roll temperature is 90 ° C., the linear pressure is 0.8 MPa, the linear velocity is 3.0 m / min. The laminate was laminated on a PET substrate with a copper layer under the following lamination conditions. The area in which the photosensitive layer was in close contact with the copper layer without bubbles or float was visually evaluated, and the area ratio in which the photosensitive 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 (%) less than 80%: 1

<Sensitivity (exposure sensitivity) evaluation>
The prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa, a linear velocity of 3.0 m / min. The laminate was laminated on a PET substrate with a copper layer under the following lamination conditions. In addition, in the case of 4 or less of lamination suitability in the case of roll temperature 90 degreeC, laminor temperature was raised and the sample was created until lamination suitability became 5 determination. Lamination suitability was evaluated by the above-mentioned method.
After exposing the photosensitive layer with a super high pressure mercury lamp through a line and space pattern mask (Duty ratio 1: 1) with a line width of 3 to 20 μm without peeling off the temporary support, the temporary support is peeled off after being left for 1 hour And developed. The development was performed by shower development for 40 seconds using a 0.9% aqueous sodium carbonate solution at 22 ° C. When a 20 μm line-and-space pattern was formed by the above method, the residue in the space was observed and evaluated by a scanning electron microscope (SEM), and the exposure amount completely free of the residue was determined. An exposure dose of 200 mJ / cm ² or less is a practical level. The smaller the exposure amount, the better the exposure sensitivity.
〔Evaluation criteria〕
Less than 80 mJ / cm ² : 5
80mJ / cm ² or more 150mJ / cm less than ^2: 4
150 mJ / cm ² or more and 200 mJ / cm ^{2 or} less: 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 prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa, a linear velocity of 3.0 m / min. The laminate was laminated on a PET substrate with a copper layer under the following lamination conditions. In addition, when the evaluation result of the above-mentioned lamination aptitude is 4 or less at roll temperature 90 degreeC, laminor temperature was raised and the sample was produced until the evaluation result of lamination aptitude became 5 (area (%) is 95% or more).
After exposing the photosensitive layer with an exposure amount determined by sensitivity evaluation with an ultrahigh pressure mercury lamp through a line and space pattern (Duty ratio 1: 1) mask with a line width of 3 μm to 20 μm without peeling off the temporary support, 1 After leaving for a while, the temporary support was peeled off and developed. The development was carried out for 40 seconds by shower development using a 1.0% aqueous solution of sodium carbonate at 22 ° C. Among the line and space patterns thus obtained, the pattern with the smallest line width is taken as the ultimate resolution. When the ultimate resolution was determined, the pattern was observed with a scanning electron microscope (SEM), and it was determined that resolution was not possible when large roughness occurred in the side wall portion of the pattern. It can be said that, as the ultimate resolution is smaller, a pattern with excellent resolution can be obtained even when left after exposure. (Made by Tokyo Chemical Industry Co., Ltd.)
〔Evaluation criteria〕
Reaching resolution less than 6 μm: 5
Achieved resolution is less than 8 μm, 6 μm or more: 4.5
Achieved resolution less than 10 μm, 8 μm or more: 4
Achieved resolution less than 15 μm, 10 μm or more: 3
Achieved resolution is less than 20 μm, 15 μm or more: 2
Reaching resolution of 20 μm or more: 1

The results are shown in Table 2 below.
As shown in Table 2, by using the polymer solution for photosensitive transfer material obtained by the method for producing a polymer solution for photosensitive transfer material according to this embodiment, a pattern excellent in resolution can be obtained. A photosensitive transfer material was obtained.
In addition, as shown in Table 2, a pattern having excellent resolution can be obtained by using the composition for photosensitive transfer material obtained by the method for producing a composition for photosensitive transfer material according to the present embodiment. A photosensitive transfer material was obtained.
Further, as shown in Table 2, according to the method for producing a photosensitive transfer material, a photosensitive transfer material which can obtain a pattern excellent in resolution was obtained.

In Table 2, the description of "-" indicates that the corresponding compound is not contained.
Moreover, in Table 2, I / O value, Tg, vapor pressure, and Mw were measured by the above-mentioned method.

(Example 101)
Indium tin oxide (ITO) is deposited by sputtering as a conductive layer of the second layer on a 100 μm-thick PET substrate by sputtering to a thickness of 150 nm, and copper is vacuum deposited thereon as a conductive layer of the first layer. A film was formed at a thickness of 200 nm to form 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.). The contact pattern was exposed using a photomask provided with a pattern (hereinafter also referred to as “pattern A”) shown in FIG. 3 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 illustrates the alignment alignment frame.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, the copper layer is etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), The board | substrate with which copper (solid line part SL) and ITO (gray part G) were both drawn by the pattern A was obtained.

Next, pattern alignment was performed using a photomask provided with an opening of a pattern (hereinafter, also referred to as “pattern B”) shown in FIG. 4 in a state where alignment is aligned, 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 virtually illustrates the alignment alignment frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board.
Thus, a circuit wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and it was a beautiful pattern.

(Example 102)
ITO is deposited as a conductive layer of the second layer by sputtering to a thickness of 150 nm on a 100 μm-thick PET substrate, and copper is deposited thereon by a vacuum evaporation method to a thickness of 200 nm as a conductive layer of the first layer. The film was formed as a circuit formation substrate.
The photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (linear pressure 0.6 MPa, linear velocity 3.6 m / min, roll temperature 90 ° C.).
The photosensitive layer was pattern-exposed using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads are 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, the copper layer is etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), The board | substrate with which copper (solid line part SL) and ITO (gray part G) were both drawn by the pattern A was obtained.
Then, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern alignment was performed using a photomask provided with the opening of pattern B shown in FIG. 4 in a state of alignment, and after PET (A) was peeled off, development and water washing were performed.
Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board.
When observed with a microscope, there was no peeling or chipping, and it was a beautiful pattern.

12 temporary support 14 photosensitive layer 14A first pattern 14B second pattern 16 cover film 20 substrate for circuit formation 22 base material 24 first conductive layer 24A first conductive layer (after first etching step)
24B first conductive layer (after second etching step)
26 second conductive layer 26A second conductive layer (after the first etching step and the second etching step)
30 mask 40 mask 100 photosensitive transfer material SL solid line portion G gray portion DL dotted portion

Claims (14)

A polymerization solvent component containing a polymerization initiator, a polymerization solvent, and having a vapor pressure of 1 kPa to 16 kPa at 20 ° C., and at least one monomer having an acid-degradable group-protected acid group Having a step of carrying out a polymerization reaction in a composition containing a monomer component,
Method for producing a polymer solution for photosensitive transfer material.   The method for producing a polymer solution for photosensitive transfer material according to claim 1, wherein a vapor pressure at 20 ° C of the polymerization solvent component is 1 kPa or more and 10 kPa or less.   The polymerization solvent according to claim 1 or 2, wherein the polymerization solvent component comprises a polymerization solvent having at least one group selected from an ester group, an ether group and a carbonyl group and having 4 to 6 carbon atoms. Method for producing a polymer solution for photosensitive transfer material.   The polymerization solvent component does not contain a polymerization solvent containing a hydroxy group, or the content of the polymerization solvent containing a hydroxy group is more than 0% by mass and less than 5% by mass with respect to the total mass of the polymerization solvent component The manufacturing method of the polymer solution for photosensitive transfer materials of any one of Claims 1-3.   The manufacturing method of the polymer solution for photosensitive transfer materials of any one of Claims 1-4 in which the said monomer component contains the monomer which has an acidic radical.   The monomer according to any one of claims 1 to 5, wherein the monomer containing an acid group that is protected by an acid degradable group is a monomer that contains a carboxy group that is protected by an acid degradable group. Method of producing a polymer solution for photosensitive transfer material according to   A polymer solution for a photosensitive transfer material produced by the method for producing a polymer solution for a photosensitive transfer material according to any one of claims 1 to 6, a photoacid generator, and a vapor pressure at 20 ° C. The manufacturing method of the composition for photosensitive transfer materials including the process of mixing the dilution solvent which is 1 kPa or more and 16 kPa or less.   8. The photosensitive material according to claim 7, wherein the content of the structural unit having an acid group is 0.5% by mass to 10% by mass with respect to the total mass of the polymer component contained in the composition for photosensitive transfer material obtained. Method of a composition for a flexible transfer material.   The average value of I / O values obtained by dividing the inorganicity value I based on the organic conceptual diagram of the polymer component contained in the composition for photosensitive transfer material obtained by the organicity value O is 0.52 or more. 9. A method of producing a composition for a photosensitive transfer material according to claim 7 or 8.   The photosensitive transfer material according to any one of claims 7 to 9, wherein the average value of the glass transition temperatures of all the polymer components contained in the composition for photosensitive transfer material obtained is 90 ° C or less. Method of producing the composition for   The composition for photosensitive transfer materials according to any one of claims 7 to 10, wherein the weight average molecular weight of the polymer component contained in the composition for photosensitive transfer materials obtained is 60,000 or less. Method of manufacturing objects.   A photosensitive layer is formed on a temporary support using the composition for photosensitive transfer materials obtained by the method for producing a composition for photosensitive transfer materials according to any one of claims 7 to 11. Method of producing a photosensitive transfer material comprising the steps of A step of bringing the photosensitive layer of the photosensitive transfer material obtained by the method of producing a photosensitive transfer material according to claim 12 into contact with a substrate and laminating the substrate;
Pattern exposing the photosensitive layer of the photosensitive transfer material after the laminating step;
Developing the photosensitive layer after the exposing step to form a pattern;
And E. etching the substrate in the area where the pattern is not disposed.
Method of manufacturing circuit wiring. A step of bringing the photosensitive layer of the photosensitive transfer material obtained by the method of producing a photosensitive transfer material according to claim 12 into contact with a substrate and laminating the substrate;
Pattern exposing the photosensitive layer of the photosensitive transfer material after the laminating step;
Developing the photosensitive layer after the exposing step to form a pattern;
And E. etching the substrate in the area where the pattern is not arranged.