TW201902956A - Photosensitive transfer material and method of manufacturing circuit wiring - Google Patents

Abstract

This photosensitive transferring material comprises a temporary support, an intermediate layer, and a photosensitive resin composition layer in this order. The photosensitive resin composition layer includes: a polymer including a constituent unit including an acid group protected by an acid-degradable group; and a photoacid generator. The intermediate layer is water-soluble or alkali-soluble, and includes a resin C including a constituent unit including a phenolic hydroxyl group or an alcoholic hydroxyl group that is not directly bonded to the main chain. Also provided is a method for producing a circuit wiring using said photosensitive transferring material.

Description

Method for manufacturing photosensitive transfer material and circuit wiring

The present disclosure relates to a photosensitive transfer material and a method for manufacturing circuit wiring.

In display devices (such as organic electroluminescence (EL) display devices and liquid crystal display devices) provided with a touch panel, such as an electrostatic capacitance type input device, the electrode pattern corresponding to the sensor of the visible part is provided inside the touch panel, Conductive layer patterns such as the wiring at the edge wiring part and the lead-out wiring part. Generally, in the formation of a patterned layer, the number of processes for obtaining a desired pattern shape is small, and therefore, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is widely used. A method of developing a mask of a desired pattern after exposure.

For example, Japanese Patent Laid-Open No. 2015-118202 discloses a photosensitive transfer material characterized by having a support and a photosensitive resin composition layer, the photosensitive resin composition layer containing (A) containing a polymer The polymer component and (B) a photo-acid generator. The polymer contains a structural unit (a1) having an acid group protected by an acid-decomposable group, and the photosensitive resin composition does not have an ethylenic cross-linked structure.

The problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material with less distortion in the pattern shape obtained. In addition, a problem to be solved by another embodiment of the present invention is to provide a method for manufacturing circuit wiring using the photosensitive transfer material.

The means for solving the above problems include the following. <1> A photosensitive transfer material having a pseudo support, an intermediate layer, and a photosensitive resin composition layer in this order, the photosensitive resin composition layer containing a polymer and a photoacid generator, the polymer containing acid decomposability The structural unit of the acid group protected by the group, the intermediate layer contains a resin C, which is water-soluble or alkali-soluble, and contains a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain. <2> The photosensitive transfer material according to the above <1>, further comprising a thermoplastic resin layer between the dummy support and the intermediate layer. <3> The photosensitive transfer material according to the above <1> or <2>, wherein the resin C is at least one selected from the group consisting of novolak resin, modified cellulose resin, and acrylic resin having a hydroxyl group Resin. <4> The photosensitive transfer material according to any one of <1> to <3>, wherein the intermediate layer further contains a water-soluble or alkali-soluble resin D other than the resin C. <5> The photosensitive transfer material according to the above <4>, wherein the resin D is selected from polyacrylic acid, sodium polyacrylate, polypropylene amide, polyethylene oxide, polyethyleneimine, polyethylene At least one resin of the group consisting of alcohol and polyvinylpyrrolidone. <6> The photosensitive transfer material according to the above <4> or <5>, wherein the resin D is at least one resin selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone. <7> The photosensitive transfer material according to any one of the above <4> to <6>, wherein the content ratio of the resin C and the resin D in the intermediate layer is based on the mass ratio resin C: resin D = 5: 1 ～ 1: 2. <8> The photosensitive transfer material according to the above <7>, wherein the content ratio of the resin C and the resin D in the intermediate layer is resin C: resin D = 4: 1 to 2: 1. <9> The photosensitive transfer material according to any one of the above <1> to <8>, wherein the structural unit having an acid group protected by the acid-decomposable group is a structural unit represented by the following formula A.

[Chemical Formula 1]

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

<10> The photosensitive transfer material according to any one of the above <1> to <9>, wherein the glass transition temperature of the polymer in the photosensitive resin composition layer is 90 ° C. or lower. <11> A method for manufacturing circuit wiring, which sequentially includes the following processes: For a substrate, the photosensitive resin composition layer of the photosensitive transfer material according to any one of the above <1> to <10> is brought into contact with the substrate And the lamination process; the process of pattern exposing the photosensitive resin composition layer of the photosensitive transfer material after the lamination process; the development of the photosensitive resin composition layer after the exposure process And a process of forming a pattern; and a process of etching the substrate in the area where the pattern is not configured. <12> A method of manufacturing circuit wiring, which sequentially includes the following processes: For a substrate, the photosensitive resin composition layer of the photosensitive transfer material according to any one of the above <1> to <10> is brought into contact with the substrate The process of laminating; the process of peeling the pseudo-support of the photosensitive transfer material; the process of pattern exposing the photosensitive resin composition layer; the process of developing the photosensitive resin composition layer and forming the pattern; And a process of etching the substrate in the area where the pattern is not arranged. [Effect of invention]

According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material with little distortion of the obtained pattern shape. Furthermore, according to another embodiment of the present invention, it is possible to provide a method for manufacturing circuit wiring using the above-mentioned photosensitive transfer material.

The content of the present disclosure will be described below. In addition, although the description is made with reference to the drawings, the component symbols are sometimes omitted. In addition, the numerical range represented by "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In addition, in this specification, "(meth) acrylic acid" means both or either acrylic acid and methacrylic acid, and "(meth) acrylate" means both or any one of acrylate and methacrylate. In addition, in this specification, regarding the amount of each component in the composition, when a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, it indicates the corresponding plurality of substances present in the composition Total measurement. In this specification, the term "process" not only means an independent process, but even if it cannot be clearly distinguished from other processes, as long as the intended purpose of the process can be achieved, it is included in this term. In the labeling of groups (atomic groups) in this specification, unlabeled and unsubstituted labels include those with substituents and those without substituents. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In addition, the chemical structural formula in this specification may be described as a simplified structural formula in which a hydrogen atom is omitted. In the present disclosure, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning. Also, in the present disclosure, a combination of two or more preferred aspects is a better aspect. In addition, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in this disclosure are columns using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION) The gel permeation chromatography (GPC) analyzer uses a solvent THF (tetrahydrofuran) and a differential refractometer to detect molecular weights converted from polystyrene as a standard substance.

(Photosensitive transfer material) The photosensitive transfer material of the present disclosure has a pseudo support, an intermediate layer, and a photosensitive resin composition layer in this order. The photosensitive resin composition layer contains a polymer and a photoacid generator, and the polymer contains A structural unit having an acid group protected by an acid-decomposable group, the intermediate layer contains a resin C, the resin C is water-soluble or alkali-soluble, and contains a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain unit.

The roll-to-roll process may be considered as a process of continuously performing the transfer process-exposure process-development process on the substrate to be transported, and the process of winding on the roll after the development process, but the inventor found that the following problems exist, That is to say, in actual production, when a failure occurs in any process, the conveyance of the substrate has to be stopped. At this time, the performance of the part stopped during the transfer process and the development process is significantly deteriorated and has to be discarded. Furthermore, in the exposure process, it is technically impossible to realize exposure through a mask while transferring the substrate at a constant speed, and it is necessary to assemble a complicated device such as a device that locally stops the transfer of the substrate. Furthermore, the inventors concluded that the processes of transfer, exposure, and development are independently arranged, and the processes of unwinding and winding are embedded before and after each process, which is ideal within the scope of the prior art. However, the present inventors found that in the method including each process of transfer, exposure, and development, if an image is formed using a layer of a chemically amplified positive photosensitive resin composition, the obtained pattern may sometimes occur Deformation. In addition, when a conventional resist other than the chemically amplified positive photosensitive resin composition is used, the above phenomenon is not found. As a result of intensive studies conducted by the present inventors, it was found that this phenomenon is a characteristic phenomenon when a chemically amplified positive resin composition is used, and it is found that the deformation of the obtained pattern shape is reduced by using the photosensitive transfer material of the above-mentioned configuration . Although the detailed discovery mechanism of the above effect is not clear, the deformation of the obtained pattern shape appears especially when a chemically amplified positive-type resin composition is used, from which the present inventors infer that the acid decomposability is based on the generated acid Phenomenon caused by the reaction of radical detachment and the diffusion of compounds from acid-decomposable radicals that detach later. Furthermore, the inventors inferred that the intermediate layer decomposes the acid derived from the resin by containing a resin unit that is water-soluble or alkali-soluble and contains a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain. The compound of the sex group is captured by the above-mentioned hydroxyl group in the intermediate layer, thereby relatively reducing the diffusion of the compound from the acid-decomposable group that has been detached to a similar pixel, and suppressing the film based on the volume change accompanying the above diffusion Generation of internal stress, thereby suppressing deformation of the obtained pattern shape.

Hereinafter, the photosensitive transfer material of the present disclosure will be described in detail.

FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material of the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a pseudo support 10, an intermediate layer 12, a photosensitive resin composition layer 14 and a cover film 16 are sequentially stacked. The intermediate layer 12 contains a resin C, which is water-soluble or alkali-soluble, and includes a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group that is not directly connected to the main chain. The photosensitive resin composition layer 14 contains a polymer and a photoacid generator. The polymer contains a structural unit having an acid group protected by an acid-decomposable group. Hereinafter, constituent materials and the like of the photosensitive transfer material of the present disclosure will be described. In addition, in this specification, the above-mentioned configuration in the present disclosure is sometimes referred to as follows. A polymer containing a structural unit having an acid group protected by an acid-decomposable group is sometimes called a "specific polymer". The above-mentioned photosensitive resin composition layer is a positive photosensitive resin composition layer, and is sometimes referred to as a "positive photosensitive resin composition layer".

<Pseudo Support> The pseudo support system supports the intermediate layer and the photosensitive resin composition layer and can be peeled from the intermediate layer or the photosensitive resin composition layer. The dummy support used in the present disclosure is preferably light-transmissive from the viewpoint that the photosensitive resin composition layer can be exposed via the dummy support when the photosensitive resin composition layer is pattern exposed. 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 more than 60% from the viewpoint of improving the exposure sensitivity Good, more than 70% is even better. In addition, the upper limit of the transmittance is 100%. As a method of measuring the transmittance, a method of measuring with MCPD Series manufactured by Otsuka Electronics Co., Ltd. can be mentioned. Examples of the pseudo support include glass substrates, resin films, and paper. From the viewpoint of strength and flexibility, resin films are particularly preferred. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among them, the biaxially stretched polyethylene terephthalate film is particularly preferred.

The thickness of the pseudo support is not particularly limited, and the range of 5 μm to 200 μm is preferable, and the range of 10 μm to 150 μm is more preferable from the viewpoints of ease of handling and versatility. The thickness of the dummy support may be selected according to the strength of the support, flexibility required for bonding to the circuit wiring forming substrate, and light transmittance required in the initial exposure process.

A preferred form of the pseudo-support is described in paragraphs 0017 to 0018 of Japanese Patent Laid-Open No. 2014-85643, and the contents of this publication are incorporated in this specification.

<Intermediate layer> The photosensitive transfer material of the present disclosure has an intermediate layer containing a resin C between the pseudo-support and the photosensitive resin composition layer. The aforementioned resin C is water-soluble or alkali-soluble and contains a phenolic hydroxyl group or Constituent units of alcoholic hydroxyl groups that are not directly linked to the main chain (also simply called "Resin C"). In addition, the present inventors have found that when only a resin containing a structural unit having an alcoholic hydroxyl group directly connected to the main chain, such as a resin such as polyvinyl alcohol, is used, a deformation of the obtained pattern shape occurs. The inventors inferred that in the alcoholic hydroxyl group directly linked to the main chain, due to the steric hindrance of the main chain, the compound derived from the acid-decomposable group that has been detached cannot be captured by the above-mentioned hydroxyl group, and sufficient effects cannot be obtained. . Also, in the present disclosure, "main chain" means a relatively longest bonding chain among molecules of a polymer compound constituting a resin, and "sidelock" means a carbon chain branched from the main chain.

-Resin C- Resin C is a water-soluble or alkali-soluble resin and contains a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group that is not directly linked to the main chain, and a resin containing the above structural unit repeatedly is preferably. As a structural unit, by having a large number of the above-mentioned hydroxyl groups in the resin C, the deformation of the obtained pattern shape is more suppressed. In addition, in the present disclosure, “water-soluble” means soluble in water at pH 7.0 at 25 ° C., and “alkali-soluble” means soluble in alkaline aqueous solution at pH 8.5 or higher at 25 ° C. In addition, the "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or may be water-soluble and alkali-soluble.

As the resin C, a resin containing a structural unit having a phenolic hydroxyl group and a resin containing a structural unit having an alcoholic hydroxyl group not directly linked to the main chain can be mentioned. Examples of the resin containing a structural unit having a phenolic hydroxyl group include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, and phenol / cresol (can be m-, p- or m- / p-mixing) mixed with novolak resins such as formaldehyde resins, pyrogallol acetone resins, polyhydroxystyrene resins, etc. Examples of the resin containing a structural unit having an alcoholic hydroxyl group not directly linked to the main chain include modified cellulose resins, acrylic resins having a hydroxyl group (for example, individual polymers or copolymers of hydroxyalkyl (meth) acrylates) Substances), starches, glycogen, chitins, agaroses, carrageenans, pullulan, gum arabic, soy gum, etc.

Among these, from the viewpoint of suppressing the deformation of the pattern shape, the resin C is preferably at least one resin selected from the group consisting of novolak resin, modified cellulose resin, and acrylic resin having a hydroxyl group. At least one resin of the group consisting of free modified cellulose resin and acrylic resin having hydroxyl group is more preferable, and modified cellulose resin is more preferable. In addition, as the modified cellulose resin, hydroxyalkylated cellulose is preferred from the viewpoint of suppressing the deformation of the pattern shape. As the hydroxyalkylated cellulose, preferably hydroxymethyl cellulose, hydroxyethyl cellulose, polyhydroxyethylated cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethylene glycol Hydroxypropyl methyl cellulose, hydroxypropyl methyl cellulose phthalate, etc. Among them, from the viewpoint of suppressing the deformation of the pattern shape, at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is preferred, and hydroxypropyl methyl cellulose is more preferred .

The weight average molecular weight of the resin C is preferably 1,000 or more, preferably 2,000 to 100,000, and more preferably 10,000 to 50,000 from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure. Better.

The intermediate layer may contain one kind of resin C alone or two or more kinds. The content of the resin C in the intermediate layer is 10% by mass or more and 100% by mass or less relative to the total mass of the intermediate layer from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure. Preferably, 20 mass% or more and 100 mass% or less is more preferable, 40 mass% or more and 100 mass% or less is more preferably, and 65 mass% or more and 85 mass% or less is particularly preferable.

-Resin D- From the viewpoint of the solubility and transferability in the developer after exposure, the photosensitive transfer material of the present disclosure further preferably contains a water-soluble or alkali-soluble resin D other than the above-mentioned resin C . Examples of the resin D include polyamide resins other than resin C, epoxy resins, polyacetal resins, acrylic resins, polystyrene resins, polyurethane resins, polyvinyl alcohol, polyvinyl formal, and polyester resins. , Polyethyleneimine, polyallylamine, polyalkylene glycol, etc. Among them, the resin D is selected from the group consisting of polyacrylic acid, sodium polyacrylate, polyacrylamide, polyethylene oxide, and polyethyleneimine from the viewpoint of solubility and transferability in the developer after exposure. At least one resin of the group consisting of polyvinyl alcohol and polyvinylpyrrolidone is preferred, and at least one resin selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone is more preferred.

From the viewpoint of solubility and transferability in the developer after exposure, the weight average molecular weight of the resin D is preferably 1,000 or more, more preferably 2,000 to 100,000, and even more preferably 10,000 to 50,000.

The intermediate layer may contain one kind of resin D alone or two or more kinds. The content of the resin D in the intermediate layer is 1% by mass or more and 80% by mass or less relative to the total mass of the intermediate layer from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure. Preferably, 5 mass% or more and 50 mass% or less are more preferable, 10 mass% or more and 40 mass% or less are more preferably, and 15 mass% or more and 35 mass% or less are particularly preferable. In addition, the content of the resin D in the intermediate layer is preferably the content of the resin C or less in terms of mass from the viewpoint of suppressing the deformation of the pattern shape.

In addition, the content ratio of the resin C and the resin D in the intermediate layer is from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer after exposure, and the resin C: resin D = 5: 1 to 1: 2 is preferred, 4: 1 to 2: 1 is more preferred, and 3.5: 1 to 2.5: 1 is further preferred.

-Other Additives- The above-mentioned intermediate layer in the present disclosure may contain well-known additives in addition to the resin C and the resin D as needed. As other additives, other additives used in the photosensitive resin composition layer described later can be preferably mentioned.

-Thickness of the intermediate layer- From the viewpoint of suppressing the deformation of the pattern shape, the thickness of the intermediate layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 8 μm, and particularly preferably 0.5 μm to 5 μm. Furthermore, the thickness of the intermediate layer is preferably thinner than the thickness of the photosensitive resin composition layer.

-Method for forming the intermediate layer- The method for forming the intermediate layer is not particularly limited, and the components and the solvent can be mixed in a specific ratio and in any method, and stirred and dissolved to prepare an intermediate layer forming composition for forming the intermediate layer Thing (also called "intermediate layer composition."). For example, it is also possible to prepare a solution in which each component is dissolved in a solvent in advance, and then mix the obtained solution at a specific ratio to prepare a composition. The composition prepared as described above can be provided for use after filtration using a filter with a pore size of 5 μm or the like.

By applying the intermediate layer composition to the dummy support and drying it, the intermediate layer can be easily formed on the dummy support. The coating method is not particularly limited, and can be applied by a well-known method such as slit coating, spin coating, curtain coating, and inkjet coating. In addition, it is also possible to form another layer (for example, a thermoplastic resin layer, etc.) described later on the dummy support and apply an intermediate layer thereon.

<Photosensitive resin composition layer> The photosensitive transfer material of this disclosure has a pseudo support, an intermediate layer, and a photosensitive resin composition layer in this order, and the said photosensitive resin composition layer contains a polymer and a photo-acid generator, the said polymer Consists of constituent units with acid groups protected by acid-decomposable groups. In addition, the photosensitive resin composition layer in the present disclosure is a positive photosensitive resin composition layer, and the chemically amplified positive photosensitive resin composition layer is preferable. In a photoacid generator such as an onium salt or an oxime sulfonate compound described later, the acid generated by induction of active radiation (actinic rays) deprotects the protected acid group in the specific polymer as a catalyst, Therefore, the acid generated by the action of one light quantum contributes to most deprotection reactions, and the quantum yield exceeds 1 to a value as large as a power of 10, for example. As a result of so-called chemical amplification, high sensitivity can be obtained. On the other hand, when a quinonediazide compound is used as a photoacid generator for inductively active radiation, the carboxyl group is generated by successive photochemical reactions, and its quantum yield must be 1 or less, but it is not in the chemical amplification type in this way.

-A polymer component containing a polymer containing a structural unit having an acid group protected by an acid-decomposable group- The above-mentioned photosensitive resin composition layer contains a polymer (also referred to as "specific polymer".), And the aforementioned polymer contains Constituent units with acid groups protected by acid-decomposable groups (also called "constituent unit A"). Furthermore, the photosensitive resin composition layer may contain other polymers in addition to the polymer having the structural unit A. In the present disclosure, the polymer having the constituent unit A and other polymers are also collectively referred to as "polymer component". The specific polymer has an acid group protected by an acid-decomposable group, and the structural unit A in the specific polymer is deprotected by the action of an acidic substance in the amount of catalyst generated by exposure to become an acid group. With this acid group, a curing reaction can proceed. Hereinafter, preferred aspects of the constituent unit A will be described.

The photosensitive resin composition layer may further contain a polymer other than the polymer containing a structural unit having an acid group protected by an acid-decomposable group. In addition, it is preferable that all of the polymers contained in the above-mentioned polymer components each include at least a structural unit having an acid group described later. In addition, the chemically amplified positive photosensitive resin composition may further contain polymers other than these. Unless otherwise specified, the above-mentioned polymer component in the present disclosure means that it contains other polymers added as necessary. In addition, the compounds corresponding to the crosslinking agent and the dispersing agent described later are not included in the above-mentioned polymer component even if it is a polymer compound.

A specific polymer is preferably an addition polymerization type resin, and a polymer having a structural unit derived from (meth) acrylic acid or its ester is more preferable. In addition, it may have a structural unit other than the structural unit derived from (meth) acrylic acid or its ester, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

The above-mentioned photosensitive resin composition layer contains the structural unit represented by the following formula A1 as the above-mentioned structural unit A as the polymer component from the viewpoint of suppressing the deformation of the pattern shape and the solubility and transferability in the developer. The polymer of A1 is preferable, and as the polymer component, a specific polymer having the above-mentioned structural unit A having a structural unit A1 represented by the following formula A1 and having a glass transition temperature of 90 ° C. or less is preferable. As the above-mentioned structural unit A, a specific polymer having a structural unit A1 represented by the following formula A1 and a structural unit B having an acid group to be described later, and having a glass transition temperature of 90 ° C. or lower, is more preferable. The specific polymer contained in the photosensitive resin composition layer may be only one kind, or two or more kinds.

<< Constitutional unit A >> The polymer component includes a polymer, and the polymer includes at least a structural unit A having an acid group protected by an acid-decomposable group. By including the polymer having the structural unit A in the polymer component, a chemically amplified positive photosensitive resin composition layer with extremely high sensitivity can be produced. The “acid group protected by an acid-decomposable group” in the present disclosure can be used as well-known as an acid group and an acid-decomposable group, and is not particularly limited. Specific acid groups preferably include carboxyl groups and phenolic hydroxyl groups. In addition, as the acid group protected by an acid-decomposable group, an acetal such as an ester group protected by a group represented by Formula A1, a tetrahydropyranyl group, or a tetrahydrofuran ester group can be used, which is relatively easily decomposed by an acid It is a functional group) or a group that is relatively difficult to be decomposed by acid (for example, tertiary alkyl group such as tert-butyl ester group, tertiary alkyl carbonate group such as tert-butyl carbonate group). Among these, as the acid-decomposable group, a group having a structure protected in the form of an acetal is preferred.

<< Constitutional Unit A >> The structural unit A having an acid group protected by an acid-decomposable group is preferably a structural unit A1 represented by the following formula A1 from the viewpoint of sensitivity and resolution.

[Chemical Formula 2]

In formula A1, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ represents an alkyl group or an aryl group, R ³¹ or R ³² may be linked to R ³³ to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an aryl group.

In formula A1, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ³¹ or R ³² is an aryl group, phenyl is preferred. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A1, 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. In addition, the alkyl group and the aryl group in R ³¹ to R ³³ may have a substituent. In Formula A1, R ³¹ or R ³² may be linked to R ³³ to form a cyclic ether, and R ³¹ or R ³² to R ^{33 may be} linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferred, and 5 is more preferred. In formula A1, X ⁰ represents a single bond or an aryl group, and a single bond is preferred. The arylene group may have a substituent. The structural unit A1 represented by the above formula A1 is a structural unit having a carboxyl group protected by an acid-decomposable group. The specific polymer includes the structural unit A1 represented by the formula A1, whereby the sensitivity at the time of pattern formation is excellent, and the resolution is more excellent.

In Formula A1, R ³⁴ represents a hydrogen atom or a methyl group, and from the viewpoint of being able to further lower the Tg of a specific polymer, a hydrogen atom is preferred. More specifically, it is preferable that the structural unit in which R ³⁴ in the formula A is a hydrogen atom is 20% by mass or more with respect to the total amount of the structural unit A1 contained in the specific polymer. In addition, the content of the structural unit in which R ³⁴ in the structural unit A1 is a hydrogen atom (content ratio: mass ratio) can be measured by ¹³ C-nuclear magnetic resonance (NMR) and calculated by a conventional method of peak intensity Strength ratio to confirm.

In the structural unit A1 represented by the formula A1, the structural unit represented by the following formula A2 is also preferable from the viewpoint of further improving the sensitivity at the time of pattern formation.

[Chemical Formula 3]

In formula A2, 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 A2, R ³⁴ is preferably a hydrogen atom. In formula A2, R ³⁵ to R ⁴¹ are preferably hydrogen atoms.

As a preferred specific example of the structural unit A1 represented by the formula A1 having a carboxyl group protected by an acid-decomposable group, the following structural units can be exemplified. In addition, R ³⁴ represents a hydrogen atom or a methyl group.

[Chemical Formula 4]

In addition, as the above-mentioned structural unit A, a structural unit represented by the following formula A3 is preferable from the viewpoint of suppressing the deformation of the pattern shape.

[Chemical Formula 5]

In formula A3, R ^B1 and R ^B2 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^B1 and R ^B2 is an alkyl or aryl group, and R ^B3 represents an alkyl or aryl group, R ^B1 or R ^B2 can be linked to R ^B3 to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, X ^B represents a single bond or a divalent linking group, R ^B12 represents a substituent, n represents an integer of 0 to 4 .

In formula A3, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ^B1 or R ^B2 is an aryl group, phenyl is preferred. R ^B1 and R ^B2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A3, 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. In addition, the alkyl group and the aryl group in R ^B1 to R ^B3 may have a substituent. In formula A3, R ^B1 or R ^B2 may be linked to R ^B3 to form a cyclic ether, and R ^B1 or R ^B2 and R ^{B3 may be} linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and 5 or 6 is preferred, and 5 is more preferred. In formula A3, X ^B represents a single bond or a divalent linking group, a single bond or an alkylene group, -C (= O) O-, -C (= O) NR ^N- , -O- or these Is better, and single bonds are better. The alkylene group may be linear and may have a branch or a cyclic structure, or may have a substituent. The number of carbon atoms of the alkylene group is preferably 1-10, and more preferably 1-4. When X ^B contains -C (= O) O-, the carbon atom contained in -C (= O) O- and the carbon atom bonded to R ^B4 are directly bonded. When X ^B contains -C (= O) NR ^N- , the carbon atom contained in -C (= O) NR ^N -is directly bonded to the carbon atom bonded to R ^B4 . R ^N represents an alkyl group or a hydrogen atom. An alkyl group having 1 to 4 carbon atoms or a hydrogen atom is preferred, and a hydrogen atom is more preferred. In formula A3, it is preferable that the group including R ^B1 to R ^B3 and X ^B be bonded in a relative position. In formula A3, R ^B12 preferably represents a substituent, an alkyl group, or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1-10, and more preferably 1-4. In formula A3, n represents the integer of 0-4, 0 or 1 is preferable, and 0 is more preferable.

In Formula A3, R ^B4 represents a hydrogen atom or a methyl group, and from the viewpoint of further reducing the Tg of a specific polymer, a hydrogen atom is preferred. More specifically, it is preferable that the structural unit in which R ^B4 in the formula A3 is a hydrogen atom is 20% by mass or more with respect to the total content of the structural unit A contained in the specific polymer. Further, in the constituting unit A of the formula A3, R ^B4 is a hydrogen atom content of the constituent units (content ratio: mass ratio) of the peak intensity can be ¹³ C- nuclear magnetic resonance (NMR) measurements and is calculated according to the conventional manner by the Strength ratio to confirm.

Among the structural units represented by the formula A3, the structural unit represented by the following formula A4 is also preferable from the viewpoint of suppressing the deformation of the pattern shape.

[Chemical Formula 6]

In Formula A4, 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 n represents an integer of 0 to 4. In formula A4, R ^B4 is preferably a hydrogen atom. In formula A4, R ^B5 to R ^B11 are preferably hydrogen atoms. In formula A4, R ^B12 represents a substituent, and an alkyl group or a halogen atom is preferred. The number of carbon atoms of the alkyl group is preferably 1-10, and more preferably 1-4. In formula A4, n represents the integer of 0-4, 0 or 1 is preferable, and 0 is more preferable.

As a preferable specific example of the structural unit A4 represented by the formula A4, the following structural units can be exemplified. In addition, R ^B4 represents a hydrogen atom or a methyl group.

[Chemical Formula 7]

The structural unit A contained in the specific polymer may be one kind, or two or more kinds. The content of the structural unit A in the specific polymer is preferably 20% by mass or more relative to the total mass of the specific polymer, more preferably 20% by mass to 90% by mass, and still more preferably 30% by mass to 70% by mass. The content (content ratio: mass ratio) of the constituent unit A in the specific polymer can be confirmed by the intensity ratio of the peak intensity measured by ¹³ C-NMR and calculated by a conventional method. Furthermore, after decomposing all the polymer components into structural units (monomer units), the proportion of the structural unit A is preferably 5% to 80% by mass relative to the total mass of the polymer components, and 10% by mass ～ 80% by mass is better, and 30% to 70% by mass is particularly good.

<< Constitutional Unit B >> It is preferable that the specific polymer contains a structural unit B having an acid group. The constituent unit B is a constituent unit that includes an acid group that is not protected by a protective group such as an acid-decomposable group, that is, an acid group that does not have a protective group. The specific polymer contains the constituent unit B, whereby the sensitivity at the time of pattern formation becomes good, it becomes easily soluble in an alkaline developer in the development process after pattern exposure, and the development time can be shortened. The acid group in this specification means a proton dissociative group with a pKa of 12 or less. As the acid group, a monomer capable of forming an acid group is used, and it is preferable to be embedded in the polymer as a structural unit (constituent unit B) containing an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. In addition, the pKa of the acid group is preferably -5 or more.

The specific polymer contains the structural unit A and the structural unit B having an acid group that is not protected by a protective group as a copolymerization component. By setting the glass transition temperature to 90 ° C. or lower, the positive sensitivity containing the specific polymer The resin composition layer maintains the transferability and the peelability from the pseudo support at a good level, and the resolution and sensitivity at the time of pattern formation become better.

Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonimide group. Among them, at least one acid group selected from the group consisting of carboxylic acid groups and phenolic hydroxyl groups is preferred. The introduction of structural units containing an acid group into a specific polymer can be carried out by copolymerizing a monomer having an acid group. The structural unit containing the acid group as the structural unit B is a structural unit in which an acid group is substituted with respect to a structural unit derived from styrene or a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid is Better.

As the structural unit B, a structural unit having a carboxylic acid group or a structural unit having a phenolic hydroxyl group is preferred from the viewpoint of further improving the sensitivity during pattern formation. The monomer having an acid group capable of forming the constituent unit B is not limited to the examples described above.

The structural unit B contained in the specific polymer may be only one kind, or two or more kinds. In the specific polymer, it is preferable to contain 0.1% to 20% by mass of a structural unit (constituent unit B) having an acid group with respect to the total mass of the specific polymer, and more preferably to contain 0.5% to 15% by mass. 1% by mass to 10% by mass is further preferable. Within the above range, the pattern formability becomes better. The content (content ratio: mass ratio) of the constituent unit B in the specific polymer can be confirmed by the intensity ratio of the peak intensity measured by ¹³ C-NMR and calculated by a conventional method.

<< Other structural units >> Within the range that does not impair the effect of the photosensitive transfer material of the present disclosure, the specific polymer may include other structural units (hereinafter sometimes referred to as hereinafter referred to as structural unit A and structural unit B). As constituent unit C.). The monomer forming the structural unit C is not particularly limited, and examples thereof include styrene, alkyl (meth) acrylate, cyclic alkyl (meth) acrylate, aryl (meth) acrylate, and unsaturated dimethacrylate. Carboxylic diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, with fats Group of cyclic skeletons and other unsaturated compounds. By using the structural unit C to adjust at least any one of the kind and the content, various characteristics of the specific polymer can be adjusted. In particular, by appropriately using the structural unit C, the Tg of the specific polymer can be easily adjusted to 90 ° C or lower. The specific polymer may include only one type of structural unit C, or two or more types.

Specific examples of the structural unit C include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, and ethoxystyrene. , Chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate Propyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile or ethylene glycol monoethyl A structural unit formed by polymerization of acetyl acetate (meth) acrylate and the like. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can also be mentioned.

In addition, as the structural unit C, from the viewpoint of improving the electrical characteristics of the obtained transfer material, a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton is preferable. Specific examples of the monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentyl (meth) acrylate, and cyclic Hexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Among them, the structural unit C preferably includes a structural unit derived from cyclohexyl (meth) acrylate.

In addition, as the monomer forming the constituent unit C, from the viewpoint of adhesion, for example, alkyl (meth) acrylate is preferable. Among them, alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ester.

The content of the structural unit C is preferably 70% by mass or less relative to the total mass of the specific polymer, more preferably 60% by mass or less, and further preferably 50% by mass or less. The lower limit may be 0% by mass, but 1% by mass or more is preferable, and 5% by mass or more is more preferable. Within the above range, the resolution and adhesion are further improved.

The specific polymer contains an ester having an acid group in the above-mentioned structural unit B as the structural unit C from the viewpoint of optimizing the solubility with respect to the developer and optimizing the physical properties of the photosensitive resin composition layer The constituent unit is also preferable. Among them, it is preferable to include a structural unit having a carboxylic acid group as a structural unit B in a specific polymer, and further include a structural unit C including a carboxylic acid ester group as a copolymerization component. For example, The polymer of the structural unit B of the base) acrylic acid and the structural unit C derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferred. Hereinafter, preferred examples of the specific polymer in the present disclosure are given, but the present disclosure is not limited to the following examples. In addition, the ratio of the constituent units and the weight-average molecular weight of the exemplified compounds described below are appropriately selected in order to obtain better physical properties.

[Chemical Formula 8]

<< Glass transition temperature of polymer: Tg >> The glass transition temperature (Tg) of the specific polymer in the present disclosure is preferably 90 ° C. or lower. When the Tg is 90 ° C. or lower, the photosensitive resin composition layer has high adhesion and the transferability is more excellent. The above Tg is more preferably 60 ° C or lower, and further preferably 40 ° C or lower. In addition, the lower limit of the above-mentioned Tg is not particularly limited, but -20 ° C or higher is more preferable, and -10 ° C or higher is more preferable. When the Tg of the specific polymer is -20 ° C. or higher, good pattern formability can be maintained, and, for example, when a cover film is used, a decrease in peelability when the cover film is peeled off is suppressed. From the viewpoint of transferability, the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or lower, more preferably 60 ° C. or lower, and further preferably 40 ° C. or lower.

The glass transition temperature of a polymer can be measured using differential scanning calorimetry (DSC). The specific measurement method is carried out sequentially in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature in this specification uses an extrapolated glass transition onset temperature (hereinafter sometimes referred to as Tig). The method for measuring the glass transition temperature will be described more specifically. When determining the glass transition temperature, keep the temperature about 50 ° C lower than the expected Tg of the polymer until the device is stable, and then heat it at a heating rate of 20 ° C / min to a temperature about 30 ° C higher than the temperature at which the glass transition ends. , And draw the DTA curve or DSC curve. The extrapolated glass transition starting temperature (Tig), which is the glass transition temperature Tg in this specification, is a curve that extends the baseline of the low temperature side of the DTA curve or DSC curve to the high temperature side and the stepwise change part of the glass transition The gradient becomes the temperature at the intersection of the tangent lines drawn at the point where the maximum is obtained.

As a method of adjusting the Tg of the polymer to the preferred range described above, for example, the FOX formula can be used as a guide to control based on the Tg of the individual polymer of each constituent unit of the target polymer and the mass ratio of each constituent unit Target Tg for specific polymers. Regarding the FOX formula, the Tg of the individual polymer of the first constitutional unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constitutional unit is W1, and the individual polymer of the second constitutional unit When Tg is Tg2 and the mass fraction in the copolymer of the second constitutional unit is W2, Tg0 (K) of the copolymer including the first constitutional unit and the second constitutional unit can be estimated according to the following formula. FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2) Using the FOX formula described above, and adjusting the types and mass fractions of the constituent units contained in the copolymer, it is possible to obtain the desired Tg copolymer. Moreover, by adjusting the weight average molecular weight of the polymer, the Tg of the polymer can also be adjusted.

<< Molecular weight of polymer: Mw >> The molecular weight of the specific polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. When the weight-average molecular weight of the specific polymer is 60,000 or less, the melt viscosity of the photosensitive resin composition layer can be suppressed to be low, and bonding at a low temperature (for example, 130 ° C. or less) can be achieved when bonding to the substrate. In addition, the weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000. In addition, the weight-average molecular weight of the polymer can be measured by GPC (gel permeation chromatography). As a measuring device, various commercially available devices can be used. The details of the device and the measurement technique are well known to those in the industry. In the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by TOSOH CORPORATION) can be used as the measuring device, and TSKgel (registered trademark) Super HZM can be used as the column -M (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ4000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ3000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION), Super HZ2000 (4.6mmID × 15cm, manufactured by TOSOH CORPORATION) ) In series connection, THF (tetrahydrofuran) can be used as the eluent. Furthermore, as the measurement conditions, the sample concentration can be set to 0.2% by mass, the flow rate to 0.35 ml / min, the sample injection volume to 10 μl, and the measurement temperature to 40 ° C., using differential refractive index (RI ) The detector. The calibration curve can use "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500 "and" A-1000 "are made of any of the seven samples.

The ratio (dispersion degree) of the number average molecular weight to the weight average molecular weight of the specific polymer is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

＜< Specific polymer manufacturing method >> The specific polymer manufacturing method (synthesis method) is not particularly limited, and for example, the polymerizable monomer for forming the structural unit A1 represented by the formula A and The polymerizable monomer forming the structural unit B having an acid group, and, if necessary, is contained in an organic solvent used to form the polymerizable monomer of the other structural unit C, and is synthesized by polymerization using a polymerization initiator. Furthermore, synthesis can also be carried out by a so-called polymer reaction.

The above-mentioned photosensitive resin composition layer in the present disclosure is included in a ratio of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive resin composition layer from the viewpoint of showing good adhesion to the substrate. The above-mentioned polymer component is preferable, and it is more preferable to be contained in a proportion of 70% by mass to 98% by mass. In addition, from the viewpoint of showing good adhesion to the substrate, the photosensitive resin composition layer contains the above-mentioned specificity at a ratio of 50% by mass to 99.9% by mass relative to the total solid content of the photosensitive resin composition layer. The polymer is preferable, and it is more preferable to be included in a ratio of 70% by mass to 98% by mass.

<< Other Polymers >> The polymer component in the photosensitive resin composition layer described above may further contain, in addition to the specific polymer, the formula A in addition to the effect of the effect of the photosensitive transfer material of the present disclosure. The polymer represented as the constituent unit (a) (sometimes called "other polymer"). When the photosensitive resin composition layer contains other polymers, the blending amount of other polymers is preferably 50% by mass or less in the total polymer component, more preferably 30% by mass or less, and further more than 20% by mass. good.

The above-mentioned photosensitive resin composition layer may contain only one kind of other polymer than the specific polymer, or may contain two or more kinds. As other polymers, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer Company, Inc), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (above, manufactured by TOAGOSEI CO., LTD.) And Joncryl 690, Joncryl 678, Joncryl l67 and Joncryl 586 (above, manufactured by BASF JAPAN LTD.), Etc.

-Photoacid generator- The photosensitive resin composition layer contains a photoacid generator. As the photoacid generator used in the present disclosure, it is a compound capable of generating an acid by irradiating radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. As the photo-acid generator used in the present disclosure, actinic rays with a wavelength of 300 nm or more, preferably with a wavelength of 300 nm to 450 nm are induced, and a compound that generates an acid is preferable, but its chemical structure is not limited. Furthermore, even if it is a photoacid generator that does not directly induce actinic rays with a wavelength of 300 nm or more, as long as it is a compound that induces actinic rays with a wavelength of 300 nm or more and generates an acid by using a sensitizer in combination, it can be combined with a sensitizer To better use. As the photoacid generator used in the present disclosure, a photoacid generator that generates an acid with a pKa of 4 or less is preferred, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferred, and a photoacid generator that generates a pKa of 2 or less The acid photoacid generator is particularly good. The lower limit value of pKa is not particularly limited, but for example, it is preferably -10.0 or more.

Examples of the photoacid generator include ionic photoacid generators and nonionic photoacid generators. Further, as the photoacid generator, from the viewpoint of sensitivity and resolution, it is preferable to include at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later, and include an oxime sulfonic acid Salt compounds are more preferred.

Examples of the nonionic photoacid generator include trichloromethyl mesitane, diazomethane compounds, amide imine sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoint of sensitivity, resolution, and adhesion, it is preferable that the photoacid generator is an oxime sulfonate compound. These photoacid generators can be used alone or in combination of two or more. As specific examples of trichloromethyl mesitanes and diazomethane derivatives, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be exemplified.

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

[Chemical Formula 9]

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

Any group of the compound having the oxime sulfonate structure represented by formula (B1) may be substituted, and the alkyl group in R ²¹ may be linear, may have a branched structure, or may have a ring structure. The allowed substituents are described below. The alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be bridged with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (including 7,7-dimethyl-2-oxonorbornyl group, etc.) Formula alicyclic group, bicycloalkyl group, etc. are preferred) or halogen atom substitution. The aryl group of R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, alkoxy groups, and halogen atoms.

The compound having the oxime sulfonate structure represented by the formula (B1) is also preferably the oxime sulfonate compound described in paragraphs 0078 to 0111 of Japanese Patent Laid-Open No. 2014-85643.

Examples of the ionic photoacid generators include onium salt compounds such as diarylionium salts and triarylammonium salt compounds, and quaternary ammonium salts. Among these, onium salt compounds are preferred, and triaryl alkoxide salts and diaryl sulfonium salts are particularly preferred.

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.

One type of photoacid generator may be used alone, or two or more types may be used in combination. The content of the photoacid generator in the photosensitive resin composition layer is preferably 0.1% by mass to 10% by mass relative to the total mass of the photosensitive resin composition layer from the viewpoint of sensitivity and resolution, and 0.5 The mass% to 5 mass% is better.

-Solvent- The photosensitive resin composition layer may contain a solvent. In addition, in order to easily form the photosensitive resin composition layer, the photosensitive resin composition forming the photosensitive resin composition layer contains a solvent to adjust the viscosity of the photosensitive resin composition, and then the photosensitive resin composition containing the solvent By coating and drying the material, the photosensitive resin composition layer can be preferably formed. As the solvent used in the present disclosure, a known solvent can be used. As the solvent, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol mono Alkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetic acid Esters, esters, ketones, amides, and lactones. In addition, as specific examples of the solvent, the solvents described in paragraphs 0174 to 0178 of Japanese Patent Laid-Open No. 2011-221494 can also be cited, and these contents are incorporated in this specification.

In addition, in the solvent described above, benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, Hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate Diester and other solvents. Only one type of solvent may be used, or two or more types may be used. Solvents that can be used in the present disclosure may be used alone, and it is more preferable to use two kinds. When two or more solvents are used, for example, the combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, the combined use of diacetates and diethylene glycol dialkyl ethers, or the combination of esters and butylene glycol The combined use of alkyl ether acetates is preferred.

In addition, as the solvent, a solvent having a boiling point of 130 ° C. or higher and less than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture of these are preferred. Examples of solvents having a boiling point of 130 ° C or higher and less than 160 ° C include propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), and propylene glycol methyl-n-butyl ether (boiling point 155 ° C) ) And propylene glycol methyl-n-propyl ether (boiling point 131 ℃). Examples of solvents having a boiling point of 160 ° C or higher include ethoxy acrylate (boiling point 170 ° C), diethylene glycol methyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), and dipropylene glycol methyl ether Acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol di Acetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃) and 1,3-butanediol diacetate (boiling point 232 ℃) .

As the content of the solvent when coating the photosensitive resin composition, 50 parts by mass to 1,900 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition is more preferable, and 100 parts by mass to 900 parts by mass is more good. Further, the content of the solvent in the photosensitive resin composition layer is preferably 2% by mass or less relative to the total mass of the photosensitive resin composition layer, more preferably 1% by mass or less, and further preferably 0.5% by mass or less good.

-Other Additives-The above-mentioned photosensitive resin composition layer in the present disclosure may contain well-known additives in addition to specific polymers and photoacid generators as needed.

[Plasticizer] The photosensitive resin composition layer may contain a plasticizer for the purpose of improving plasticity. It is preferable that the weight average molecular weight of the plasticizer is less than that of a specific polymer. From the viewpoint of imparting plasticity, 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 even more preferably 800 or more and less than 4,000. The plasticizer is not particularly limited as long as it is a compound compatible with a specific polymer and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkoxy group in the molecule. The alkoxy group contained in the plasticizer preferably has the following structure.

[Chemical Formula 10]

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

In addition, for example, even if it is an alkoxylated compound having the above structure (set to "Compound X"), the chemically amplified positive photosensitive resin composition obtained by mixing Compound X, a specific polymer, and a photoacid generator When the plasticity of the chemically amplified positive photosensitive resin composition formed without the compound X is not improved, the plasticizer in the present disclosure is not satisfied. For example, arbitrarily added surfactants are usually not used in an amount to impart plasticity to the photosensitive resin composition, and therefore do not comply with the plasticizer in this specification.

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

[Chemical Formula 11]

From the viewpoint of adhesion, the content of the plasticizer is preferably 1% by mass to 50% by mass relative to the total mass of the photosensitive resin composition layer, and more preferably 2% by mass to 20% by mass. The photosensitive resin composition layer may contain only one kind of plasticizer, or may contain two or more kinds.

[Sensitizer] The photosensitive resin composition layer may further contain a sensitizer. The sensitizer absorbs actinic rays and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photoacid generator to produce electron movement, energy movement and heat generation. Thereby, the photoacid generator chemically decomposes and generates acid. By containing a sensitizer, exposure sensitivity can be improved.

As a sensitizer, a compound selected from the group consisting of anthracene derivatives, acridinone derivatives, oxythiopin derivatives, coumarin derivatives, basic styrene derivatives, and distyrylbenzene derivatives is Preferably, anthracene derivatives are more preferred. As anthracene derivatives, anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromo Anthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene or 9,10-dimethoxyanthracene is preferred.

Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/093271.

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

[Basic Compound] The photosensitive resin composition layer preferably further contains a basic compound. As the basic compound, it can be arbitrarily selected from the basic compounds used in the chemical amplifier. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids. As specific examples of these, the compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open No. 2011-221494 can be cited, and these contents are incorporated in this specification.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n-pentyl group. Amine, diethanolamine, triethanolamine, dicyclohexylamino, dicyclohexylmethylamine, etc. Examples of aromatic amines include aniline, benzylamine, N, N-dimethylaniline, and dianiline. Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-hexylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, Niacin, nicotinamide, quinoline, 8-oxoquinoline, pyridine, pyrazole, pyridine, purine, pyrrolidine, piperidine, piper, morpholine, 4-methylmorpholine, 1,5-diaza Bicyclo [4.3.0] -5-nonene and 1,8-diazabicyclo [5.3.0] -7-undecene etc. Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide. Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

These basic compounds may be used alone or in combination of two or more. The content of the basic compound is preferably 0.001% by mass to 5% by mass relative to the total mass of the photosensitive resin composition layer, and more preferably 0.005% by mass to 3% by mass.

[Heterocyclic Compound] The photosensitive resin composition layer in the present disclosure can contain a heterocyclic compound. The heterocyclic compound in the present disclosure is not particularly limited. For example, compounds containing epoxy groups or oxetanyl groups, heterocyclic compounds containing alkoxymethyl groups, other various cyclic ethers, cyclic esters (lactones), etc. can be added to the molecules described below Nitrogen-containing monomers such as acid monomers, cyclic amines, and oxazoline groups can be further added with heteroatom-containing ring monomers having atoms with d electrons, such as silicon, sulfur, and phosphine.

When the heterocyclic compound is added, the addition amount of the heterocyclic compound in the photosensitive resin composition layer is preferably 0.01% by mass to 50% by mass relative to the total mass of the photosensitive resin composition layer, and 0.1% by mass -10% by mass is more preferable, and 1% by mass to 5% by mass is even more preferable. Within the above range, it is preferable from the viewpoint of adhesion and etching resistance. Only one type of heterocyclic compound may be used, or two or more types may be used in combination.

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, etc.

Compounds having epoxy groups in the molecule can be purchased as commercial products. Examples include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc., and commercially available products described in paragraph 0189 of Japanese Patent Laid-Open No. 2011-221494. . As other commercially available products, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC- 7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), DENACOL EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX- 830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, 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 (manufactured by Nagase ChemteX Corporation above), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD. ), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, CELVENUS B0134, B0177 (made by Daicel Corporation), etc. The compound having an epoxy group in the molecule may be used alone or in combination of two or more.

Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin can be more preferably mentioned, especially Good examples include aliphatic epoxy resins.

As specific examples of compounds having oxetanyl groups in the molecule, Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX ( Above, manufactured by TOAGOSEI CO., LTD.).

Furthermore, the compound containing oxetanyl group is preferably used alone or in combination with the compound containing epoxy group.

In the photosensitive resin composition layer in the present disclosure, the heterocyclic compound is a compound having an epoxy group, which is preferable from the viewpoint of etching resistance and line width stability.

[Alkoxysilane compound] The photosensitive resin composition layer may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound is preferably mentioned. Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropylalkoxysilane, and γ-epoxy Propoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloro Propyl trialkoxy silane, γ-mercaptopropyl trialkoxy silane, β- (3,4-epoxycyclohexyl) ethyl trialkoxy silane, ethylene trialkoxy silane. Among these, γ-glycidoxypropylalkoxysilane or γ-methacryloxypropyltrialkoxysilane is better, γ-glycidoxypropylalkoxy Silane is further preferred, and 3-glycidoxypropyltrimethoxysilane is particularly preferred. These can be used alone or in combination of two or more.

[Surfactant] The photosensitive resin composition layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic, or amphoteric 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, polysilicone, Fluorine surfactant. In addition, the following KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Japan Electronic Monetary Claim Organization), Megaface (manufactured by DIC Corporation), Fluorad can be cited. (Sumitomo 3M Limited), AsahiGuard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA SOLUTIONS INC.) And SH-8400 (manufactured by Dow Corning Toray Co., Ltd.) and other product names . In addition, as a surfactant, the weight of polystyrene measured by gel permeation chromatography including the structural unit A and the structural unit B represented by the following formula I-1 and using tetrahydrofuran (THF) as a solvent can be measured Copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less are cited as preferred examples.

[Chemical Formula 12]

In formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or the number of carbon atoms Alkyl groups of 1 or more and 4 or less, L represents an alkylene group having a carbon number of 3 or more and 6 or less, p and q represent mass percentages of polymerization ratio, p represents a value of 10% by mass or more and 80% by mass or less, and q represents 20% Values of% or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, s represents an integer of 1 or more and 10 or less, and * represents a bonding site with another structure.

L is preferably a bifurcated alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of compatibility and wettability with respect to the coated surface, 1 to 3 carbon atoms The alkyl group is preferable, and the alkyl group having 2 or 3 carbon atoms is more preferable. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

[Chemical Formula 13]

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

Moreover, the surfactant described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362 can also be used.

One type of surfactant may be used alone, or two or more types may be used in combination. The added amount of the surfactant is preferably 10% by mass or less relative to the total mass of the photosensitive resin composition layer, more preferably 0.001% by mass to 10% by mass, and further preferably 0.01% by mass to 3% by mass.

[Other Components] In the photosensitive resin composition layer of the present disclosure, metal oxide particles, antioxidants, dispersants, acid multiplication agents, development accelerators, conductive fibers, colorants, thermal radical polymerization can be further added Known additives such as initiators, thermal acid generators, ultraviolet absorbers, tackifiers, crosslinking agents, and organic or inorganic precipitation inhibitors. Preferred aspects of other components are described in paragraphs 0165 to 0184 of Japanese Patent Laid-Open No. 2014-85643, and the contents of this bulletin are incorporated in this specification.

[Method for Forming Photosensitive Resin Composition Layer] The components and the solvent can be mixed in any ratio and in any method, and stirred and dissolved to prepare a photosensitive resin composition for forming the photosensitive resin composition layer. For example, after dissolving each component in a solvent in advance to prepare a solution, the obtained solution can be mixed at a specific ratio to prepare a composition. The composition prepared as described above can also be used after being filtered through a filter with a pore size of 0.2 μm or the like.

By coating and drying the photosensitive resin composition on the intermediate layer, the photosensitive transfer material of the present disclosure having the photosensitive resin composition layer on the dummy support can be obtained. The coating method is not particularly limited, and can be applied by a well-known method such as slit coating, spin coating, curtain coating, and inkjet coating. In addition, after forming another layer described later on the intermediate layer, a photosensitive resin composition layer may be coated thereon.

<Other Layers> The photosensitive transfer material of the present disclosure may have layers other than the above-mentioned photosensitive resin composition layer (hereinafter, sometimes referred to as “other layers”). Examples of other layers include a contrast enhancement layer, a cover film, and a thermoplastic resin layer.

-Thermoplastic resin layer, cover film, etc.-From the viewpoint of transferability, the photosensitive transfer material of the present disclosure preferably further has a thermoplastic resin layer between the dummy support and the intermediate layer. In addition, the photosensitive transfer material of the present disclosure may have a cover film for the purpose of protecting the photosensitive resin composition layer. The preferred aspects of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of Japanese Patent Laid-Open No. 2014-85643, and the preferred aspects of the other layers are described in paragraphs 0194 to 0196 of Japanese Patent Laid-Open No. 2014-85643, respectively. The contents of this bulletin are incorporated in this specification. Among them, it is preferable that the thermoplastic resin layer contains at least one thermoplastic resin selected from the group consisting of acrylic resin and styrene / acrylic copolymer from the viewpoint of transferability.

When the photosensitive transfer material of the present disclosure has other layers such as a thermoplastic resin layer, it can be produced in accordance with the production method of the photosensitive transfer material described in paragraphs 094 to 0098 of JP-A 2006-259138. For example, when manufacturing the photosensitive transfer material of the present disclosure having a thermoplastic resin layer, a dissolving solution (coating solution for thermoplastic resin layer) in which a thermoplastic organic polymer and additives are dissolved is applied on a pseudo support and the After drying to provide a thermoplastic resin layer, a preparation liquid (intermediate layer composition) prepared by adding resin and additives to a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the obtained thermoplastic resin layer To build up the middle layer. The photosensitive resin composition prepared by using a solvent that does not dissolve the intermediate layer is further coated and dried on the formed intermediate layer, thereby laminating the photosensitive resin composition layer, whereby the present disclosure can be preferably produced The photosensitive transfer material.

-Contrast Enhancement Layer-The photosensitive transfer material of the present disclosure can include a contrast enhancement layer in addition to the above-mentioned photosensitive resin composition layer. The Contrast Enhancement Layer (CEL) absorbs a large amount of exposure wavelength before exposure, but gradually becomes smaller as it is exposed, that is, it contains a material with a higher transmittance of light (called achromatic pigment Ingredients). As photochromic pigment components, diazonium salts, styryl pyridinium (stilbazolium) salts, aryl nitroso salts and the like are known. As a film forming component, a phenol resin or the like is used. In addition, as the contrast enhancement layer, paragraphs 0004 to 0051 of Japanese Patent Laid-Open No. 6-97065, paragraphs 0012 to 0055 of Japanese Patent Laid-Open No. 6-332167, photopolymer handbook, photopolymerization symposium can be used , Industrial Investigation Association (1989), Photopolymerization Technology (Technology), Yamagata, Yongsong, THE NIKKAN KOGYO SHIMBUN, LTD. (1988) described in the material.

(Manufacturing method of circuit wiring) The manufacturing method of circuit wiring of the present disclosure is not particularly limited as long as the manufacturing method of the photosensitive transfer material of the present disclosure is used, and it is preferable to sequentially include the following processes: The process of contacting and laminating the photosensitive resin composition layer of the disclosed photosensitive transfer material with the substrate; pattern exposing the photosensitive resin composition layer of the photosensitive transfer material after the lamination process Process; a process of developing the photosensitive resin composition layer after the exposure process to form a pattern, and a process of etching the substrate in the area where the pattern is not arranged. In addition, the manufacturing method of the circuit wiring of the present disclosure sequentially includes the following processes: It is preferable that the photosensitive resin composition layer of the photosensitive transfer material of the present disclosure is in contact with and bonded to the substrate relative to the substrate; peeling The process of the dummy support of the photosensitive transfer material; the process of pattern exposing the photosensitive resin composition layer; the process of developing the pattern of the photosensitive resin composition layer to form a pattern; The above-mentioned substrate in the region is subjected to an etching process.

Conventionally, the photosensitive resin composition is divided into a negative type in which a part irradiated with actinic rays remains as an image and a positive type in which a part not irradiated with actinic rays remains as an image, depending on the photosensitive system. In the positive type, by irradiating actinic rays, for example, using a sensitizer that irradiates actinic rays to generate an acid, etc., the solubility of the exposed portion is improved. Therefore, when the pattern is exposed, neither the exposed portion nor the unexposed portion is cured. When the pattern shape is defective, the substrate can be reused (reprocessed) by full exposure or the like. Therefore, from the viewpoint of so-called excellent reworkability, the positive type is preferable. In addition, the technique of re-exposure of the remaining photosensitive resin composition layer to produce different patterns cannot be achieved unless it is a photosensitive resin composition layer. Therefore, in the manufacturing method of the circuit wiring of the present disclosure, it is preferable to Appeared to perform two or more exposures.

<Lamination process> The manufacturing method of the circuit wiring of the present disclosure includes a process (lamination process) in which the photosensitive resin composition layer of the photosensitive transfer material of the present disclosure is in contact with the substrate and bonded to the substrate as: Better. In the above-mentioned bonding process, it is preferable that the photosensitive transfer material is brought into contact with the substrate provided with a conductive layer and bonded. In addition, in the above-mentioned bonding process, it is preferable that the conductive layer and the photosensitive resin composition layer are brought into contact with each other by pressure bonding. In the above-mentioned aspect, the photosensitive resin composition layer formed by the pattern after exposure and development can be preferably used as an etching resist when etching the conductive layer. The method of pressure-bonding the base material and the photosensitive transfer material is not particularly limited, and a known transfer method and lamination method can be used. Specifically, for example, it is preferable to superimpose the photosensitive resin composition layer side of the photosensitive transfer material on the conductive layer and apply pressure by a roller or the like, or pressurization and heating. For lamination, well-known build-ups such as build-up, vacuum build-up, and auto-cut laminator that can further improve productivity can be used. The pressure pressure and temperature in the above-mentioned bonding process are not particularly limited, and can be appropriately set according to the materials, the transmission speed of the conductive layer and the photosensitive resin composition layer, the pressure bonding machine used, and the like. In addition, when a cover film is provided on the photosensitive resin composition layer of the photosensitive transfer material, the cover film may be removed from the photosensitive resin composition layer and then pressure-bonded. When the above substrate is a resin film, roll-to-roll type pressure bonding can be performed.

[Substrate] Among the substrates in which a plurality of conductive layers are laminated on the substrate, the substrate is preferably a glass substrate or a film substrate, and the film substrate is more preferable. In the manufacturing method of the circuit wiring of this disclosure, when it is circuit wiring for touch panels, it is especially preferable that the base material is a sheet-like resin composition. Moreover, it is preferable that the base material is transparent. The refractive index of the substrate is preferably 1.50 to 1.52. The base material may be made of a light-transmitting base material such as a glass base material, and tempered glass typified by Gorilla Glass of Corning Incorporated Co., Ltd. can be used. In addition, as the transparent substrate, materials used in Japanese Patent Laid-Open No. 2010-86684, Japanese Patent Laid-Open No. 2010-152809, and Japanese Patent Laid-Open No. 2010-257492 can be preferably used. When using a film substrate as the substrate, a substrate without optical strain and a substrate with high transparency are better. Specific materials include polyethylene terephthalate (PET) and polynaphthalene dicarboxylic acid. Ethylene glycol ester, polycarbonate, triethyl cellulose, cycloolefin polymer.

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

In the method for manufacturing circuit wiring of the present disclosure, it is preferable that at least one of the plurality of conductive layers contains a metal oxide. As the conductive layer, the electrode pattern of the sensor corresponding to the visible portion used in the capacitance-type touch panel or the wiring of the edge extraction portion is preferable.

[Substrate for Circuit Wiring Formation] The substrate for circuit wiring formation used in the present disclosure is preferably a substrate having a conductive layer on the surface of the base material. The circuit wiring is formed by patterning the conductive layer. In this example, it is preferable to provide a plurality of conductive layers such as metal oxide or metal on a film substrate such as PET.

<Exposure process> In the manufacturing method of the circuit wiring of the present disclosure, a process (exposure process) including pattern exposure of the photosensitive resin composition layer of the photosensitive transfer material after the lamination process is preferred. In the above exposure process, it is preferable to irradiate actinic rays through a mask having a specific pattern on a substrate provided with a coating film. In this process, the photoacid generator decomposes to generate acid. By the catalyst action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate an acid group such as carboxyl group or phenolic hydroxyl group. In the present disclosure, the detailed configuration and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (such as a touch panel) equipped with an input device having a circuit board manufactured in the present disclosure, and minimize the area occupied by the lead wiring, at least a part of the pattern (especially the electrodes of the touch panel The pattern and the portion where the wiring is drawn) are preferably thin lines of 100 μm or less, and more preferably thin lines of 70 μm or less. In addition, the exposure in the above-mentioned exposure process may be exposure through a mask, or digital exposure using a laser or the like, but exposure through a mask for exposure is preferable. The method for manufacturing a patterned substrate of the present disclosure preferably includes a process of bringing the photosensitive transfer material into contact with the exposure mask between the laminating process and the exposure process. With the above-mentioned aspect, the resolution of the obtained pattern is more excellent. Furthermore, the method for manufacturing a circuit wiring of the present disclosure is preferably a process including a dummy support for peeling the photosensitive transfer material between the bonding process and the exposure process. At this time, the surface of the photosensitive transfer material becomes an intermediate layer, but the intermediate layer and the exposure mask can be brought into contact for exposure, and exposure can also be performed at a distance of tens of μm or less. In particular, it is preferable to expose the intermediate layer in contact with the exposure mask.

Examples of actinic rays include visible light, ultraviolet light, and electron beams, but visible light or ultraviolet light is preferred, and ultraviolet light is particularly preferred. As an exposure light source based on actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a fluorescent lamp, a light-emitting diode (LED) light source, an excimer laser generator, etc. can be used, and a g-ray (436 nm) can be preferably used , I-ray (365nm), h-ray (405nm) and other actinic rays with a wavelength of 300nm to 450nm. Furthermore, if necessary, the irradiation light can be adjusted by a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter. As the exposure device, various types of exposure machines such as mirror projection aligner, stepper, scanner, proximity, contact, microlens array, laser exposure, etc. can be used . The use of an exposure amount based on the photosensitive resin composition layer may be appropriately selected, but ^{5mJ / cm 2 ~ 200mJ / cm} 2 is ^{preferred, 10mJ / cm 2 ~ 100mJ /} cm 2 is more preferred. Furthermore, it is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. The so-called PEB (Post Exposure Bake) process can reduce the roughness of the pattern edges caused by standing waves generated in the photosensitive resin composition layer during exposure.

In addition, the pattern exposure may be performed after peeling the dummy support from the intermediate layer and the photosensitive resin composition layer, or may be exposed through the dummy support before peeling the dummy support, and then the dummy support may be peeled off. In order to prevent mask contamination based on the contact between the intermediate layer and the mask, and to avoid the influence of foreign objects attached to the mask on exposure, it is preferable to perform exposure without peeling off the dummy support. In addition, the pattern exposure may be exposure through a mask, or digital exposure using a laser or the like.

<Development Process> A process for manufacturing a circuit wiring of the present disclosure includes a process (development process) in which the photosensitive resin composition layer after the exposure process is developed to form a pattern (development process). In addition, in the development process, the exposed intermediate layer is removed together with the exposed photosensitive resin composition layer. Moreover, in the development process, the intermediate layer of the unexposed portion is also removed in the form of dissolution or dispersion in the developer. The development of the exposed photosensitive resin composition layer in the development process can be performed using a developer. The developer is not particularly limited as long as it can remove the exposed portion of the photosensitive resin composition layer. For example, a known developer such as the developer described in Japanese Patent Application Laid-Open No. 5-72724 can be used. In addition, the developer is preferably a developer in which the exposed portion of the photosensitive resin composition layer undergoes a dissolution-type development behavior. As the developing solution, an alkaline aqueous solution is preferable, and for example, an alkaline aqueous solution containing a compound having a pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is more preferable. The developer may further contain an organic solvent and surfactant that are miscible with water. Examples of the developer that is preferably used in the present disclosure include the developer described in paragraph 0194 of International Publication No. 2015/093271.

The development method is not particularly limited, and may be any of rotary immersion development, shower development, shower and rotary development, and immersion development. Here, shower development will be described. By spraying the developer solution onto the exposed photosensitive resin composition layer and the intermediate layer, the exposed portion can be removed. In addition, after development, it is preferable to spray cleaning agents and the like by spraying, and to remove development residues while wiping with a brush or the like. The liquid temperature of the developer is preferably 20 ° C to 40 ° C. In addition, the long time from exposure to development can further exert the effect of suppressing the deformation of the pattern shape in the present disclosure. Development can be performed immediately after exposure, but the time from exposure to development is preferably 0.5 hours or more after exposure, more preferably 1 hour or more, and even more preferably 6 hours or more. In addition, the effect of suppressing the deformation of the pattern shape in the present disclosure is more exerted. In addition, the method for manufacturing a patterned substrate of the present disclosure may include known processes such as a process of washing with water or the like after development, or a process of drying the obtained patterned substrate.

Moreover, it may have a baking process after heat-processing the pattern obtained by development. Post-baking heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably performed in an environment of 50.66 kPa or more. On the other hand, it is better to perform in an environment of 111.46 kPa or less, and particularly preferably in an environment of 101.3 kPa or less. The post-baking temperature is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C. The post-baking time is preferably from 1 minute to 30 minutes, more preferably from 2 minutes to 10 minutes, and particularly preferably from 2 minutes to 4 minutes. Post-baking can be carried out in an air environment, or in a nitrogen replacement environment.

The conveying speed of the above-mentioned base material in each process in the manufacturing method of the circuit wiring of the present disclosure is not particularly limited, and it is preferably 0.5 m / min to 10 m / min when removing exposure, and 2.0 m / min to when removing exposure 8.0m / min is better.

<Etching Process> The manufacturing method of the circuit wiring of the present disclosure includes a process (etching process) in which the above substrate in the region where the above pattern is not arranged is subjected to an etching process (etching process). In the etching process, the pattern formed by the photosensitive resin composition layer through the development process is used as an etching resist to perform the etching process of the substrate. The etching of the above substrate can be applied by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155, etc., and a dry etching method based on a known plasma etching. For example, as an etching method, a wet etching method which is usually performed by immersing in an etching solution can be mentioned. The etching liquid used in the wet etching appropriately selects an acid type or alkaline type etching liquid according to the etching target. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or phosphoric acid, acidic components, and salts of ferric chloride, ammonium fluoride, or potassium permanganate. Mixed aqueous solution, etc. As the acid component, a combination of plural acid components can be used. Examples of alkaline type etching solutions include aqueous solutions of alkaline components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, or salts of organic amines such as tetramethylammonium hydroxide, alkaline components, and permanganese. Mixed aqueous solutions of salts such as potassium acid. As the alkali component, a combination of a plurality of alkali components can be used.

The temperature of the etching solution is not particularly limited, but it is preferably 45 ° C or lower. In the present disclosure, it is preferable that the pattern used as an etching mask (etching pattern) exhibits excellent resistance to acidic and alkaline etching solutions in a temperature region of 45 ° C. or lower. Therefore, the above pattern is prevented from peeling off during the etching process, and portions where the above pattern does not exist are selectively etched.

After the above etching process, in order to prevent contamination of the process line, a process of cleaning the substrate (cleaning process) and a process of drying the substrate (drying process) may be performed as needed. Regarding the cleaning process, for example, the substrate may be cleaned with pure water at normal temperature (10 ° C to 35 ° C) for 10 seconds to 300 seconds. Regarding the drying process, for example, a blower may be used, and the pressure of the blower (approximately 0.1 kg / cm ² to 5 kg / cm ² ) may be adjusted for drying.

<Peeling Process> The method for manufacturing a circuit wiring of the present disclosure is preferably a process (peeling process) including peeling the photosensitive resin composition layer using a peeling liquid after the etching process. After the etching process is completed, the patterned photosensitive resin composition layer remains. If the above-mentioned photosensitive resin composition layer is not required, all the remaining above-mentioned photosensitive resin composition layer may be removed. As a method of peeling using a peeling liquid, for example, a base having the above-mentioned photosensitive resin composition layer and the like in a stirring peeling liquid of preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. can be mentioned. The method of immersing the material for 5 minutes to 30 minutes. Examples of the stripping liquid include an inorganic base component such as sodium hydroxide or potassium hydroxide, or an organic base component such as tertiary amine or quaternary ammonium salt dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone Or the stripping solution in these mixed solutions. The peeling liquid can be used for peeling by a spray method, a spray method, or a rotary immersion method.

Moreover, the manufacturing method of the circuit wiring of the present disclosure may repeat the exposure process, the development process, and the etching process twice or more as needed. As examples of the exposure process, the development process, and other processes in the present disclosure, the methods described in paragraphs 0035 to 0051 of Japanese Patent Laid-Open No. 2006-23696 can also be preferably used in the present disclosure.

The manufacturing method of the circuit wiring of the present disclosure may include any other manufacturing process. For example, the following processes may be mentioned, but not limited to these processes.

<Process for Reducing Visible Light Reflectivity> The manufacturing method of the circuit wiring of the present disclosure can include a process for reducing the visible light reflectance of a part or all of the conductive layer of the substrate, such as the substrate. As the treatment for reducing the reflectance of visible rays, oxidation treatment and the like can be mentioned. For example, copper is oxidized to make copper oxide, which is blackened, thereby reducing the visible light reflectance. For preferred aspects of the treatment for reducing the reflectance of visible light, see paragraphs 0017 to 0025 of Japanese Patent Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Laid-Open No. 2013-206315 There is a description in it, and the contents of this bulletin are incorporated in this specification.

<The process of forming an insulating film on the etched substrate described above, and the process of forming a new conductive layer on the insulating film> The manufacturing method of the circuit wiring of the present disclosure includes, for example, the circuit wiring formed on the substrate The process of forming the insulating film on the etched conductive layer) and the process of forming a new conductive layer on the insulating film are also preferred. The process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. In addition, an insulating film with a desired pattern may be formed by photolithography using an insulating photosensitive material. The process of forming a new conductive layer on the insulating film is not particularly limited. A photosensitive material having conductivity can be used to form a new conductive layer of a desired pattern by photolithography.

In addition, the method of manufacturing a circuit wiring of the present disclosure may form an etching resist on the above-mentioned new conductive layer by the same method as described above and etch it, or may perform etching by another known method. The circuit board obtained by the method of manufacturing a circuit wiring of the present disclosure may have only one layer of circuit wiring on the substrate, or may have two or more layers of circuit wiring.

Moreover, in the method for manufacturing circuit wiring of the present disclosure, the substrate has a plurality of conductive layers on the surfaces on both sides, and it is also more convenient to form circuits on the surfaces of the substrate on both sides sequentially or simultaneously. good. With this configuration, the first conductive pattern (first circuit wiring) can be formed on one surface of the substrate and the second conductive pattern (second circuit wiring) can be formed on the surface on the other side. The circuit wiring is preferably formed as a circuit wiring for a touch panel.

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

(Input device and display device) As a device provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring of this disclosure, an input device can be mentioned. The input device of the present disclosure may be any input device having at least circuit wiring manufactured by the circuit wiring manufacturing method of the present disclosure, and an electrostatic capacitance type touch panel is preferred. It is preferable that the display device of the present disclosure is provided with the input device of the present disclosure. The display device of the present disclosure 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) The touch panel of the present disclosure is a touch panel having at least circuit wiring manufactured by the method of manufacturing a circuit wiring of the present disclosure. Moreover, it is preferable that the touch panel of the present disclosure has at least a transparent substrate, electrodes, and an insulating layer or a protective layer. The touch panel display device of the present disclosure is a touch panel display device having at least the circuit wiring manufactured by the circuit wiring manufacturing method of the present disclosure, and the touch panel display device having the touch panel of the present disclosure is preferred. As the detection method in the touch panel of the present disclosure and the touch panel display device of the present disclosure, any one of known methods such as a resistive film method, an electrostatic capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among them, the electrostatic capacitance method is preferred.

As the touch panel type, a so-called in-cell type (for example, those described in FIG. 5, FIG. 6, FIG. 7, and FIG. 8 of Japanese Patent Publication No. 2012-517051), and a so-called in-cell type (for example, in JP 19 described in FIG. 19 of 2013-168125, and described in FIGS. 1 and 5 of JP 2012-89102), OGS (One Glass Solution) type, TOL (Touch- on-Lens (lens touch) type (for example, described in FIG. 2 of JP-A-2013-54727), other configurations (for example described in FIG. 6 of JP-A-2013-164871), various Plug-in type (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).

As the touch panel of the present disclosure and the touch panel display device of the present disclosure, it can be applied to "the latest touch panel technology" (published on July 6, 2009 by Techno Times Co., Ltd.), edited by Mitsuo Yuji, " The technology and development of touch panel "(published by CMC in December 2004), FPD International 2009 Forum T-11 lecture textbook, Cypress Semiconductor Corporation application note AN2292, etc. [Example]

The embodiments of the present invention will be described more specifically below with examples. The materials, usage amounts, ratios, processing contents, and processing order shown in the following examples can be appropriately changed as long as they do not depart from the gist of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[Polymer in photosensitive resin composition layer] In the following examples, the following abbreviations represent the following compounds, respectively. ATHF: 2-tetrahydrofuryl acrylate (synthetic product) MATHF: 2-tetrahydrofuran methacrylate (synthetic product) MAEVE: Ethoxyethyl 1-methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) PHSTHF: 4- (2-Tetrahydrofuranyloxy) styrene (synthetic product) PHSEVE: 1-ethoxyethyloxystyrene (synthetic product) PHS: p-hydroxystyrene (synthetic product) AA: acrylic acid (Tokyo Chemical Industry Co., Ltd.) CHA: cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.) PGMEA (propylene glycol monomethyl ether acetate): (manufactured by SHOWA DENKO KK) V-601: dimethyl 2,2 '-Azobis (2-methyl propionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of ATHF> Acrylic acid (72.1 parts, 1.0 mole equivalent) and hexane (72.1 parts) were added to a 3-necked flask and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts, 1.0 molar equivalent) and stirring at 20 ℃ ± 2 ℃ for 1.5 hours, the temperature was raised to 35 ℃ and carried out Stir for 2 hours. After the suction filter is covered with Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) in this order, by The reaction liquid was filtered to obtain a filtrate. After adding hydroquinone monomethyl ether (MEHQ, 0.0012 parts) to the obtained filtrate, by concentration under reduced pressure at 40 ° C, 140.8 parts of tetrahydrofuran-2-yl acrylate (ATHF) was obtained as a colorless oil. (Yield 99.0%).

<Synthesis of MATHF> In a 3-necked flask, methacrylic acid (86.1 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts, 1.0 molar equivalent) and stirring at 20 ℃ ± 2 ℃ for 1.5 hours, the temperature was raised to 35 ℃ Stir for 2 hours. After the suction filter was covered with Kyoward 200 and Kyoward 1000 in this order, the filtered solution was obtained by filtering the reaction solution. After MEHQ (0.0012 parts) was added to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C to obtain 156.2 parts (yield) of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oil. 98.0%).

<Synthesis of PHS> In a 3-necked flask, 4-vinylphenyl acetate (25.0 parts, 0.154 mole equivalent) and ethyl acetate (34.2 parts) were added and cooled to 5 ° C. After dripping 28% sodium methoxide methanol solution (59.5 parts), it stirred for 2 hours. Ethyl acetate (100 parts), water (200 parts) and ammonium chloride (33.0 parts) were added, and a liquid separation operation was performed to extract the organic layer. The obtained organic layer was washed sequentially with saturated ammonium chloride aqueous solution and saturated brine, and concentrated under reduced pressure at 40 ° C to obtain 17.0 parts of p-hydroxystyrene (PHS) as a yellow oil ( Yield 91.9%).

<Synthesis of PHSTHF> In a 3-necked flask, p-hydroxystyrene (120.0 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and 2-dihydrofuran (70.1 parts, 1.0 molar equivalent) and stirring at 20 ℃ ± 2 ℃ for 1.5 hours, the temperature was raised to 35 ℃ and carried out Stir for 2 hours. After the suction filter was covered with Kyoward 200 and Kyoward 1000 in this order, the filtered solution was obtained by filtering the reaction solution. After MEHQ (0.0012 parts) was added to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C to obtain 4- (2-tetrahydrofuryloxy) styrene (PHSTHF) 186.3 as a colorless oil. Portion (yield 98.0%).

<Synthesis of PHSEVE> In a 3-necked flask, p-hydroxystyrene (120.0 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After dripping camphorsulfonic acid (0.0070 parts, 0.03 millimolar equivalent) and ethyl vinyl ether (72.1 parts, 1.0 molar equivalent) and stirring at 20 ° C ± 2 ° C for 1.5 hours, the temperature was raised to 35 ° C and carried out Stir for 2 hours. After the suction filter was covered with Kyoward 200 and Kyoward 1000 in this order, the filtered solution was obtained by filtering the reaction solution. After MEHQ (0.0012 parts) was added to the obtained filtrate, it was concentrated under reduced pressure at 40 ° C to obtain 188.2 parts of 1-ethoxyethyloxystyrene (PHSEVE) as a colorless oil. (Yield 98.0%).

<Synthesis Example of Polymer A-1> PGMEA (75.0 parts) was added to a 3-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. The solution mixed with ATHF (38.70 parts), AA (1.47 parts), CHA (59.83 parts), V-601 (4.1 parts), PGMEA (75.0 parts) was dripped to maintain the temperature at 90 ℃ ± 2 ℃ for 2 hours 3-neck flask solution. After completion of the dripping, the polymer A-1 (solid content concentration 40.0% by mass) was obtained by stirring at 90 ° C ± 2 ° C for 2 hours.

<Synthesis Examples of Polymers A-2 to A-5> The types of monomers and the like were changed as shown in the following table, and other conditions were synthesized by the same method as A-1. The solid content concentration of the polymer was set to 40% by mass. The content unit of each structural unit (monomer unit which polymerized each monomer) of Table 1 is mol%.

[Table 1]

[Photoacid generator] B-1: Irgacure PAG-103 manufactured by BASF JAPAN LTD., The following compounds

[Chemical Formula 14]

B-2: The compound of the structure shown below (the compound described in paragraph 2227 of JP-A-2013-47765 and synthesized according to the method described in paragraph 2227.)

[Chemical Formula 15]

B-3: Compounds of the structure shown below (Synthesized according to the method described in paragraph 0160 of International Publication No. 2014/020984.)

[Chemical Formula 16]

B-4: A compound of the structure shown below (the compound described in paragraph 0208 of Japanese Unexamined Patent Publication No. 2012-163937, and synthesized according to the method described in paragraph 0212.)

[Chemical Formula 17]

[Sensitizer] E-1: ANTHRACURE (registered trademark) UVS-1331 manufactured by Kawasaki Kasei Chemicals Ltd., the following compound (In addition, Bu represents butyl.)

[Chemical Formula 18]

[Surfactant] E-1: Compound with the structure shown below

[Chemical Formula 19]

[Basic compound] D-1: Compound of the structure shown below (CMTU)

[Chemical Formula 20]

<Synthesis Example of Polymer C-1> In the following examples, the following abbreviations represent the following compounds, respectively. AANa: sodium acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) HEMA: 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) PGME: propylene glycol monomethyl ether (manufactured by SHOWA DENKO K.K.)

PGME (75.0 parts) was added to the 3-necked flask, and the temperature was raised to 90 ° C under a nitrogen atmosphere. A solution mixed with AANa (45.37 parts), HEMA (54.63 parts), V-601 (4.1 parts), and PGME (75.0 parts) was dropped into a 3-neck flask solution maintained at 90 ° C ± 2 ° C over 2 hours. After completion of dripping, the polymer C-1 (solid content concentration 40.0% by mass) was obtained by stirring at 90 ° C ± 2 ° C for 2 hours.

(Example 1) <Preparation of intermediate layer composition> Mix and dissolve according to the following composition, and filter with a polytetrafluoroethylene filter having a pore diameter of 5.0 μm to obtain an intermediate layer composition (solid content concentration 5.0 mass %). Ion-exchanged water: 47.5 parts by mass Methanol: 47.5 parts by mass Hydroxypropyl methyl cellulose (HPMC, TC-5E manufactured by Shin-Etsu Chemical Co., Ltd.): 5.0 parts by mass

<Preparation of photosensitive resin composition> It was prepared according to the following composition, and filtered through a filter made of polytetrafluoroethylene with a pore diameter of 0.2 μm to obtain a photosensitive resin composition. PGMEA: 424.5 parts by mass Polymer A-1: 237.0 parts by mass Photoacid generator B-1: 5.0 parts by mass Surfactant E-1: 0.1 parts by mass Basic compound D-1: 0.1 parts by mass

<Preparation of photosensitive transfer material> On a 50 μm-thick polyethylene terephthalate film (hereinafter also referred to as “PET (A)”) that becomes a pseudo-support, the intermediate layer composition is made into a slit shape The nozzle was coated so that the dry film thickness became 1.0 μm. After that, it was dried in a convection oven at 100 ° C. for 2 minutes, and then the photosensitive resin composition was applied with a slit-shaped nozzle so that the dry film thickness became 3.0 μm. After that, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Co., Ltd., OSM-N) was pressure-bonded as a cover film to produce a photosensitive transfer material .

(Example 2) A photosensitive transfer material was produced in the same manner as in Example 1 except that the intermediate layer composition was prepared so that the mass ratio of the content in the solid content became the composition described in Table 2.

(Examples 3 to 25 and 27 to 31) <Preparation of thermoplastic resin composition H1> Methanol: 11.1 parts by mass of propylene glycol monomethyl ether acetate: 6.36 parts by mass of methylhexyl ketone: 52.4 parts by mass of methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (mole ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ℃): 5.83 mass Parts styrene / acrylic acid copolymer (copolymerization composition ratio (mole ratio) = 63/37, weight average molecular weight = 10,000, Tg ≒ 100 ° C): 13.6 parts by mass of monomer 1 (ethylene oxide (EO) modification) Bisphenol A dimethacrylate (EO10 molar equivalent), product name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 parts by mass of fluorine-based polymer: 0.54 parts by mass of the above-mentioned fluorine-based polymer Copolymer of 40 parts C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ and 55 parts H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH = CH ₂ and 5 parts H (OCHCH ₂ ) ₇ OCOCH = CH ₂ A solution having a weight average molecular weight of 30,000 and a methylhexyl ketone 30% by mass solution (product name: Megaface F780F, manufactured by DIC Corporation).

<Preparation of the intermediate layer composition> The intermediate layer composition was prepared so that the mass ratio of the content in the solid content became the composition described in Table 2, except that the intermediate layer composition was mixed and dissolved in the same manner as in Example 1. It was filtered with a polytetrafluoroethylene filter having a pore size of 5.0 μm, and thereby the intermediate layer compositions (solid content concentration 5.0% by mass) of Examples 3 to 25 and 27 to 31 were obtained, respectively.

<Preparation of photosensitive transfer material> On a polyethylene terephthalate film (PET (A)) with a thickness of 50 μm that becomes a pseudo support, the thermoplastic resin composition H1 was dried with a slit-shaped nozzle to a thickness of The coating was carried out in the manner of 5.0 μm. After that, it was dried in a convection oven at 100 ° C. for 2 minutes, and then the intermediate layer composition was applied with a slit-shaped nozzle so that the dried film thickness became 1.0 μm. After that, it was dried in a convection oven at 100 ° C. for 2 minutes, and then the photosensitive resin composition was applied with a slit-shaped nozzle so that the dried film thickness became 3.0 μm. After that, it was dried in a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Co., Ltd., OSM-N) was pressure-bonded as a cover film to produce a photosensitive transfer material .

(Example 26) B-4 was used as a photoacid generator, and 5.0 parts by mass of a sensitizer was added, and the amount of polymer added was reduced by 5.0 parts by mass, in the same manner as Example 23 except that A photosensitive transfer material was produced.

(Examples 32 and 33) As the thermoplastic resin composition, the following thermoplastic resin compositions H2 or H3 were used, respectively, and the photosensitive transfer materials of Examples 32 and 33 were produced in the same manner as in Example 17.

<Preparation of thermoplastic resin composition H2> Methanol: 11.1 parts by mass of propylene glycol monomethyl ether acetate: 6.36 parts by mass of methylhexyl ketone: 52.4 parts by mass of styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63 / 37, weight average molecular weight = 10,000, Tg ≒ 100 ℃): 19.43 parts by mass of monomer 1 (product name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 parts by mass of fluorine-based polymer ( Product name: Megaface F780F, manufactured by DIC Corporation): 0.54 parts by mass

<Preparation of thermoplastic resin composition H3> Methanol: 11.1 parts by mass of propylene glycol monomethyl ether acetate: 6.36 parts by mass of methylhexyl ketone: 52.4 parts by mass of methyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid Benzyl ester / methacrylic acid copolymer (copolymer composition ratio (mole ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ℃): 19.43 parts by mass of monomer 1 (product name: BPE-500 , Manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.6 parts by mass of fluorine-based polymer (product name: Megaface F780F, manufactured by DIC Corporation): 0.54 parts by mass

(Comparative Examples 1 and 5 to 8) In the same manner as in Example 1, except that the thermoplastic resin composition and the intermediate layer composition were not applied but the photosensitive resin compositions described in Table 2 below were applied separately. The photosensitive transfer materials of Comparative Examples 1 and 5 to 8 were prepared respectively.

(Comparative Examples 2 to 4) The photosensitive transfer materials of Comparative Examples 2 to 4 were prepared in the same manner as in Example 3, except that the intermediate layer compositions described in Table 2 below were used, respectively.

[Performance Evaluation] A PET substrate with a copper layer and a copper layer was prepared by a sputtering method on a polyethylene film of polyethylene terephthalate (PET) with a thickness of 188 μm and a thickness of 500 nm.

<Evaluation of transferability> The prepared photosensitive transfer material was cut into 50 cm squares, the cover film was peeled off, and the copper layer was deposited under the stacking conditions of roller temperature 90 ° C., line pressure 0.6 MPa, line speed 3.6 m / min. Lamination was carried out on the PET substrate. The area where the photosensitive resin composition layer and the copper layer are closely adhered was measured, and the area ratio of the adhesion was determined from the area where the photosensitive resin composition layer was adhered / the area of the cut transfer material (%). 5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: less than 80%

<Evaluation of Pixel Deformation> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear speed (laminating speed) of 3.6 m / min. In addition, when the above transferability evaluation was 4 or less at a roller temperature of 90 ° C., until the above transferability evaluation became judgment 5, the roller temperature was increased to prepare a sample. Without exposing the dummy support, after exposing with a line-and-space pattern (duty ratio 1: 1) with a line width of 3 μm to 20 μm and an ultra-high pressure mercury lamp, at 23 ° C. After being left for 6 hours, the dummy support was peeled off and developed. The development was carried out using a 1.0% by mass sodium carbonate aqueous solution at 28 ° C. for 40 seconds by spray development. The 10 μm line and space pattern was formed by the above method, the exposure amount at which the ratio of line width and space width was 1: 1 was obtained, and the 5 μm line and space pattern in the exposure amount was observed by scanning electron microscope (SEM) The amount of deformation of the front end was evaluated for pixel deformation. 3 or more is a level that can be actually used. 5: No pixel distortion is observed 4: Pixel distortion is less than 0.5 μm 3: Pixel distortion is 0.5 μm or more and less than 1.0 μm 2: Pixel distortion is 1.0 μm or more and less than 3.0 μm 1: Pixel distortion is 3.0 μm Above or no pixel residue

<Evaluation of Solubility of Developer> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating speed) of 3.6 m / min. In addition, when the above-mentioned transferability evaluation was 4 or less at a roller temperature of 90 ° C., until the above-mentioned transferability evaluation became judgment 5, the roller temperature was increased to prepare a sample. Full exposure was carried out at an exposure of 300 mJ / cm ² without peeling off the dummy support, and the dummy support was peeled off after being left at 23 ° C. for 1 hour, and a 28 ° C. 1.0% by mass sodium carbonate aqueous solution was used while changing the development time. Spray development. The solubility of the developer was evaluated by determining the time from the start of development until the residual film disappeared. 5: The time from the start of development to the disappearance of the residual film is less than 5 seconds 4: The time from the start of development to the disappearance of the residual film is 5 seconds or more and less than 10 seconds 3: The time from the start of development to the disappearance of the residual film is 10 seconds Above and less than 30 seconds 2: The time from the start of development until the residual film disappears is 30 seconds or more and less than 60 seconds 1: The time from the start of development to the disappearance of residual film is 60 seconds or more

[Table 2]

In addition, the value of the content (mass%) of each resin of the intermediate layer in Table 2 represents the ratio in 5.0 parts by mass of the resin used in the intermediate layer composition.

The details of the abbreviations described in Table 2 are as follows. HPMC: Hydroxypropyl methylcellulose, TC-5E manufactured by Shin-Etsu Chemical Co., Ltd. Low molecular weight type HPMCH: Hydroxypropyl methylcellulose, TC-5S manufactured by Shin-Etsu Chemical Co., Ltd. High Molecular weight type HPC: Hydroxypropyl cellulose, Nisso HPC SSL manufactured by NIPPON SODA CO., LTD. Molecular weight 40,000 HPCH: Hydroxypropyl cellulose, Nisso HPC L manufactured by NIPPON SODA CO., LTD. Molecular weight 140,000 PhNv: Phenol novolak resin , RM-25 PA manufactured by ASAHI YUKIZAI CORPORATION: acrylic resin (polymer C-1), sodium acrylate / hydroxyethyl acrylate copolymer (mole ratio = 50: 50), molecular weight 20,000 PVA: polyvinyl alcohol, Kuraray Co. , Ltd. KURARAY PVA-205 PVP: polyvinylpyrrolidone, NIPPON SHOKUBAI CO., LTD. Polyvinylpyrrolidone K-30 PAA: polyacrylic acid, TOAGOSEI CO., LTD. Aron A-10SL PAANa: Sodium polyacrylate, manufactured by TOAGOSEI CO., LTD. Aron A-210 PEO: polyethylene oxide, manufactured by MEISEI CHEMICAL WORKS, LTD. ALK0X L-6 PEI: polyethylenimine, manufactured by NIPPON SHOKUBAI CO., LTD. EPOMIN SP-018

(Example 41) A photosensitive transfer material using the intermediate layer and the photosensitive resin composition described in Example 1 was prepared by the method described in Example 1, and evaluated for pixel distortion and developer The following changes were made in the solubility evaluation, and the same performance evaluation was carried out except for the following.

<Evaluation of Pixel Deformation> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear speed (laminating speed) of 3.6 m / min. In addition, in this buildup, until the above transferability evaluation became determination 5, the roller temperature was increased to prepare a sample. After peeling off the dummy support, the line with a line width of 3 μm to 20 μm was brought into contact with the space pattern (Duty ratio 1: 1) mask and the intermediate layer, and exposed with an ultra-high pressure mercury lamp, and then placed at 23 ° C for 6 hours. development. The development was carried out using a 1.0% by mass sodium carbonate aqueous solution at 28 ° C. for 40 seconds by spray development. The 10 μm line and space pattern was formed by the above method, the exposure amount at which the ratio of line width and space width was 1: 1 was obtained, and the 5 μm line and space pattern in the exposure amount was observed with a scanning electron microscope (SEM) The amount of deformation of the front end was evaluated for pixel deformation. 3 or more is a level that can be actually used. 5: No pixel distortion is observed 4: Pixel distortion is less than 0.5 μm 3: Pixel distortion is 0.5 μm or more and less than 1.0 μm 2: Pixel distortion is 1.0 μm or more and less than 3.0 μm 1: Pixel distortion is 3.0 μm Above or no pixel residue

<Evaluation of Solubility of Developer> The prepared photosensitive transfer material was laminated on a PET substrate with a copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminating speed) of 3.6 m / min. In addition, when the above-mentioned transferability evaluation was 4 or less at a roller temperature of 90 ° C., until the above-mentioned transferability evaluation became judgment 5, the roller temperature was increased to prepare a sample. After peeling off the dummy support, it was fully exposed at an exposure of 300 mJ / cm ² , and after standing at 23 ° C for 1 hour, a 28 ° C 1.0% by mass sodium carbonate aqueous solution was used to perform spray development while changing the development time. . The solubility of the developer was evaluated by determining the time from the start of development until the residual film disappeared. 5: The time from the start of development to the disappearance of the residual film is less than 5 seconds 4: The time from the start of development to the disappearance of the residual film is 5 seconds or more and less than 10 seconds 3: The time from the start of development to the disappearance of the residual film is 10 seconds Above and less than 30 seconds 2: The time from the start of development until the residual film disappears is 30 seconds or more and less than 60 seconds 1: The time from the start of development to the disappearance of residual film is 60 seconds or more

(Examples 42 to 44) A photosensitive transfer material using the intermediate layer and the photosensitive resin composition described in Examples 2 to 4 was prepared by the method described in Example 1 and evaluated for pixel distortion In addition, in the evaluation of the solubility of the developer, the same changes as those in Example 41 were carried out, and all the same performance evaluations were carried out.

[table 3]

(Example 101) On a 100-μm-thick PET substrate, indium tin oxide (ITO) was formed as a second-layer conductive layer by sputtering at a thickness of 150 nm, and the first layer was conductive The copper layer was formed into a 200 nm thick layer by vacuum evaporation method as a conductive layer, thereby forming a circuit-forming substrate. The photosensitive transfer material 1 obtained in Example 1 (linear pressure 0.8 MPa, linear speed 3.0 m / min, roller temperature 90 ° C.) was laminated on the copper layer. The contact pattern exposure was performed using the photomask provided with the pattern shown in FIG. 2 (hereinafter also referred to as “pattern A”) having a configuration in which a conductive layer pad was connected in one direction without peeling the dummy support. In addition, in the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are light-shielding portions, and the broken line portion DL is a frame that tentatively indicates alignment. After that, the dummy support was peeled, developed, and washed with water to obtain the pattern A. Next, the copper layer was etched using a copper etching solution (Cu-02 made by KANTO CHEMICAL CO., INC.), And then the ITO layer was etched using an ITO etching solution (ITO-02 made by KANTO CHEMICAL CO., INC.). This obtained a substrate in which the pattern A was drawn by copper (solid line portion SL) and ITO (gray portion G) together.

Next, pattern exposure, development, and water washing were performed using the photomask in which the pattern shown in FIG. 3 (hereinafter also referred to as “pattern B”) was provided in an aligned state. In the pattern B shown in FIG. 3, the gray portion G is a light-shielding portion, and the broken line portion DL is a frame that tentatively indicates alignment. Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin composition layer was stripped using a stripping solution (10% by mass sodium hydroxide aqueous solution) to obtain a circuit wiring board. Thereby, a circuit wiring board was obtained. When observed with a microscope, there is no flaking or missing, which is a perfect pattern.

(Examples 102 to 133) The photosensitive transfer materials obtained in Examples 2 to 33 were used to perform the same evaluation as in Example 101. As a result, there was no peeling, missing, etc., and they were perfect patterns.

(Example 141) An indium tin oxide (ITO) film was formed by sputtering at a thickness of 150 nm on a 100-μm-thick PET substrate as a conductive layer of the second layer, and a conductive layer of the first layer was formed thereon. The copper layer was formed into a 200 nm thick layer by vacuum evaporation method as a conductive layer, thereby forming a circuit-forming substrate. The photosensitive transfer material 1 obtained in Example 1 (linear pressure 0.8 MPa, linear speed 3.0 m / min, roller temperature 90 ° C.) was laminated on the copper layer. The dummy support was peeled off, and contact pattern exposure was performed using the photomask provided with the pattern A. The pattern exposure was carried out after peeling the dummy support body in this way, and the same evaluation as in Example 101 was performed except for this. Thereby, a circuit wiring board was obtained. When observed with a microscope, there is no flaking or missing, which is a perfect pattern.

(Examples 142 to 144) The photosensitive transfer materials obtained in Examples 2 to 4 were used to perform the same evaluation as in Example 141. As a result, there was no peeling, missing, etc., and they were perfect patterns.

10‧‧‧Pseudo support

12‧‧‧ middle layer

14‧‧‧Photosensitive resin composition layer

16‧‧‧covering film

100‧‧‧Photosensitive transfer material

SL‧‧‧Solid line department

G‧‧‧Gray

DL‧‧‧ dotted line

FIG. 1 is a schematic diagram showing an example of the layer structure of the photosensitive transfer material of the present disclosure. FIG. 2 is a schematic diagram showing the pattern A. FIG. FIG. 3 is a schematic diagram showing pattern B. FIG.

Claims (12)

A photosensitive transfer material comprising: a pseudo-support; an intermediate layer; and a photosensitive resin composition layer, the photosensitive resin composition layer containing a polymer and a photoacid generator, and the polymer containing an acid-decomposable group The structural unit of the protected acid group, the intermediate layer contains resin C, and the resin C is water-soluble or alkali-soluble, and includes a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain. The photosensitive transfer material as described in item 1 of the patent application range, wherein a thermoplastic resin layer is further provided between the dummy support and the intermediate layer. The photosensitive transfer material according to item 1 or 2 of the patent application, wherein the resin C is at least one resin selected from the group consisting of novolak resins, modified cellulose resins, and acrylic resins having hydroxyl groups . The photosensitive transfer material according to item 1 or 2 of the patent application, wherein the intermediate layer further contains a water-soluble or alkali-soluble resin D other than the resin C. The photosensitive transfer material as described in item 4 of the patent application, wherein the resin D is selected from the group consisting of polyacrylic acid, sodium polyacrylate, polypropylene amide, polyethylene oxide, polyethyleneimine, and polyvinyl alcohol And at least one resin of the group consisting of polyvinylpyrrolidone. The photosensitive transfer material as described in item 4 of the patent application, wherein the resin D is at least one resin selected from the group consisting of polyvinyl alcohol and polyvinylpyrrolidone. The photosensitive transfer material as described in item 4 of the patent application range, wherein the content ratio of the resin C and the resin D in the intermediate layer is resin C: resin D = 5: 1 to 1: 2. The photosensitive transfer material as described in Item 7 of the patent application range, wherein the content ratio of the resin C and the resin D in the intermediate layer is resin C: resin D = 4: 1 to 2: 1. The photosensitive transfer material as described in Item 1 or Item 2 of the patent application, wherein the structural unit having an acid group protected by an acid-decomposable group is a structural unit represented by the following formula A, In formula A, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ represents an alkyl group or an aryl group, R ³¹ Or R ³² may be linked to R ³³ to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an aryl group. The photosensitive transfer material according to item 1 or 2 of the patent application, wherein the glass transition temperature of the polymer in the photosensitive resin composition layer is -20 ° C or higher and 90 ° C or lower. A method for manufacturing circuit wiring, which has the following processes in sequence: With respect to a substrate, the photosensitive resin composition layer of the photosensitive transfer material described in item 1 or 2 of the patent application scope is brought into contact with and pasted to the substrate A combined process; a process of pattern exposing the photosensitive resin composition layer of the photosensitive transfer material after the lamination process; developing and forming the photosensitive resin composition layer after the exposure process The process of the pattern; and the process of etching the substrate in the area where the pattern is not configured. A method of manufacturing a circuit wiring, which includes the following processes in sequence: With respect to a substrate, the photosensitive resin composition layer of the photosensitive transfer material described in item 1 or 2 of the patent application scope is brought into contact with and pasted to the substrate The combined process; the process of peeling off the dummy support of the photosensitive transfer material; the process of pattern exposing the photosensitive resin composition layer; the process of developing and patterning the photosensitive resin composition layer; and The etching process of the substrate in the area where the pattern is not configured.