TW201800840A - Photosensitive transfer materials and method for producing circuit wiring - Google Patents

Abstract

A photosensitive transfer printing material and a manufacturing method of circuit wiring are provided. The photosensitive transfer printing material has good sealability even lamination on a substrate is carried out at low temperature and high speed, so that circuit wiring can be formed at higher resolution. The photosensitive transfer printing material (100) includes a temporatory supporter (12) and a positive-form photosensitive resin layer (14) formed thereon. The positive-form photosensitive resin layer (14) includes a sturcture unit represented as the general formula (A), a structure unit having an acid group, a polymer which is lower than 90 DEG C in glass-transition temperature, and a photo-acid-producer. In the general formula (A), R31 and R32 independently represent H, alkyl groups or aryl groups, at least one of the R31 and R32 is the alkyl group or aryl group; R33 refers to an alkyl group or aryl group; the R31 or the R32 can be linked to the R33 to form cyclic ether; R34 refers to hydrogen atom or methyl group; and X0 refers to a single bond or an arylidene group.

Description

Manufacturing method of photosensitive transfer material and circuit wiring

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

In a display device (such as an organic electroluminescent (EL) display device and a liquid crystal display device) provided with a touch panel such as an electrostatic capacitance type input device, the electrode pattern of the sensor corresponding to the visible portion, the peripheral wiring portion, and the extraction A conductive layer pattern such as a wiring in a wiring portion is provided inside the touch panel. Generally, in the formation of a patterned layer, since the number of steps for obtaining a desired pattern shape is small, the following method is widely used: for a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material The layer is exposed through a mask having a desired pattern, and is partially cured before being developed.

For example, Patent Document 1 discloses a photosensitive transfer material including a support and a photosensitive resin composition layer, and a pattern forming method using the same, and the photosensitive resin composition layer includes a polymer A body component and a photoacid generator, the polymer component including a polymer having a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group, and the photosensitive resin composition does not have ethylene Sexual cross-linked structure.

In addition, Patent Document 2 discloses a positive-type photosensitive resin composition and a pattern forming method using the positive-type photosensitive resin composition. The positive-type photosensitive resin composition includes an acid generator and a resin. The resin has a group containing a lactone or a sultone, and its solubility with respect to an alkaline aqueous solution is increased by the action of an acid. Patent Document 2 describes that a pattern having a good rectangular cross-sectional shape can be formed even if the film thickness is increased. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2015/093271 [Patent Document 2] Japanese Patent Laid-Open No. 2015-194715

[Problems to be Solved by the Invention] In the circuit wiring for a touch panel, the electrode pattern of the sensor corresponding to the visible portion does not intersect with the wiring of the peripheral extraction portion (peripheral wiring portion and extraction wiring portion). (Bridge) and other three-dimensional connections. Therefore, in the technical field of a method for manufacturing a circuit wiring for a touch panel, as in a conventional patterning method using a photosensitive resin composition, a resist is not formed for each required pattern, and it is expected to use a single resist The agent is formed to form a circuit wiring including a conductive layer having a plurality of patterns, thereby omitting steps.

From the viewpoint of improving productivity and the like, it is desirable to use a substrate for forming circuit wiring (hereinafter, sometimes referred to as a "circuit wiring forming substrate") without reducing the resolution of the patterned circuit wiring. ) And a photosensitive transfer material, for example, laminating at a low temperature while carrying a roll to roll at a high speed, and exposing and developing.

When the photosensitive transfer material disclosed in Patent Document 1 is bonded to a circuit wiring forming substrate at a low temperature and at a high speed, there is a case where the adhesion is insufficient, and when the temporary support is peeled off, the photosensitive resin layer is also removed. At the same time, part of the photosensitive resin composition layer was accidentally peeled off during the manufacturing process of the circuit wiring. The photosensitive resin composition described in Patent Document 2 is a composition in which a thick film layer is formed by a coating method. When the configuration of the photosensitive resin composition used is considered, it is applied to a transfer material In the case of pattern formation, sensitivity and resolution may be insufficient.

An object of the present invention is to provide a photosensitive transfer material and a method for manufacturing a circuit wiring, which are used even at a low temperature and high speed (for example, the temperature of a roll used for bonding is 130 ° C or lower, and the transfer speed is 1). m / min or more) Bonded to the circuit wiring forming substrate, it also has good adhesion and can form circuit wiring with high resolution. [Means for solving problems]

The present inventors conducted intensive research and found that the objective can be solved by using a photosensitive transfer material with a positive photosensitive resin layer on a temporary support. The positive photosensitive resin layer includes a Structure and physical properties of polymers and photoacid generators. That is, the present invention includes the following embodiments.

<1> A photosensitive transfer material including: a temporary support; and a positive-type photosensitive resin layer including a structural unit represented by the following general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 Polymers below ℃ and photoacid generators.

[Chemical 1]

In Formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, and R ³¹ Alternatively, R ³² may be bonded 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 arylene group.

<2> The photosensitive transfer material according to <1>, wherein the glass transition temperature of the polymer is -20 ° C or higher. <3> The photosensitive transfer material according to <1> or <2>, wherein the polymer contains 20% by mass or more of the structural unit represented by the general formula A with respect to the total solid content of the polymer. <4> The photosensitive transfer material according to any one of <1> to <3>, wherein the polymer contains a structure having an acid group of 0.1 to 20% by mass based on the total solid content of the polymer. unit. <5> The photosensitive transfer material according to any one of <1> to <4>, wherein R ³⁴ is a hydrogen atom in the general formula A with respect to the total amount of the constituent units represented by the general formula A The constituent unit is 20% by mass or more. <6> The photosensitive transfer material according to any one of <1> to <5>, wherein the photosensitive transfer material further includes a basic compound. <7> The photosensitive transfer material according to <6>, wherein the basic compound is a morpholine-based compound. <8> The photosensitive transfer material according to any one of <1> to <7>, wherein the polymer has a weight average molecular weight Mw of 6.0 × 10 ⁴ or less. <9> The photosensitive transfer material according to any one of <1> to <8>, wherein the temporary support has a light-transmitting property.

<10> A method for manufacturing a circuit wiring, which includes the following steps: (A) a laminating step in which a positive photosensitive resin layer of the photosensitive transfer material as described in <9> is brought into contact with a substrate and bonded to the substrate; (B) an exposure step, which pattern-exposes the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step; (C) a developing step, which develops the positive-type photosensitive resin layer after the exposure step, and Forming a pattern; and (D) an etching step of performing an etching process on the substrate in a region where the pattern is not arranged.

<11> A method for manufacturing a circuit wiring, which includes: (a) a bonding step for a substrate, that is, a substrate including a plurality of conductive materials including a base material and a first conductive layer and a second conductive layer that are different from each other in constituent materials; Layer, and a substrate having a first conductive layer and a second conductive layer as the outermost layers is laminated on the surface of the substrate in order away from the surface of the substrate, so that the photosensitive transfer material according to <9> The positive photosensitive resin layer is bonded to contact with the first conductive layer; (b) in the first exposure step, the positive photosensitive resin layer is patterned through the temporary support of the photosensitive transfer material after the bonding step; Exposure; (c) a first development step, after the temporary support is peeled off from the positive photosensitive resin layer after the first exposure step, developing the positive photosensitive resin layer after the first exposure step to form a first pattern; (D) a first etching step, in which at least the first conductive layer and the second conductive layer of the plurality of conductive layers in the area where the first pattern is not arranged are etched; Figures with different patterns Performing pattern exposure on the first pattern after the first etching step; (f) a second developing step, developing the first pattern after the second exposure step to form a second pattern; and (g) a second etching step, An etching process is performed on at least a first conductive layer of the plurality of conductive layers in a region where the second pattern is not arranged. <12> The method of manufacturing a circuit wiring according to <11>, further comprising a step of attaching a light-transmitting protective film to the first pattern after the first etching step and before the second exposure step, in In the second exposure step, the first pattern is pattern-exposed via the protective film, and after the second exposure step, the protective film is peeled from the first pattern, and then the second etching step is performed. [Effect of the invention]

According to the present invention, it is possible to provide a good adhesion even when bonded to a circuit wiring forming substrate at a low temperature and high speed (for example, the temperature of a roll used for bonding is 130 ° C. or lower and the conveying speed is 1 m / min or higher). And a method for manufacturing a circuit wiring photosensitive transfer material and circuit wiring with high resolution.

Hereinafter, the manufacturing method of the photosensitive transfer material and circuit wiring of this invention is demonstrated. In addition, the description will be made with reference to the accompanying drawings, but the symbols may be omitted. In addition, in this specification, the numerical range shown using "~" 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 any one of acrylic acid and methacrylic acid, and "(meth) acrylate" means both or any one of acrylate and methacrylate. By. Furthermore, in the present specification, regarding the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, it means the presence of the plurality of substances in the composition. Total measurement. In this specification, the term "step" includes not only an independent step, but if it cannot be clearly distinguished from other steps, as long as the purpose required for the step can be achieved, it is also included in this term.

[Photosensitive transfer material] The photosensitive transfer material of this embodiment includes a temporary support and a positive-type photosensitive resin layer including a structural unit represented by the following general formula A and having A polymer having a constitutional unit of an acid group and a glass transition temperature (hereinafter, sometimes referred to as Tg) of 90 ° C. or lower and a photoacid generator.

[Chemical 2]

In Formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, and R ³¹ Alternatively, R ³² may be bonded 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 arylene group. * In General Formula A represents a connection position with an adjacent constituent unit.

FIG. 1 schematically illustrates an example of a layer configuration of a photosensitive transfer material according to this embodiment. The photosensitive transfer material 100 shown in FIG. 1 includes a temporary support 12, a positive photosensitive resin layer 14, and a cover film 16 in this order. The positive photosensitive resin layer 14 includes a polymer including a structural unit represented by the general formula A and a structural unit having an acid group and having a glass transition temperature of 90 ° C. or lower, and a photoacid generator. Hereinafter, constituent materials and the like of the photosensitive transfer material of this embodiment will be described. In addition, regarding the said structure in this invention, this specification may be called as follows. The structural unit represented by General Formula A may be referred to as a "structural unit (a)", and the structural unit having an acid group may be referred to as a "structural unit (b)". A polymer including a structural unit represented by Formula A and a structural unit having an acid group and having a glass transition temperature of 90 ° C. or lower may be referred to as a “specific polymer”. The positive-type photosensitive resin layer is sometimes referred to as a "photosensitive resin layer".

[Temporary Support] The temporary support 12 is a support that supports the positive-type photosensitive resin layer and is detachable from the positive-type photosensitive resin layer. From the viewpoint that the positive-type photosensitive resin layer can be exposed through a temporary support when pattern-exposing the positive-type photosensitive resin layer, the temporary support 12 used in this embodiment is preferably light-transmissive. Sex. The term "transparent" means that the light transmittance of the main wavelength of the pattern exposure is 50% or more. From the viewpoint of improving sensitivity, the light transmittance of the main wavelength of the pattern exposure is preferably 60% or more, and more preferably 70. %the above. Examples of the temporary support include a glass substrate, a resin film, and paper. In terms of strength and flexibility, a resin film is particularly preferred. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferred.

The thickness of the temporary support is not particularly limited, but is usually in the range of 5 μm to 200 μm. In terms of ease of operation and versatility, it is particularly preferably in the range of 10 μm to 150 μm. From the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, and light transmittance required in the first exposure step, the support may be selected based on the material temporarily.

A preferred form of the temporary support is described in, for example, paragraphs [0017] to [0018] of Japanese Patent Laid-Open No. 2014-85643, and the contents of this bulletin are incorporated into the present specification.

[Positive Photosensitive Resin Layer] The photosensitive transfer material 100 of this embodiment includes a positive photosensitive resin layer 14 disposed on a temporary support 12. The positive-type photosensitive resin layer 14 in this embodiment includes a polymer (specific polymer) including a structural unit (a) represented by the general formula A and a structural unit (b) having an acid group and having a glass transition temperature of 90 ° C. or lower. ) And photoacid generator.

<Polymer component> [Specific polymer] The positive-type photosensitive resin layer in this embodiment includes a structural unit (a) represented by the general formula A and a structural unit (b) having an acid group, and has a glass transition temperature of 90. A specific polymer at a temperature of lower than or equal to the temperature is used as a polymer component. The specific polymer contained in the positive-type photosensitive resin layer may be only one type, or may be two or more types.

(Constitutional unit (a)) The constitutional unit (a) represented by the general formula A is a constitutional unit containing a carboxyl group protected by an acid-decomposable group, and a specific copolymer is included as having a protected by an acid-decomposable group. The structural unit (a) represented by the general formula A is a preferred structural unit of a carboxyl group, and the sensitivity and resolution at the time of pattern formation are good.

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

In the general formula A, R ³⁴ 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 ³⁴ in the general formula A is a hydrogen atom with respect to the total amount of the structural unit (a) contained in the polymer is preferably 20% by mass or more. In addition, the content (content ratio: mass ratio) of the constitutional unit in which R ³⁴ in the general formula A in the constitutional unit (a) is a hydrogen atom can be measured by using 13C-Nuclear Magnetic Resonance (NMR) spectroscopy. The intensity ratio of the peak intensity calculated by the method was confirmed.

Among the structural units (a) represented by the general formula A, from the viewpoint of further improving the sensitivity at the time of pattern formation, the structural units represented by the following general formula A1 are more preferred.

[Chemical 3]

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

Preferred specific examples of the structural unit (a) having a carboxylic acid group protected by an acid-decomposable group represented by the general formula A include the following structural units. R ³⁴ represents a hydrogen atom or a methyl group. -C (R ³¹ ) (R ³² ) -OR ³³ in the general formula A corresponds to an acid-decomposable group.

[Chemical 4]

The structural unit (a) contained in the specific copolymer may be one type or two or more types. The content of the structural unit (a) represented by the general formula A in the specific polymer is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and even more preferably 30% by mass to 70% by mass. The content (content ratio: mass ratio) of the structural unit (a) in the specific polymer can be confirmed by measuring the intensity ratio of the peak intensity calculated by the ordinary method based on 13C-NMR measurement. In addition, after converting all polymer components into constituent units (monomer units), the proportion of the constituent unit (a) having a protected carboxyl group protected by an acid group with an acid-decomposable group is preferably 5% to 80% by mass. Hereinafter, it is more preferably 10% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.

(Constitutional Unit (b)) The specific polymer of the present embodiment includes a constitutional unit (b) having an acid group. The structural unit (b) is a structural unit containing an acid group which is not protected by an acid-decomposable group, that is, an acid group which does not have an acid-decomposable group. The specific copolymer contains the constituent unit (b) by the specific polymer, and the sensitivity at the time of pattern formation becomes good. In the development step after the pattern exposure, the specific copolymer is easily dissolved in an alkaline developing solution, and the development time can be achieved. Shorten. The term "acid group" as used herein means a proton dissociative group having a pKa of 12 or less. The acid group is usually incorporated into a specific polymer using a monomer capable of forming an acid group as a constituent unit containing the acid group [constituting unit (b)]. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. The pKa of the acid group is preferably -5 or more.

The specific polymer contains a structural unit (a) having a specific structure protected by the protective group described above and a structural unit (b) having an acid group not protected by a protective machine as a copolymerization component, and glass is used as a copolymerization component. The transfer temperature is set to 90 ° C or lower, and the positive-type photosensitive resin layer containing the specific polymer maintains good transferability and releasability from the temporary support, and further improves the resolution and sensitivity during pattern formation. .

Examples of the acid group possessed by a specific polymer include an acid group derived from a carboxylic acid group, an acid group derived from a sulfonamide group, an acid group derived from a phosphonic acid group, and an acid derived from a sulfonic acid group. Groups, acid groups derived from phenolic hydroxyl groups, sulfoamido groups, sulfoamido groups, and the like. Among them, at least one selected from the group consisting of an acid group derived from a carboxylic acid group and an acid group derived from a phenolic hydroxyl group is preferred. Introduction of a structural unit having an acid group into a specific copolymer can be performed by copolymerizing a monomer having an acid group. The constituent unit containing an acid group as the constituent unit (b) is more preferably a constituent unit in which an acid group substitutes a constituent unit derived from styrene or a constituent unit derived from a vinyl compound, and (meth) A structural unit derived from acrylic acid.

From the viewpoint of further improving the sensitivity at the time of pattern formation, the structural unit (b) contained in the specific polymer is preferably a structural unit having a carboxylic acid group and a structural unit having a phenolic hydroxyl group. The monomer having an acid group that can form 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. The specific polymer preferably contains, from the total solid content of the specific polymer, 0.1 to 20% by mass of a structural unit [component (b)] having an acid group. The content of the structural unit (b) in the specific polymer is more preferably 0.5% to 15% by mass, and even more preferably 1% to 10% by mass based on the total solid content of the specific polymer. When the content of the constituent unit (b) is within the above range, the pattern formability is further improved. The content (content ratio: mass ratio) of the structural unit (b) in the specific polymer can be confirmed by 13C-NMR measurement of the intensity ratio of the peak intensity calculated by the ordinary method.

(Other constituent units) As long as the effect of the present invention is not impaired, the specific polymer may include other constituent units (hereinafter, sometimes referred to as “units”) in addition to the constituent units (a) and (b) described above. Is the constituent unit (c)). The monomers constituting the unit (c) are not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, and aryl (meth) acrylates. , Unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated Dicarboxylic anhydride, a group having an aliphatic cyclic skeleton, and other unsaturated compounds. By using other constituent units (c) and adjusting at least one of the type and content, each characteristic of a specific polymer can be adjusted. In particular, the Tg of a specific polymer can be easily adjusted to 90 ° C. or lower by appropriately using the constituent unit (c). The other constitutional unit (c) may include only one kind in a specific polymer, or may include two or more kinds.

Specifically, the other structural unit (c) may be a structural unit derived from the following compounds: styrene, tertiary butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, and acetamidine Oxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxybenzoic acid (Meth) acrylate, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyethyl ester, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetamyl acetate mono (methyl) Acrylate, etc. In addition, the compounds described in paragraphs [0021] to [0024] of Japanese Patent Laid-Open No. 2004-264623 can be cited.

In addition, from the viewpoint of improving the electrical characteristics of the obtained transfer material, the other constituent unit (c) is preferably a group having an aromatic group, a styrene, and a group having an aliphatic cyclic skeleton. Specific examples include: styrene, third butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentyl (meth) acrylate, and cyclohexyl (meth) acrylate Esters, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like.

From the viewpoint of adhesion, the constituent unit (c) that can be contained in a specific polymer is, for example, an alkyl (meth) acrylate. Among these, from the viewpoint of adhesion, an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is more preferred. Specific examples include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate .

(Content of constituent unit) Among the constituent units constituting the specific polymer, the content of the constituent unit (c) is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. The lower limit value may be 0% by mass, but it may be set to 1% by mass or more, and may be set to 5% by mass or more. The copolymerization ratio of the structural unit (c) in the specific polymer is preferably 1% to 70% by mass, more preferably 5% to 60% by mass, and even more preferably 10% to 50% by mass. From the viewpoint of further improving the resolution and adhesion, it is preferably within the above-mentioned numerical range.

From the viewpoint of optimizing the solubility of the developing solution and the physical properties of the positive-type photosensitive resin layer, it is also preferable to use a constituent unit having an acid group-containing ester as the constituent unit (c). Among them, the specific polymer preferably contains a structural unit containing a carboxylic acid group as the structural unit (b), and further contains a structural unit containing a carboxylic acid ester group (c) as a copolymerization component, and more preferably contains (B) a structural unit derived from (meth) acrylic acid, a structural unit derived from cyclohexyl (meth) acrylate or 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate ( c) Specific polymers as copolymerization components. Hereinafter, preferred examples of the specific polymer usable in this embodiment are listed, but this embodiment is not limited to the following examples. In addition, in order to obtain preferable physical properties, the ratio of the constituent units and the weight average molecular weight in the following exemplary compounds can be appropriately selected.

[Chemical 5]

(Glass Transition Temperature of Specific Polymer: Tg) The glass transition temperature (Tg) of the specific polymer in this embodiment is 90 ° C or lower. When the Tg is 90 ° C. or lower, the photosensitive transfer material having a positive-type photosensitive resin layer containing a specific polymer has high adhesiveness even if it is bonded at low temperature and high speed. Tg is more preferably 60 ° C or lower, and even more preferably 40 ° C or lower. The lower limit of the Tg of the specific polymer is not particularly limited, but is preferably -20 ° C or higher, and more preferably -10 ° C or higher. 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 is suppressed.

The glass transition temperature of a polymer can be measured using differential scanning calorimetry (Differential Scanning Calorimetry (DSC)). A specific measurement method can be performed according to the method described in Japanese Industrial Standards (JIS) K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature in this specification uses an extrapolated glass transition start temperature (hereinafter, sometimes referred to as Tig). A method for measuring the glass transition temperature will be further specifically described. In the case of determining the glass transition temperature, keep it at a 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: 20 ° C / min. Up to 30 ° C, and draw a Differential Thermal Analysis (DTA) curve or DSC curve. The extrapolated glass transition start temperature (Tig), which is the glass transition temperature Tg in this specification, is calculated as the temperature at the intersection of a straight line and a tangent line, which extends the low-temperature side baseline in the DTA curve or DSC curve to high temperature The tangent line is drawn at a point where the gradient of the curve of the step-shaped changing portion of the glass transition becomes the maximum.

The method of adjusting the Tg of a specific polymer (copolymer) to the above-mentioned preferable range can be based on the mass ratio of the Tg of the homopolymer of each constituent unit of the specific polymer to the mass of each constituent unit in the FOX formula. As a guide, control the Tg of the specific polymer as the purpose. Regarding the FOX formula, the Tg of the homopolymer of the first constituent unit contained in the specific polymer as the copolymer is Tg1, the mass fraction of the copolymer of the first constituent unit is W1, and the second The Tg of the homopolymer of the constituent unit is Tg2, and when the mass fraction in the copolymer of the second constituent unit is W2, the Tg0 (K) of the copolymer including the first constituent unit and the second constituent unit can be determined based on It is estimated by the following formula. FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2) The FOX formula can be used to adjust the type and mass fraction of each constituent unit contained in the copolymer to obtain the required Tg Copolymer. The Tg of a specific polymer can also be adjusted by adjusting the weight-average molecular weight of the specific polymer.

(Molecular weight of specific polymer: Mw) The molecular weight of the specific polymer contained in the positive-type photosensitive resin layer is preferably 6.0 × 10 ⁴ or less in terms of weight average molecular weight in terms of polystyrene. When the weight-average molecular weight of the specific polymer contained in the positive-type photosensitive resin layer is 6.0 × 10 ⁴ or less, the melt viscosity of the positive-type photosensitive resin layer can be suppressed to a low level, and the positive-type photosensitive resin layer can be bonded to a substrate for circuit wiring At the time of bonding, it can be bonded at low temperature (for example, below 130 ° C). In addition, if the weight-average molecular weight of the specific polymer is too small, when the positive-type photosensitive resin layer is formed on the temporary support, it becomes too soft and easily damaged in the processing steps. The possibility of the adhesive film becoming difficult to peel off. From this viewpoint, the weight-average molecular weight of the specific polymer contained in the positive-type photosensitive resin layer is preferably in a range of 2.0 × 10 ³ to 6.0 × 10 ⁴ , and more preferably 3.0 × 10 ³ to 5.0 × 10. ⁴ range. The weight-average molecular weight of a specific polymer contained in the positive photosensitive resin layer can be measured by gel permeation chromatography (GPC). Various commercially available devices can be used as the measurement device. The content and measurement technique are well known to those having ordinary knowledge in the field to which this invention belongs. For the measurement of the weight-average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (Tosoh) can be used as a measuring device, and each can be used as a column. One TSKgel (registered trademark) Super HZM-M (4.6 mmID × 15 cm, Tosoh (stock)), Super HZ4000 (4.6 mmID × 15 cm, Tosoh (stock)), Super HZ3000 (4.6 mmID × 15 cm, Tosoh (stock)), Super HZ2000 (4.6 mmID × 15 cm, Tosoh (stock)), as the eluent, tetrahydrofuran (THF) can be used. For the measurement conditions, the sample concentration can be set to 0.2% by mass, the flow rate can be set to 0.35 ml / min, the sample injection volume can be set to 10 μl, and the measurement temperature can be set to 40 ° C. A differential refractive index (Refractive Index, RI) detector. For the calibration curve, Tosoh's "standard sample TSK standard (polystyrene)": "F-40", "F-20", "F-4", "F-1""," A-5000 "," A-2500 ", and" A-1000 ". The ratio (degree of dispersion) 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.

(Manufacturing method of a specific polymer) The manufacturing method (synthesis method) of a specific polymer is not specifically limited, If an example is given, the polymerizability including the structural unit (a) represented by General formula A can be included Monomer, an organic solvent for forming a polymerizable monosome having a constituent unit (b) having an acid group, and optionally, a polymerizable monosome for forming other constituent units (c), are polymerized The initiator is polymerized to synthesize. It can also be synthesized by a so-called polymer reaction.

From the viewpoint of exhibiting good adhesion even when bonded to a circuit wiring forming substrate at low temperature and high speed, the positive solid content of the positive photosensitive resin layer in this embodiment is positive with respect to the total solid content of the positive photosensitive resin layer. The type photosensitive resin layer preferably contains the specific polymer in a proportion of 50% to 99.9% by mass, and more preferably contains the specific polymer in a proportion of 70% to 98% by mass.

[Other Polymers] The positive-type photosensitive resin layer in the present embodiment may include, in addition to the above-mentioned specific polymer, as long as the effect of the present invention is not impaired, the polymer containing the positive-type photosensitive resin layer. A polymer (sometimes referred to as "other polymer") constituting the unit (a) is used as a polymer component. When the positive photosensitive resin layer contains other polymers, the blending amount of the other polymers is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less of the total polymer component. .

The positive-type photosensitive resin layer may include only one other polymer in addition to the specific polymer, and may include two or more.

For 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) can also be used. ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by East Asia Synthetic), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, BASF) Company)).

<Photoacid generator> The positive-type photosensitive resin layer in this embodiment contains a photoacid generator. The photoacid generator used in this embodiment is a compound capable of generating an acid by irradiating radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and a charged particle beam. The photoacid generator used in this embodiment is preferably a compound that generates an acid by sensing actinic rays having a wavelength of 300 nm or more, and more preferably 300 nm to 450 nm, but the chemical structure is not limited. In addition, regarding a photoacid generator that does not directly sense actinic rays with a wavelength of 300 nm or more, if it is a compound that generates an acid by sensing the actinic rays with a wavelength of 300 nm or more by using it in combination with a sensitizer, It can also be preferably used in combination with a sensitizer. The value of the pKa of the acid generated by radiation irradiation is preferably 4.0 or less, and particularly preferably 3.0 or less. The lower limit value is not particularly limited, and may be, for example, -10.0 or more.

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

Examples of the non-ionic photoacid generator include trichloromethyl-mesytriazines, diazomethane compounds, amidine sulfonate compounds, oxime sulfonate compounds, and the like. Among these compounds, the photo-acid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used alone or in combination of two or more. Specific examples of the trichloromethyl-triazine and diazomethane derivatives include compounds described in paragraphs [0083] to [0088] of Japanese Patent Laid-Open No. 2011-221494.

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

[Chemical 6]

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

Any group of the compound containing an oxime sulfonate structure represented by formula (B1) may be substituted, and the alkyl group in R ²¹ may be linear, branched, or cyclic. The allowable 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 through an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including 7,7-dimethyl-2-oxonorbornyl group) The cyclic group is preferably a bicycloalkyl group or the like), and a halogen atom is substituted. 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 by a lower alkyl group, an alkoxy group or a halogen atom.

The compound containing an oxime sulfonate structure represented by the formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B2).

[Chemical 7]

In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X ¹⁰ represents an alkyl group, an alkoxy group, or a halogen atom, and m 4 represents an integer of 0 to 3. When m 4 is 2 or 3, multiple X ¹⁰ may be the same. It can be different.

The alkyl group as X ¹⁰ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group as X ¹⁰ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X ¹⁰ is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In formula (B2), it is particularly preferred that m4 is 1, X ¹⁰ is methyl, the substitution position of X ¹⁰ is ortho, and R ⁴² is a linear alkyl group having 1 to 10 carbon atoms and 7,7-dimethyl group. A 2-oxonorbornyl methyl or p-toluidine group compound.

The compound containing an oxime sulfonate structure represented by the formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B3).

[Chemical 8]

In formula (B3), R ⁴³ has the same meaning as R ⁴² in formula (B2), and X ¹¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. Or nitro, n4 represents an integer from 0 to 5.

R ⁴³ in formula (B3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-n Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl. X ^{1 is} preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group. n4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the formula (B3) include α- (methylsulfonyloxyimino) benzonitrile, α- (ethylsulfonyloxyimino) benzonitrile, and α- (N-propylsulfonyloxyimino) benzonitrile, α- (n-butylsulfonyloxyimino) benzonitrile, α- (4-toluenesulfonyloxyimino) benzylmethyl Nitrile, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] Acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxybenzene Group] acetonitrile, α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and they may be used alone or in combination of two or more. Compounds (i) to (viii) can be obtained as commercially available products. It can also be used in combination with other types of photoacid generators.

[Chemical 9]

The compound containing an oxime sulfonate structure represented by the formula (B1) is also preferably a compound represented by the following formula (OS-1).

Formula (OS-1)

In Formula (OS-1), R ⁴¹¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a fluorenyl group, a carbamoyl group, an amine sulfonyl group, a sulfo group, a cyano group, and an aryl group. Or heteroaryl. R ⁴¹² represents an alkyl group or an aryl group. X ⁴⁰¹ represents -O-, -S-, -NH-, -NR ^415- , -CH _2- , -CR ⁴¹⁶ H-, or -CR ⁴¹⁵ R ^417- , and R ⁴¹⁵ to R ⁴¹⁷ represent alkyl or aryl. R ⁴²¹ to R ⁴²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amidino group, a sulfo group, and a cyano group Or aryl. Two of R ⁴²¹ to R ⁴²⁴ may be bonded to each other to form a ring. R ⁴²¹ to R ^{424 are} preferably a hydrogen atom, a halogen atom, and an alkyl group. In addition, a form in which at least two of R ⁴²¹ to R ⁴²⁴ are bonded to each other to form an aryl group is also preferable. Among these, from the viewpoint of sensitivity, the form in which all of R ⁴²¹ to R ⁴²⁴ are hydrogen atoms is preferred. Each of the above-mentioned functional groups may further have a substituent.

Specific examples of the compound represented by the formula (OS-1) that can be preferably used in this embodiment include the compounds described in paragraphs [0128] to [0132] of Japanese Patent Laid-Open No. 2011-221494 (exemplification) Compounds b-1 to exemplified compounds b-34), but this embodiment is not limited to these compounds.

In the present invention, the compound containing the oxime sulfonate structure represented by the formula (B1) is preferably represented by the following formula (OS-3), the following formula (OS-4), or the following formula (OS-5) Oxime sulfonate compound.

[Chemical 11]

In formulas (OS-3) to (OS-5), R ²² , R ^25, and R ²⁸ each independently represent an alkyl group, an aryl group, or a heteroaryl group, and R ²³ , R ^26, and R ²⁹ each independently represent hydrogen Atom, alkyl group, aryl group or halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic group, an amine sulfonyl group or an alkoxysulfonyl group X ¹ to X ³ each independently represent an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represent 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6.

In the formulae (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent. In the formulae (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

In the formulae (OS-3) to (OS-5), the aryl groups in R ²² , R ^25, and R ²⁸ are preferably aryl groups having a total carbon number of 6 to 30 which may have a substituent.

In the formulae (OS-3) to (OS-5), the heteroaryl group in R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent.

In formulas (OS-3) to (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one ring that is a heteroaromatic ring. For example, a heteroaromatic ring and a benzene ring may be condensed. .

In the formulae (OS-3) to (OS-5), R ²³ , R ²⁶ and R ^{29 are} preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. In the formulae (OS-3) to (OS-5), two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, preferably one or two are alkyl, aryl or halogen atoms, more One is preferably an alkyl group, an aryl group or a halogen atom, particularly preferably one is an alkyl group and the rest are hydrogen atoms.

The alkyl group in R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and more preferably an alkyl group having a total carbon number of 1 to 6 which may have a substituent.

The aryl group in R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

In the formulae (OS-3) to (OS-5), X ¹ to X ³ each independently represent O or S, and preferably O. In the formulas (OS-3) to (OS-5), the ring including X ¹ to X ³ as the ring member is a 5-member ring or a 6-member ring. In the formulae (OS-3) to (OS-5), n ¹ to n ³ each independently represent 1 or 2; and when X ¹ to X ³ are O, n ¹ to n ^{3 are} preferably independent of each other. The ground is 1, and when X ¹ to X ³ are S, it is preferable that n ¹ to n ³ are independently 2.

In the formulae (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic group, an amine sulfonyl group, or an alkoxy group. Sulfosulfenyl. Among them, R ²⁴ , R ²⁷ and R ^{30 are} preferably each independently an alkyl group or an alkyloxy group. The alkyl group, alkyloxy group, sulfonic acid group, amine sulfonyl group, and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent. In the formulae (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

In the formulae (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyloxy group having a total carbon number of 1 to 30 which may have a substituent.

In formulas (OS-3) to (OS-5), m ¹ to m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably Is 0. In addition, regarding each substituent of the formula (OS-3) to the formula (OS-5), (OS-3) to paragraphs described in paragraphs [0092] to [0109] of Japanese Patent Laid-Open No. 2011-221494 The preferable range of the substituent of (OS-5) is also preferable.

The compound containing the oxime sulfonate structure represented by the formula (B1) is particularly preferably an oxime sulfonate compound represented by any one of the following formulae (OS-6) to (OS-11).

[Chemical 12]

In the formulae (OS-6) to (OS-11), R ³⁰¹ to R ³⁰⁶ each independently represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ^316, and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and R ³¹² , R ³¹⁵ , R ^317, and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.

The preferred ranges in the formulas (OS-6) to (OS-11) are as described in paragraphs [0110] to [0112] of Japanese Patent Laid-Open No. 2011-221494 (OS-6) to (OS The preferred range of -11) is the same.

Specific examples of the oxime sulfonate compound represented by formula (OS-3) to formula (OS-5) include the compounds described in paragraphs [0114] to [0120] of Japanese Patent Laid-Open No. 2011-221494, However, this embodiment is not limited to these compounds.

Examples of the ionic photoacid generator include diarylphosphonium salts, triarylphosphonium salts, and quaternary ammonium salts. Among these compounds, triarylsulfonium salts and diarylsulfonium salts are preferred.

Triarylsulfonium salts used as the ionic photoacid generator are represented by the following formula (1).

[Chemical 13]

In formula (1), R ⁵⁰⁵ , R ^506, and R ⁵⁰⁷ each represent an alkyl group or an aromatic group which may have a substituent, and in the case of an alkyl group, they may be connected to each other to form a ring; X ^- represents a conjugate base.

The alkyl group in R ⁵⁰⁵ , R ^506, and R ⁵⁰⁷ is preferably an alkyl group having 1 to 10 carbon atoms, and may have a substituent. Examples of the alkyl group described above include methyl, ethyl, propyl, isopropyl, butyl, third butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, and octyl. Among them, a methyl group, an ethyl group, or a third butyl group is preferred. In addition, when two or more of R ⁵⁰⁵ , R ^506, and R ⁵⁰⁷ are alkyl groups, it is preferable that the two or more alkyl groups are connected to each other to form a ring. As described above, the ring form includes a sulfur atom. The form is preferably a 5-membered ring (thietane) and a 6-membered ring (thietane). The aromatic group in R ⁵⁰⁵ , R ^506, and R ⁵⁰⁷ is preferably an aromatic group having 6 to 30 carbon atoms, and may have a substituent. Examples of the aromatic group include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tert-butylphenyl, and 4-phenylthio. Phenyl, 2,4,6-trimethylphenyl, 4-methoxy-1-naphthyl or 4- (4'-diphenylfluorenylphenylthio) phenyl. In addition, the ionic photoacid generator represented by formula (1) may be bonded by any of R ⁵⁰⁵ to R ⁵⁰⁷ to form a multimer such as a dimer. For example, 4- (4'-diphenyl sulfonium) phenyl is an example of the dimer, 4- (4'-diphenyl sulfonium phenylthio) phenyl counter anion of X ^- the same.

The substituent which the alkyl group and the aromatic group in R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ may have is an aromatic group, and specifically, a phenyl group, a 4-methoxyphenyl group, and a 4-chlorophenyl group are particularly preferred. , 4- (4'-diphenylfluorenylphenylthio) phenyl. These substituents may be further substituted with a substituent.

X ^- is the conjugate base is preferably the conjugate base of alkylsulfonic acid, arylsulfonic acid conjugate base, BY ₄ ^- (Y represents a halogen atom; hereinafter also the _{^{same), PY 6 -, AsY 6}} -, SbY ₆ ^- or a monovalent anion represented by the following formula (3) or formula (4), particularly preferably a conjugate base of an alkylsulfonic acid, a conjugate base of an arylsulfonic acid, or PY ₆ ^- or formula (3 ) Is a monovalent anion.

The conjugate base of an alkylsulfonic acid and an arylsulfonic acid is preferably a conjugate base of an alkylsulfonic acid having 1 to 7 carbon atoms, and more preferably a conjugate base of an alkylsulfonic acid having 1 to 4 carbon atoms. When expressed in an acid form, particularly preferred are methanesulfonic acid, trifluoromethanesulfonic acid, n-propanesulfonic acid, and heptanesulfonic acid. When the conjugate base of an arylsulfonic acid is expressed in the form of an acid, for example, benzenesulfonic acid, chlorobenzenesulfonic acid, and p-toluenesulfonic acid may be mentioned.

The BY _{4 ^{- -, PY 6 -, AsY}} 6 -, SbY 6 - X in Y is preferably a fluorine atom, a chlorine atom, particularly preferably a fluorine atom.

[Chemical 14]

In formulae (3) and (4), R ⁵²¹ , R ^522, and R ⁵²³ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkyl group having a fluorine atom having 1 to 10 carbon atoms, or R ⁵²¹ A ring bonded to R ⁵²² by an alkylene group having 2 to 6 carbon atoms or an alkylene group having 2 to 6 carbon atoms having a fluorine atom.

Examples of the alkyl group having 1 to 10 carbon atoms in R ⁵²¹ , R ^522, and R ⁵²³ in formulas (3) and (4) include methyl, ethyl, butyl, third butyl, and cyclohexyl. , Hinky, etc. Examples of the alkyl group having a fluorine atom having 1 to 10 carbon atoms include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, dodecylfluoropentyl, and perfluorooctyl. . Among these groups, R ⁵²¹ , R ⁵²² and R ^{523 are} preferably an alkyl group having a fluorine atom having 1 to 10 carbon atoms, and particularly preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms. In formulae (3) and (4), when R ⁵²¹ and R ⁵²² are bonded to each other to form a ring, the alkylene group having 2 to 6 carbon atoms can be exemplified by ethylene, propyl, butyl, and Amyl, hexyl, etc. Examples of the alkylene group having a fluorine atom having 2 to 6 carbon atoms include tetrafluoroethylene, hexafluoropropyl, octafluorobutyl, decafluoropentyl, and undecylfluorohexyl. Among these groups, when R ⁵²¹ and R ⁵²² are bonded to each other to form a ring, it is preferably bonded with an alkylene group having 2 to 6 carbon atoms having a fluorine atom, and particularly preferably a carbon atom An alkylene group having a fluorine atom of 2 to 4 is bonded.

The ionic photoacid generator represented by the formula (1) is preferably a photoacid generator represented by the following formula (5).

[Chemical 15]

In the formula, R ⁵¹⁰ , R ⁵¹¹ , R ⁵¹² and R ⁵¹³ each independently represent an alkyl group or an aromatic group which may have a substituent, and Ar ³ and Ar ⁴ each independently represent a divalent aromatic group which may have a substituent, X ^1- and X ^2- each independently represent a conjugate base.

The alkyl and aromatic groups in R ⁵¹⁰ , R ⁵¹¹ , R ^512, and R ⁵¹³ have the same meaning as the alkyl and aromatic groups represented by R ⁵⁰⁵ , R ^506, and R ⁵⁰⁷ in formula (1), and the preferred form is also the same. The same substituents may be used.

X X ^1- and conjugate base of formula (1), X ^2- is ^- conjugate base is the same meaning, the same preferred form also represented.

The divalent aromatic group in Ar ³ and Ar ⁴ is preferably a phenylene group or a naphthyl group, and particularly preferably a phenylene group.

Specific examples of the triarylsulfonium salts used as the ionic photoacid generator include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, and 4-methoxyphenyldiphenyl. Trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyl Diphenylphosphonium trifluoroacetate and the like. Commercially available compounds include: TPS-102, 103, 105, 106, 109, 300, 1000, MDS-103, 105, 109, 205, 209, BDS-109, DTS-103, 105, MNPS-109, HDS -109 (above, manufactured by Green Chemical Company); GSID-26-1, Cyracure UVI-6976 (above, manufactured by BASF).

The diarylsulfonium salts used as the ionic photoacid generator are represented by the following formula (2).

[Chemical 16]

In formula (2), R ⁵⁰⁸ and R ⁵⁰⁹ each independently represent an aromatic group which may have a substituent, and X ^- represents a conjugate base.

In formula (2), the aromatic groups in R ⁵⁰⁸ and R ⁵⁰⁹ have the same meanings as the aromatic groups represented by R ⁵⁰⁵ , R ^506, and R ⁵⁰⁷ in formula (1), and the preferred forms are also the same. X of formula (2), X ^l- conjugated base of formula (1) ^- conjugate base is the same meaning, the same preferred form also represented. The photoacid generator represented by the formula (2) may be bonded by R ⁵⁰⁸ to R ⁵⁰⁹ to form a multimer such as a dimer. For example, 4- (4'-diphenyl sulfonium) phenyl is an example of the dimer, 4- (4'-diphenyl sulfonium phenylthio) phenyl counter anion of X ^- the same.

Specific examples of the diarylphosphonium salt used as the ionic photoacid generator include diphenylphosphonium trifluoroacetate, diphenylphosphonium trifluoromethanesulfonate, and 4-methoxyphenylbenzene. Sulfonium trifluoromethanesulfonate, 4-methoxyphenylphenylsulfonium trifluoroacetate, phenyl, 4- (2'-hydroxy-1'-tetradecanyloxy) phenylsulfonium trifluoromethane Sulfonate, 4- (2'-hydroxy-1'-tetradecanyloxy) phenyl sulfonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetradecanyloxy) Phenylhydrazone-p-toluenesulfonate and the like. Commercially available compounds include: DPI-105, 106, 109, 201, BI-105, MPI-105, 106, 109, BBI-102, 103, 105, 106, 109, 110, 201, 300, 301 (above , Manufactured by Green Chemical Company).

Specific examples of the quaternary ammonium salts used as the ionic photoacid generator include tetramethylammonium butyltri (2,6-difluorophenyl) borate, and tetramethylammonium hexyltri (p-chloro) Phenyl) borate, tetramethylammonium hexyltri (3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium butyltri (2,6-difluorophenyl) borate, benzyl Dimethyl phenylphenyl ammonium hexyl tri (p-chlorophenyl) borate, benzyl dimethylphenyl ammonium hexyl tri (3-trifluoromethylphenyl) borate, and the like.

Specific examples of the photoacid generator other than the specific examples include the compounds described below, but the photoacid generator used in this embodiment is not limited to these compounds. [Chemical 17]

[Chemical 18]

[Chemical 19]

In the positive photosensitive resin layer, in terms of sensitivity and resolution, the photoacid generator is preferably used in an amount of 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content in the positive photosensitive resin layer. Parts, more preferably 0.5 to 5 parts by mass. Two or more of them may be used in combination.

[Solvent] The positive photosensitive resin composition (hereinafter, sometimes referred to as a "photosensitive resin composition") for forming the positive photosensitive resin layer is preferably a resin for forming a positive photosensitive resin layer. It is prepared as a solution in which components are dissolved in a solvent. As the solvent used in the positive photosensitive resin composition for forming the positive photosensitive resin layer, a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, and propylene glycol monoalkyl ethers. Ether ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Acetates, esters, ketones, amidines, lactones, etc. Specific examples of the solvent used in the positive-type photosensitive resin composition for forming the positive-type photosensitive resin layer include those described in paragraphs [0174] to [0178] of Japanese Patent Laid-Open No. 2011-221494. These solvents are incorporated into this specification.

In addition, it can be added to the solvent described above, if necessary: benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isopropyl Furone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate Ester, ethyl carbonate, propylene carbonate and other solvents. Only one kind of solvent may be used, or two or more kinds may be used. The solvents that can be used in this embodiment can be used singly or more preferably in combination. When two or more solvents are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butyl Glycol alkyl ether acetates are used in combination.

The solvent is preferably a solvent having a boiling point of 130 ° C or higher and lower than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture of these solvents. Examples of solvents having a boiling point of 130 ° C or higher and less than 160 ° C are: propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), propylene glycol methyl-n-butyl ether (boiling point 155 ° C) ), Propylene glycol methyl-n-propyl ether (boiling point: 131 ° C). Examples of solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C) , Dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether ( Boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butanediol di Acetate (boiling point: 232 ° C).

The content of the solvent in the positive-type photosensitive resin composition for forming the positive-type photosensitive resin layer is preferably 50 to 1900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is preferably 100 parts by mass to 900 parts by mass.

<Other additives> In addition to the specific polymer and the photoacid generator, the positive photosensitive resin layer in the transfer material of this embodiment may contain a known additive as needed.

[Plasticizer] The positive photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity. In addition, the positive-type photosensitive resin layer of the present embodiment is excellent in plasticity by including the specific polymer described above, and therefore it is not necessary to contain a plasticizer. The plasticizer which can be contained in the positive-type photosensitive resin layer preferably has a weight average molecular weight smaller than 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 that is compatible with a specific polymer and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

[Chemical 20]

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

In addition, for example, even a compound having the above-mentioned alkyleneoxy group (referred to as "compound X"), the compound X and the specific polymer are polymerized more specifically than a positive photosensitive resin composition formed without the compound X. When the plasticity of the positive photosensitive resin composition obtained by mixing the polymer and the photoacid generator is not improved, it does not conform to the plasticizer in this embodiment. For example, an arbitrarily added surfactant is generally not used in an amount that imparts plasticity to the positive photosensitive resin composition, and therefore does not conform to the plasticizer in this specification.

Examples of the plasticizer that can be used in this embodiment include compounds having the following structures, but the compounds are not limited to these compounds.

[Chemical 21]

When a plasticizer is used, from the viewpoint of adhesion, the content of the plasticizer in the positive photosensitive resin layer is better than 100 parts by mass of the total solid content in the positive photosensitive resin layer. It is 1 to 50 parts by mass, and more preferably 2 to 20 parts by mass. When the positive photosensitive resin layer contains a plasticizer, only one kind may be used, or two or more kinds may be used.

[Sensitizer] The positive-type photosensitive resin layer in this embodiment may further include a sensitizer. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state comes into contact with the photoacid generator to produce effects such as electron transfer, energy transfer, and heat generation. Thereby, the photoacid generator is chemically changed and decomposed, and an acid is generated. By containing a sensitizer, exposure sensitivity can be improved.

The sensitizer is preferably an anthracene derivative, acridone derivative, thia anthrone derivative, coumarin derivative, basic styryl derivative, distyrylbenzene derivative, and more preferably anthracene derivative Thing. Anthracene derivatives are preferably anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9- Bromoanthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 2-ethylanthracene, 9,10-dimethoxyanthracene.

Examples of the sensitizer usable in this embodiment include the compounds described in paragraphs [0139] to [0141] of International Publication No. 2015/093271.

The content of the sensitizer in the positive-type photosensitive resin layer is preferably 0 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content.

[Basic Compound] The positive photosensitive resin layer in this embodiment preferably further contains a basic compound. The basic compound can be arbitrarily selected from the basic compounds used in chemically amplified resists and used. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids. Specific examples of these compounds include the compounds described in paragraphs [0204] to [0207] of Japanese Patent Laid-Open No. 2011-221494, and these contents are incorporated herein.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-n Amylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like. Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine. Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N-methyl 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, Nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine compounds, 4-methyl? Phthaloline, 1,5-diazabicyclo [4.3.0] -5-nonene, 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 a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds usable in this embodiment may be used alone or in combination of two or more.

The content of the basic compound in the positive photosensitive resin layer is preferably 0.001 to 5 parts by mass, and more preferably 0.005 to 3 parts by mass based on 100 parts by mass of the total solid content in the positive-type photosensitive resin layer. Serving.

[Heterocyclic compound] The positive photosensitive resin layer in this embodiment may contain a compound containing a heterocyclic compound. The heterocyclic compound in this embodiment is not particularly limited. For example, a compound having an epoxy group or an oxetanyl group and an alkoxymethyl group-containing heterocyclic compound described below can be added, and various cyclic ethers and cyclic esters (internal Oxygen-containing compounds such as esters), nitrogen-containing compounds such as cyclic amines and oxazolines, and heterocyclic compounds such as silicon, sulfur, and phosphorus having d electrons can be added.

When the heterocyclic compound is transferred, the addition amount of the heterocyclic compound in the positive photosensitive resin layer is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the total solid content of the positive photosensitive resin layer. Parts, more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 1 part by mass to 5 parts by mass. From the viewpoints of adhesion and etching resistance, it is preferable to add in this range. The heterocyclic compound may be used alone or in combination of two or more. When two or more kinds are used in combination, the preferable content means the total content of two or more kinds of heterocyclic compounds.

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

A compound having an epoxy group in the molecule can be obtained as a commercially available product. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings (stock)), etc. are described in paragraph [0189] of Japanese Patent Laid-Open No. 2011-221494 Commercial products. Other commercially available products can also be cited: ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN) EP-4011S (above, manufactured by ADEKA); NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, Edico ( (ADEKA) (stock); 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 (above , Manufactured by Nagase ChemteX); YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by Nippon Steel & Sumitomo Chemical); Syracuse ( Celloxide) 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Celvenus B0134, B0177 (above, Daicel (shares)) and so on. The compound having an epoxy group in the molecule may be used singly or in combination of two or more kinds.

Among the compounds having an epoxy group in the molecule, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and aliphatic epoxy resin can be more preferably listed. List aliphatic epoxy resins.

Specific examples of the compound having an oxetanyl group in the molecule can be used: Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221 , OX-SQ, PNOX (above, manufactured by East Asia Synthetic).

The compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

Among the compounds having an oxetanyl group in the molecule, from the viewpoints of etching resistance and line width stability, the positive photosensitive resin layer in this embodiment is preferably a heterocyclic compound having an epoxy group. Compound.

In addition, a compound having both an alkoxysilane structure and a heterocyclic structure in the molecule can also be suitably used. Examples include: γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltriol Alkoxysilane. Among these, γ-glycidoxypropyltrialkoxysilane is more preferable. The compound having an alkoxysilane structure and a heterocyclic structure in the molecule may be used alone or in combination of two or more.

[Surfactant] From the viewpoint of uniform film thickness, the positive-type photosensitive resin layer in the present embodiment preferably contains a surfactant. The surfactant can be any of anionic, cationic, nonionic or amphoteric, but a preferred surfactant is a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based, and fluorine-based interfaces. Active agent. In addition, the following product names can be listed: KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (made by Kyoeisha Chemical Co., Ltd.), Eftop (Mitsubishi Materials Electronics Co., Ltd. ( (Made by JEMCO), Megafac (made by DIC), Fluorad (made by Sumitomo 3M), Asahi Guard, Safulon ( Surflon (manufactured by Asahi Glass), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone) and other series. In addition, as the surfactant, a copolymer may be mentioned as a preferable example, the copolymer includes a structural unit A and a structural unit B represented by the following formula (I-1), and tetrahydrofuran (THF) is used as a solvent In the case of polystyrene, the weight average molecular weight (Mw) measured by gel permeation chromatography is 1.0 × 10 ³ or more and 1.0 × 10 ⁴ or less.

Formula (I-1)

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 1 or more carbon atom. , Alkyl group of 4 or less, L represents an alkylene group having 3 or more and 6 carbon atoms, p and q represent mass percentages of a polymerization ratio, p represents a value of 10 mass% or more and 80 mass% or less, and q represents 20 mass For numerical values of not less than 90% by mass, r is an integer of 1 or more and 18 or less, and s is an integer of 1 or more and 10 or less.

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

Formula (I-2)

The weight average molecular weight (Mw) of the copolymer is more preferably 1.5 × 10 ³ or more and 5.0 × 10 ³ or less.

In addition, 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.

The surfactant may be used singly or in combination of two or more kinds. The addition amount of the surfactant in the positive photosensitive resin layer is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass, with respect to 100 parts by mass of the total solid content in the positive photosensitive resin layer. It is particularly preferably 0.01 to 3 parts by mass.

[Radiation Absorber] The positive-type photosensitive resin layer in this embodiment may contain a radiation absorber. As the radiation absorber, an ultraviolet absorber can be preferably used, and a radiation absorber exhibiting a so-called photobleaching property whose absorbance is reduced by ultraviolet absorption is particularly preferably used. Specific examples include photochromic materials such as naphthoquinonediazide derivatives, nitron, and diazonium salts (for example, Japanese Patent Publication No. 62-40697, and M. Sasano) Compounds described in "Society of Photo-Optical Instrumentation Engineers (SPIE Symp. Proc.)" (631, 321 (1986)). The materials described above are used for the purpose of averaging the light intensity distribution in the photosensitive resin layer using a radiation absorber, and bring about the so-called Contrast Enhancement Lithography (CEL) effect. Obtain the effect of improving the rectangular shape of the pattern and improving the edge roughness (refer to "Semiconductor Process Materials and Chemicals", edited by Masaka Sakamoto, published by CMC (2006)).

[Other components] The positive-type photosensitive resin layer in this embodiment may further contain metal oxide particles, a cross-linking agent other than a heterocyclic compound, an alkoxysilane compound, an antioxidant, a dispersant, and an acid multiplier. , Well-known additives such as development accelerators, conductive fibers, colorants, thermal radical generators, thermal acid generators, ultraviolet absorbers, tackifiers, and organic or inorganic precipitation inhibitors. Regarding preferred forms of the other components, they are described in paragraphs [0165] to [0184] of Japanese Patent Laid-Open No. 2014-85643, and the contents of this bulletin are incorporated into the present specification.

<Thickness of Positive Photosensitive Resin Layer> The thickness of the positive photosensitive resin layer is preferably 0.5 μm to 20 μm. When the thickness of the positive photosensitive resin layer is 20 μm or less, the resolution of the pattern is good, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity. The thickness of the positive photosensitive resin layer is particularly preferably 0.8 μm to 15 μm, and particularly preferably 1.0 μm to 10 μm.

<Formation method of positive-type photosensitive resin layer> The positive-type photosensitive resin composition for forming a positive-type photosensitive resin layer can be prepared by mixing each component in a predetermined ratio and using any method, stirring and dissolving. For example, each component may be previously formed into a solution dissolved in a solvent, and the obtained solution may be mixed at a predetermined ratio to prepare a composition. The composition prepared as described above can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

The photosensitive transfer material of this embodiment having a positive photosensitive resin layer on the temporary support can be obtained by applying the photosensitive resin composition to a temporary support and drying it. The coating method is not particularly limited, and can be applied by a known method such as slit coating, spin coating, curtain coating, or inkjet coating. Moreover, you may apply a photosensitive resin composition layer on the temporary support which has another layer mentioned later on the temporary support, and the laminated body of another layer.

<Other layer> The photosensitive transfer material of this embodiment may have a layer other than a positive type photosensitive resin layer (henceforth a "other layer"). Other layers include a contrast enhancement layer, an intermediate layer, a cover film, and a thermoplastic resin layer.

<Contrast Enhancement Layer> The photosensitive transfer material of this embodiment may have a contrast enhancement layer in addition to a positive photosensitive resin layer. The Contrast Enhancement Layer (CEL) is a material that has a large absorption of the exposure wavelength before exposure, but gradually decreases with exposure, that is, a material (called a photochromic pigment component) that increases the transmittance of light. Floor. As the photochromic pigment component, a diazonium salt, a stilbazolium salt, an arylnitroso salt, and the like are known. As the film-forming component, a phenol resin or the like can be used. In addition, the contrast enhancement layer can use 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, edited by photopolymer symposium, industrial survey (1989); photopolymer technology, edited by Yamaoka, Nagatsu, and published in Nikkan Kogyo Shimbun (1988).

(Intermediate layer) An intermediate layer may be formed on the positive-type photosensitive resin layer, and a contrast enhancement layer may be formed on the intermediate layer (hereinafter, sometimes referred to as "CEL" or "CE layer"). The intermediate layer here is provided to prevent mixing of the CEL and the positive photosensitive resin layer and the like.

<Thermoplastic resin layer, cover film, etc.> The photosensitive transfer material of this embodiment may include a temporary support, a thermoplastic resin layer, and a positive photosensitive resin layer in this order, for example. Furthermore, for the purpose of protecting the positive-type photosensitive resin layer, a cover film may be included. A preferred form of the thermoplastic resin layer is described in paragraphs [0189] to [0193] of Japanese Patent Laid-Open No. 2014-85643, and a preferred form of the other layers is described in paragraphs of Japanese Patent Laid-Open No. 2014-85643 [ It is described in paragraphs [0196] to [0196], and the contents of this publication are incorporated into this specification.

When the photosensitive transfer material of this embodiment includes another layer such as a thermoplastic resin layer, the photosensitive transfer material described in paragraphs [0094] to [0098] of Japanese Patent Laid-Open No. 2006-259138 can be used. To make. For example, when the photosensitive transfer material of this embodiment including a thermoplastic resin layer and an intermediate layer is prepared, a temporary support is coated with a solution (thermoplastic resin) obtained by dissolving a thermoplastic organic polymer and an additive. A coating solution for a layer) is dried to provide a thermoplastic resin layer, and then a prepared solution (for an intermediate layer) prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer is coated on the obtained thermoplastic resin layer. Coating solution), and dried to laminate the intermediate layer. A coating solution for a positive-type photosensitive resin layer prepared by using a solvent that does not dissolve the intermediate layer is further coated on the formed intermediate layer, and the positive-type photosensitive resin layer is laminated and dried, thereby making it preferable The photosensitive transfer material of this embodiment.

[Manufacturing method of circuit wiring] A first embodiment of a manufacturing method of a circuit wiring using the photosensitive transfer material of this embodiment will be described. The first embodiment of the method for manufacturing a circuit wiring is a method for manufacturing a circuit wiring, which includes the following steps in order: (A) a laminating step for the substrate, so that the temporary support described above has light-transmitting sensitivity in this embodiment The positive-type photosensitive resin layer of the transfer material is bonded to the substrate in contact with the substrate; (B) an exposure step for pattern-exposing the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step; (C) a developing step , Developing the positive photosensitive resin layer after the exposure step to form a pattern; and (D) an etching step, performing an etching treatment on the substrate in the region where the pattern is not arranged. Regarding the substrate in the first embodiment of the method for manufacturing a circuit wiring, a substrate such as glass, silicon, or a film may be used as the substrate, or a conductive layer may be provided on the substrate such as glass, silicon, or a film as needed. Arbitrary layers of substrates. According to the first embodiment of the method for manufacturing a circuit wiring, a fine pattern can be formed on a substrate surface.

The second embodiment of the circuit wiring manufacturing method preferably includes in order: (a) a bonding step, for a substrate, that is, a substrate including a substrate and a plurality of components including a first conductive layer and a second conductive layer that are different from each other in constituent materials; A conductive layer, and a substrate having a first conductive layer and a second conductive layer as the outermost layer is laminated on the surface of the substrate in the order away from the surface of the substrate, so that the photosensitivity of this embodiment is changed The positive photosensitive resin layer of the printing material is bonded to contact with the first conductive layer; (b) in the first exposure step, the positive photosensitive resin layer is aligned through the temporary support of the photosensitive transfer material after the bonding step; Performing pattern exposure; (c) a first developing step, after peeling the temporary support from the positive photosensitive resin layer after the first exposure step, developing the positive photosensitive resin layer after the first exposure step to form a first Pattern; (d) a first etching step, performing an etching treatment on at least the first conductive layer and the second conductive layer in the plurality of conductive layers in the region where the first pattern is not arranged; (e) a second exposure step, and First pattern Pattern exposure of the first pattern after the first etching step with different patterns; (f) a second development step of developing the first pattern after the second exposure step to form a second pattern; and (g) the second The etching step performs an etching process on at least a first conductive layer of the plurality of conductive layers in a region where the second pattern is not arranged.

Conventionally, the photosensitive resin composition is classified into a negative type in which a portion irradiated with actinic rays remains as an image and a positive type in which a portion irradiated with actinic rays remains as an image according to a difference in a photosensitive system. In the positive type, the solubility of the exposed portion is improved by irradiating actinic rays, for example, using a photosensitizer that generates acid by irradiation with actinic rays. Therefore, neither the exposed portion nor the unexposed portion is hardened during pattern exposure. When the pattern shape is not good, the substrate can be reused (rework) by full exposure or the like. Therefore, from the viewpoint of the so-called excellent secondary workability, a positive type is preferred. In addition, only a positive-type photosensitive resin layer can realize a technique of re-exposing the remaining photosensitive resin layer to produce a different pattern.

According to the second embodiment of the method for manufacturing a circuit wiring, even if the photosensitive transfer material is bonded to the circuit wiring forming substrate at a low temperature and a high speed, high adhesion can be ensured. In addition, the circuit wiring manufacturing method of the present embodiment can form circuit wirings including conductive layers of various patterns by lamination (lamination) in the circuit wiring manufacturing method of the present embodiment at a time, and therefore has excellent manufacturing efficiency. In addition, alignment of conductive layers of various patterns is not required, and therefore, it is preferably used for an input device, especially for a touch panel.

Hereinafter, a preferable aspect in the second embodiment of the method for manufacturing a circuit wiring will be described in detail. FIG. 2 schematically illustrates an example of a method for manufacturing a circuit wiring for a touch panel, which is one embodiment of the present invention. Here, a case where a circuit wiring substrate including two patterns of conductive layers is manufactured using the substrate 20 for forming a circuit is described. The substrate 20 for forming a circuit includes a base material 22 and one of the surfaces away from the base material 22. The first conductive layer 24 and the second conductive layer 26 are sequentially.

A case where a positive-type photosensitive resin layer in the photosensitive transfer material of this embodiment is used as an anti-etching agent (etching pattern) to obtain a conductive layer pattern of a capacitance-type input device will be described. In addition, the electrostatic capacitance type input device includes a base material (front panel or film base material) and at least the following elements (2) to (5) on the non-contact side of the base material, and it is preferable to use the circuit wiring of this embodiment. To form at least one of (2), (3) and (5). (2) a plurality of first electrode patterns formed by extending a plurality of pad portions in a first direction via a connection portion (3) electrically insulated from the first electrode pattern and including a plurality of formed extending in a direction crossing the first direction A plurality of second electrode patterns of the pad portion (4) an insulating layer that electrically insulates the first electrode pattern from the second electrode pattern and (5) electrically connected to at least one of the first electrode pattern and the second electrode pattern and The conductive elements different from the first electrode pattern and the second electrode pattern are described below in detail for each step.

(A) Bonding step First, in the bonding step, the substrate (substrate for circuit wiring formation) 20, that is, the substrate 22 and the first conductive layer 24 and the second conductive layer 26 including constituent materials different from each other are included. A plurality of conductive layers, and a substrate (circuit wiring forming substrate) on which the first conductive layer 24 and the second conductive layer 26 as the outermost layers are laminated on the surface of the substrate 22 in the order away from the surface of the substrate 22. 20. The positive-type photosensitive resin layer 14 of the photosensitive transfer material 100 of the present embodiment is brought into contact with and bonded to the first conductive layer 24. In addition, the bonding of the circuit wiring forming substrate and the photosensitive transfer material as described above may be referred to as "transfer" or "lamination".

As shown in FIG. 1, when the cover film 16 is provided on the positive photosensitive resin layer 14 of the photosensitive transfer material 100, the cover is removed from the photosensitive transfer material 100 (the positive photosensitive resin layer 14). After the film 16, the positive photosensitive resin layer 14 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and bonded. The lamination (transfer) of the photosensitive transfer material on the first conductive layer is preferably such that the positive-type photosensitive resin layer side of the photosensitive transfer material is superposed on the first conductive layer, pressurized with a roller or the like, and Heating is performed. For lamination, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator that can further improve productivity can be used. When the base material of the circuit wiring forming substrate is a resin film, roll-to-roll bonding may be performed.

(Substrate) The substrate having a plurality of conductive layers laminated on the substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. In the case of a circuit wiring for a touch panel, the method of manufacturing a circuit wiring according to this embodiment is particularly preferably such that the substrate is a sheet-like resin composition. The substrate is preferably transparent. The refractive index of the substrate is preferably 1.5 to 1.52. The substrate may include a light-transmitting substrate such as a glass substrate, and tempered glass represented by Gorilla Glass of Corning Corporation may 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. In the case of using a film substrate as the substrate, it is more preferable to use a substrate without optical strain and a substrate with high transparency. Specific raw materials include polyethylene terephthalate (PET). , Polyethylene naphthalate, polycarbonate, triethyl cellulose, cycloolefin polymer.

(Conductive Layer) The plurality of conductive layers formed on the substrate may be any conductive layer used for general circuit wiring or touch panel wiring. Examples of the material of the conductive layer include metals and metal oxides. Examples of the metal oxide include indium tin oxide (ITO), indium zinc oxide (IZO), and SiO ₂ . Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, and the like.

In the method of manufacturing a circuit wiring according to this embodiment, it is preferable that at least one of the plurality of conductive layers includes a metal oxide. The conductive layer is preferably a first electrode pattern, a second electrode pattern, and different conductive elements used in a capacitance-type input device described later. A preferred form of the other conductive layer will be described later in the description of the capacitive input device.

(Substrate for Circuit Wiring Formation) The substrate has a conductive layer on the surface of the substrate. The circuit wiring is formed by patterning the conductive layer. In this example, a film substrate such as PET is preferably provided with a plurality of conductive layers such as a metal oxide or a metal.

(B) First exposure step In the first exposure step, the positive-type photosensitive resin layer 14 is pattern-exposed through the temporary support 12 of the photosensitive transfer material after the bonding step.

As examples of the exposure step, the development step, and other steps in this embodiment, the methods described in paragraphs [0035] to [0051] of Japanese Patent Laid-Open No. 2006-23696 can also be preferably used in this embodiment. .

For example, a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (the side opposite to the side in contact with the first conductive layer 24), and then A method in which the mask 30 is exposed from above the mask using ultraviolet rays, and the like. In this embodiment, the detailed arrangement and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device including circuit wiring manufactured in this embodiment, and to reduce the area occupied by the wiring as much as possible, at least a part of the pattern (particularly It is the electrode pattern of the touch panel and the portion where the wiring is taken out). The thin wire is preferably 100 μm or less, and more preferably 70 μm or less. Here, as long as the light source used in the exposure can irradiate light in a wavelength region (for example, 365 nm, 405 nm, etc.) that can dissolve the exposed portion of the photosensitive transfer material in a developing solution, it can be appropriately selected and used. Specific examples include ultrahigh-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps. The exposure amount is usually about 5 mJ / cm ² to 200 mJ / cm ² , and preferably about 10 mJ / cm ² to 100 mJ / cm ² . In addition, for the purpose of improving the rectangularity and linearity of the pattern after the exposure, it is also preferable to perform heat treatment before development. The so-called step called Post Exposure Bake (PEB) can reduce the roughness of the pattern edges caused by standing waves generated in the photosensitive resin layer during exposure.

In addition, even if pattern exposure is performed after peeling a temporary support from a positive-type photosensitive resin layer, you may expose before passing a temporary support through a temporary support, and peeling a temporary support. In order to prevent mask contamination caused by the contact between the photosensitive resin layer and the mask, or to avoid the influence on the exposure caused by the foreign matter adhering to the mask, it is preferable to perform the exposure without peeling off the temporary support. In addition, the pattern exposure may be exposure through a mask, or digital exposure using laser or the like.

(C) First developing step In the first developing step, after the temporary support 12 is peeled off from the positive photosensitive resin layer 14 after the first exposure step, the positive photosensitive resin layer 14 after the first exposure step is developed. A first pattern 14A is formed.

The first development step is a step of forming a first pattern by developing the pattern-exposed positive-type photosensitive resin layer. The development of the pattern-exposed positive-type photosensitive resin layer can be performed using a developing solution. The developer is not particularly limited as long as the exposed portion of the positive-type photosensitive resin layer can be removed. For example, a known developer such as the developer described in Japanese Patent Laid-Open No. 5-72724 can be used. The developing solution is preferably a developing solution in which the exposed portion of the positive-type photosensitive resin layer performs a dissolution-type developing action. For example, an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferred. The developer may further contain an organic solvent, a surfactant, and the like, which are miscible with water. Examples of the developer that can be preferably used in this embodiment 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 liquid-covered development, shower development, spray and rotary development, and immersion development. Here, if shower development is described, the exposed portion may be removed by spraying a developing solution on the positive-type photosensitive resin layer after exposure by shower. In addition, after developing, it is preferable to spray a detergent or the like by spraying and remove the developing residue while wiping with a brush or the like. The liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.

Furthermore, you may include the post-baking process which heat-processes the pattern containing the positive-type photosensitive resin layer obtained by image development. The 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 506.6 kPa or more. On the other hand, it is more preferably performed under an environment of 1114.6 kPa or less, and particularly preferably performed under an environment of 101.3 kPa or less. The post-baking temperature is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C. The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes. Post-baking can be performed in an air environment or under a nitrogen-replaced environment.

Other steps such as a post-exposure step may also be included.

(D) First etching step In the first etching step, at least the first conductive layer 24 and the second conductive layer 26 among the plurality of conductive layers in the region where the first pattern 14A is not arranged are subjected to an etching process. The first conductive layer 24A and the second conductive layer 26A having the same pattern are formed by etching.

The conductive layer can be etched by a known method such as the method described in paragraphs [0048] to [0054] of Japanese Patent Application Laid-Open No. 2010-152155 and the like.

For example, the etching method may be a wet etching method in which an etching solution is usually immersed. The etchant used in the wet etching may be an acidic or alkaline type etching solution that is appropriately selected depending on the object to be etched. Examples of the acidic etching solution include a single aqueous solution of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and a mixed aqueous solution of acidic components with salts such as ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may use a combination of a plurality of types of acidic components. Examples of the alkaline type etching solution include a single aqueous solution of a basic component such as a salt of an organic amine such as sodium hydroxide, potassium hydroxide, ammonia, organic amine, and tetramethylammonium hydroxide, and the basic component and permanganic acid A mixed aqueous solution of a salt such as potassium. As the basic component, a component obtained by combining a plurality of types of basic components may be used.

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

After the etching step, in order to prevent contamination of the step line, a washing step and a drying step may be performed as necessary. The washing step is performed, for example, by washing the substrate with pure water for 10 seconds to 300 seconds at normal temperature, and the drying step is performed, for example, using a blower and appropriately adjusting the air pressure (about 0.1 kg / cm ² to 5 kg / cm ² ). Just dry.

(E) Second exposure step After the first etching step, the first pattern 14A after the first etching step is pattern-exposed in a pattern different from the first pattern.

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

(F) Second development step In the second development step, the first pattern 14A after the second exposure step is developed to form a second pattern 14B. The part of the first pattern exposed in the second exposure step is removed by development. In addition, in the second developing step, the same method as that in the first developing step can be applied.

(G) Second etching step In the second etching step, at least the first conductive layer 24A among the plurality of conductive layers in the region where the second pattern 14B is not arranged is subjected to an etching treatment.

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

(H) Step of removing positive-type photosensitive resin layer After the second etching step is completed, the second pattern 14B remains in a part of the first conductive layer 24B. If the positive-type photosensitive resin layer is unnecessary, all the remaining positive-type photosensitive resin layer 14B may be removed.

The method of removing the remaining positive photosensitive resin layer is not particularly limited, and examples thereof include a method of removing it by chemical treatment. The method of removing the positive-type photosensitive resin layer includes, for example, a method in which a base material having a positive-type photosensitive resin layer and the like is peeled off at 30 ° C to 80 ° C, preferably 50 ° C to 80 ° C. Medium immersion for 5 to 30 minutes.

Examples of the stripping solution include dissolving inorganic alkali components such as sodium hydroxide and potassium hydroxide or organic alkali components such as tertiary amines and quaternary ammonium salts in water, dimethylsulfinium, N-methylpyrrolidone, or the like. Peeling solution in a mixed solution. It is also possible to use a peeling solution, and peel it by a spray method, a shower method, a coating method, or the like.

The method for manufacturing a circuit wiring according to this embodiment may include any other steps. For example, the steps described below are listed, but are not limited to these steps.

<Step of attaching a protective film> After the first etching step and before the second exposure step, a step of attaching a protective film (not shown) having a light-transmitting property to the first pattern may be further included. In this case, it is preferable that the first pattern is pattern-exposed through the protective film in the second exposure step, and that the second development step is performed after the protective film is peeled from the first pattern after the second exposure step.

<Step of Decreasing Visible Light Reflectance> The method for manufacturing a circuit wiring according to this embodiment may include a step of reducing the visible light reflectance of a part or all of the plurality of conductive layers on the substrate. Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, copper oxide is formed by oxidizing copper to blacken it, thereby reducing visible light reflectance. A preferred form of the process for reducing the visible light reflectance is described in paragraphs [0017] to [0025] of Japanese Patent Laid-Open No. 2014-150118 and paragraphs [0041] of Japanese Patent Laid-Open No. 2013-206315. Paragraphs [0042], [0048], and [0058] are described, and the contents of this bulletin are incorporated into this specification.

<Procedure for Forming a New Conductive Layer on an Insulating Film> The method for manufacturing a circuit wiring in this embodiment also preferably includes a step of forming an insulating film on the formed circuit wiring and forming a new conductive layer on the insulating film. A step of. With the configuration described above, the second electrode pattern described later can be formed while being insulated from the first electrode pattern. The step of forming the insulating film is not particularly limited, and a known method for forming a permanent film can be exemplified. Alternatively, a photosensitive material having an insulating property may be used to form an insulating film in a desired pattern by a photolithography method. The step of forming a new conductive layer on the insulating film is not particularly limited. It is also possible to form a new conductive layer in a desired pattern using a photolithography method using a conductive photosensitive material.

In addition, in the description with reference to FIG. 2, a case has been described where a circuit wiring having two different patterns is formed on a circuit wiring forming substrate having two conductive layers. However, a circuit wiring manufacturing method of this embodiment is applied. The number of conductive layers of the substrate is not limited to two, and the combination of the exposure step, the development step, and the etching step may be performed three or more times by using a circuit wiring formation substrate laminated with three or more conductive layers. Therefore, three or more conductive layers are respectively formed into different circuit wiring patterns.

In addition, not shown in FIG. 2, but the manufacturing method of the circuit wiring of this embodiment is also preferably that the substrate includes a plurality of conductive layers on both sides of the surface, and for the conductive layers formed on both surfaces of the substrate, Circuits are formed sequentially or simultaneously. With the configuration described above, a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the base material and a second conductive pattern is formed on the other surface can be formed. In addition, it is also preferable that the circuit wiring for a touch panel having the above-mentioned configuration is formed by roll-to-roll from both sides of the substrate.

[Circuit Wiring] The use of the circuit wiring manufactured by the method for manufacturing a circuit wiring according to this embodiment is not limited, and for example, a circuit wiring for a touch panel is preferred. A preferred form of the circuit wiring for a touch panel will be described later in the description of the capacitance type input device.

FIG. 3 is a schematic cross-sectional view of one embodiment of a circuit wiring that can be manufactured by the method for manufacturing a circuit wiring according to this embodiment. In the circuit wiring of this embodiment, a first electrode pattern 3 is formed on a circuit substrate 1, and different conductive elements 6 are formed on the first electrode pattern 3. The circuit wiring for a touch panel shown in FIG. 3 is a circuit wiring including conductive portions having two patterns: a conductive laminated portion where the first electrode pattern 3 and a different conductive element 6 are formed, and a first electrode pattern 3 conductive parts. When the circuit wiring for a touch panel as shown in FIG. 3 is viewed from an obliquely upward direction in a planar view, it will be in the form shown in the schematic diagram of FIG. 4. In an example of the circuit wiring for a touch panel shown in FIG. 4, the dotted line portion in FIG. 4 is a conductive laminated portion in which the first electrode pattern 3 and different conductive elements 6 are formed, and the portion connected by the quadrangle in FIG. 4 is only A conductive portion having a first electrode pattern 3. The method of manufacturing a circuit wiring of this embodiment can easily manufacture a variety of different circuit wirings. For example, as shown in FIGS. 3 and 4, a circuit including a conductive laminated portion including the conductive element 6 and the electrode pattern 3 laminated and a conductive portion including only the electrode pattern 3 can be easily formed.

[Input Device and Display Device] Examples of the device including a circuit wiring manufactured by the method for manufacturing a circuit wiring according to this embodiment include an input device. The input device in this embodiment is preferably a capacitive touch panel. The display device in this embodiment includes the input device in this embodiment. The display device in this embodiment is preferably an image display device.

<Capacitance-type input device and image display device provided with the same The components of the image display device can be applied: "Latest Touch Panel Technology" (issued on July 6, 2009, Techno Times (Stock)); "Technology and Development of Touch Panels" edited by Yuji Mitani , Published by CMC (2004, 12); 2009 T-11 lecture materials of Flat Panel Display (FPD) International 2009 Forum, Cypress Semiconductor Corporation application note AN2292, etc. .

First, the configuration of a capacitance type input device will be described. FIG. 5 is a cross-sectional view showing a configuration of the capacitance type input device 10. In FIG. 5, the capacitance-type input device 10 includes a substrate 1, a masking layer 2, a first electrode pattern 3, a second transparent electrode pattern 4, an insulating layer 5, different conductive elements 6, and a transparent protective layer 7.

The base material 1 includes a light-transmitting substrate such as a glass substrate, and tempered glass such as Corning's Gorilla Glass can be used. In addition, in FIG. 5, the side on which the respective elements of the base material (front layer) 1 are provided is referred to as a non-contact surface. In the capacitance-type input device 10, a finger or the like is brought into contact with a contact surface (a surface opposite to the non-contact surface) of the substrate 1 and the like is input.

In addition, a mask layer 2 is provided on a non-contact surface of the base material 1. The mask layer 2 is a frame-shaped pattern around a display area formed on the non-contact side of the front panel of the touch panel, and is formed so that lead-back wiring and the like are not visible from the glass substrate side in appearance. The electrostatic capacitance type input device 10 may be provided with a mask layer 2 at a position covering a part of the region of the base material 1. Furthermore, an opening may be provided in a part of the base material 1. A mechanical switch can be provided at the opening by pressing.

Formed on the contact surface of the substrate 1 are a plurality of first electrode patterns 3 formed by extending a plurality of pad portions in a first direction via a connection portion, which are electrically insulated from the first electrode pattern 3 and are intersected with the first direction. The plurality of second transparent electrode patterns 4 of the plurality of pad portions extending in the direction of the substrate and the insulating layer 5 electrically insulating the first electrode pattern 3 and the second transparent electrode pattern 4. The first electrode pattern 3, the second transparent electrode pattern 4, and different conductive elements 6 described later can be made of a light-transmissive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). It is made of a conductive metal oxide film. Examples of the metal film include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, Mo; and a metal oxide film such as SiO ₂ . In the formation of the metal film, the film thickness of each element can be set to 10 nm to 200 nm. In addition, since the amorphous ITO film is formed into a polycrystalline ITO film by firing, the resistance can also be reduced. The first electrode pattern 3 and the second transparent electrode pattern 4 are preferably formed using a positive-type photosensitive resin layer as an etching resist (etching pattern). In the formation of the second electrode layer for forming the second transparent electrode pattern, a well-known method may be used in addition to the photolithography method using a resist typified by the positive-type photosensitive resin layer used in this embodiment. . In addition, it can also be manufactured using the photosensitive transfer material containing the photosensitive resin composition using a conductive fiber. When the first conductive pattern or the like is formed using ITO or the like, paragraphs [0014] to [0016] and the like of Japanese Patent No. 4506785 can be referred to.

In addition, at least one of the first electrode pattern 3 and the second transparent electrode pattern 4 may be provided across the non-contact surface of the substrate 1 and the region on both sides of the surface of the mask layer 2 on the side opposite to the substrate 1. FIG. 5 shows a view in which the second transparent electrode pattern is provided across the non-contact surface of the substrate 1 and the regions on both sides of the surface of the mask layer 2 on the side opposite to the substrate 1.

The first electrode pattern 3 and the second electrode pattern 4 will be described using FIGS. 6 and 7. 6 and 7 are also explanatory diagrams showing examples of the first electrode pattern and the second electrode pattern. As shown in FIGS. 6 and 7, the pad portion 3 a of the first electrode pattern is formed to extend in the first direction via the connection portion 3 b. In addition, the second electrode pattern 4 is electrically insulated from the first electrode pattern by the insulating layer 5 and is included in a direction crossing the first direction (the second direction in FIGS. 6 and 7: the extension of the second electrode pattern Direction) to form a plurality of pad portions. Here, in the case of forming the first electrode pattern 3, the pad portion 3a and the connection portion 3b may be made into one body, or only the connection portion 3b may be made, and the pad portion 3a and the second transparent electrode pattern 4 may be made (pattern Into one. In the case where the pad portion 3a and the second transparent electrode pattern 4 are produced (patterned) into one body, as shown in FIGS. 6 and 7, a part of the connection portion 3b is connected to a part of the pad portion 3a, and is insulated by The layers 5 are formed in a state where the first electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated.

In FIG. 5, a different conductive element 6 is provided on one surface side of the mask layer 2 opposite to the substrate 1. The different conductive elements 6 are elements that are electrically connected to at least one of the first electrode pattern 3 and the second transparent electrode pattern 4 and are different from the first electrode pattern 3 and the second transparent electrode pattern 4. FIG. 5 shows a diagram in which different conductive elements 6 are connected to the second transparent electrode pattern 4.

In addition, in FIG. 5, a transparent protective layer 7 is provided at a position covering all the constituent elements. The transparent protective layer 7 may be formed at a position covering only a part of each constituent element. The insulating layer 5 and the transparent protective layer 7 may be the same material or different materials. The materials constituting the insulating layer 5 and the transparent protective layer 7 are preferably materials having good surface hardness and heat resistance, and known photosensitive siloxane resin materials, acrylic resin materials, and the like are used, and these materials are commonly used in the field to which the present invention belongs. Known by intellectuals. In addition to the photolithography method, a well-known method such as inkjet or screen printing can be used as the patterning method of the insulating layer.

In the method for manufacturing a capacitance type input device, it is preferable that at least one of the first electrode pattern 3, the second transparent electrode pattern 4, and different conductive elements 6 use a positive photosensitive resin layer as an anti-etching agent (etching pattern). ) To form an etching process. In addition, it is also preferable that at least one element of the black mask layer 2, the insulating layer 5, and the transparent protective layer 7 as needed also uses the sensitivity including a temporary support, a thermoplastic resin layer, and a photocurable resin layer in this order. Film to form.

At least one of the first electrode pattern 3, the second transparent electrode pattern 4, and the different conductive elements 6 is preferably formed by performing an etching treatment using a positive photosensitive resin layer as an etching resist (etching pattern). When the first electrode pattern 3, the second transparent electrode pattern 4 and different conductive elements 6 are formed by an etching process, first on a non-contact surface of a substrate 1 on which a black mask layer 2 and the like are formed, At least an inorganic insulating layer is provided on a portion where the black mask layer 2 is provided, and a transparent electrode layer such as ITO is formed on the non-contact surface of the base material 1 or on the inorganic insulating layer by sputtering. Next, a positive-type photosensitive resin layer having a photocurable resin layer for etching as a photocurable resin layer on a transparent electrode layer was used to form an etching pattern by exposure and development. Then, the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first electrode pattern 3 and the like can be formed.

When the first electrode pattern 3, the second transparent electrode pattern 4 and different conductive elements 6 are formed using a photosensitive film having a conductive photocurable resin layer, the surface of the substrate 1 can be formed by At least an inorganic insulating layer is provided on a portion where the black mask layer 2 is provided, and a conductive photocurable resin layer is formed by transferring the non-contact surface of the base material 1 or the inorganic insulating layer.

The mask layer 2, the insulating layer 5, and the transparent protective layer 7 can be formed by using a photosensitive film to transfer a photocurable resin layer onto the substrate 1. For example, when the black mask layer 2 is formed, a black photocurable resin layer can be transferred onto the surface of the substrate 1 by using a photosensitive film having a black photocurable resin layer as the photocurable resin layer. form. In the case where the insulating layer 5 is formed, by using a photosensitive film including an insulating photocurable resin layer as the photocurable resin layer, the substrate on which the first transparent electrode pattern or the second transparent electrode pattern is formed can be used. The surface of 1 is formed by transferring a photocurable resin layer. When the transparent protective layer 7 is formed, a photocurable resin can be transferred to the surface of the substrate 1 on which the elements are formed by using a photosensitive film including a transparent photocurable resin layer as the photocurable resin layer. Layer. [Example]

Examples are given below to further describe the present invention in detail. The materials, usage amounts, proportions, processing contents, processing sequence, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of this embodiment. Therefore, the scope of this embodiment is not limited to the specific examples shown below. In addition, except for the value (%) of the haze value described later, "part" and "%" are mass standards unless otherwise specified.

[Example 1] A positive-type photosensitive resin composition 1 was produced according to the following formulation. (Positive photosensitive resin composition 1: Formulation) ・ Specific polymer 1 (the following compound, weight average molecular weight 1.5 × 10 ⁴ ) 9.66 parts (Tg of specific polymer 1 was measured by the method described above, and the result was − 10 ℃) ・ Photo acid generator (Compound A-1 below) 0.25 parts ・ Interfacial agent (Interfacial agent C below) 0.01 part ・ Additive (Compound D below) 0.08 part ・ Propylene glycol monomethyl ether acetate [Solvent] 90.00 parts are in the following structure, and the numerical value of each constituent unit represents the content (mass%) of the constituent unit.

[Chemical 24]

Compound A-1

Surfactant C: Perfluoroalkyl-containing non-ionic surfactant (F-554, manufactured by Di Edison (DIC) Co., Ltd.) [Chem. 26]

Compound D: Basic compound of the following structure (manufacturer: manufactured by Toyo Kasei Kogyo Co., Ltd., product number: CMTU) [Chem. 27]

Using a slit-shaped nozzle, the prepared positive photosensitive resin composition 1 was applied to a thickness of 5.0 μm in a dry film to a polyethylene terephthalate film having a thickness of 50 μm as a temporary support ( Hereinafter referred to as "PET (A)"). Then, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar Co., Ltd.) was pressure-bonded as a cover film to prepare a photosensitive transfer material 1.

In addition, the total light haze of PET (A) was 0.19%. The film haze was measured by the haze meter HZ-2 manufactured by Suga Test Instruments (stock), and the total light haze value (%) of the base sheet was measured in accordance with JIS-K-7136.

[Example 2] A photosensitive transfer material 2 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the specific polymer 2 described below. The Tg of the specific polymer 2 was measured by the method described above, and it was 20 ° C. The weight average molecular weight measured by the GPC method described above was 1.5 × 10 ⁴ .

[Chemical 28]

[Example 3] A photosensitive transfer material 3 was produced in the same manner as in Example 1, except that the specific polymer 1 was replaced with the specific polymer 3 described below. When the Tg of the specific polymer 3 was measured by the method described above, it was 40 ° C. The weight average molecular weight measured by the GPC method described above was 1.5 × 10 ⁴ .

[Chemical 29]

[Example 4] A photosensitive transfer material 4 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the specific polymer 4 described below. The Tg of the specific polymer 4 was measured by the method described above, and it was 50 ° C. The weight average molecular weight measured by the GPC method described above was 1.5 × 10 ⁴ .

[Chemical 30]

[Example 5] A photosensitive transfer material 5 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the specific polymer 5 described below. When the Tg of the specific polymer 5 was measured by the method described above, it was 56 ° C. The weight average molecular weight measured by the GPC method described above was 1.5 × 10 ⁴ .

[Chemical 31]

[Example 6] A positive-type photosensitive resin composition 3 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the specific polymer 3. Using a slit-shaped nozzle, the prepared positive-type photosensitive resin composition 3 was applied to a 50 μm-thick polyethylene terephthalate film with a dry film thickness of 5.0 μm ( Hereinafter, it is referred to as "PET (B)"). Then, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar) was pressure-bonded as a cover film to prepare a photosensitive transfer material 6. In addition, the total light haze value (%) of PET (B) was measured by the same method as PET (A) in Example 1. As a result, the total light haze value was 0.78%.

[Comparative Example 1] A photosensitive transfer material C1 of Comparative Example 1 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the following comparative polymer C1. The Tg of the comparative polymer C1 was measured by the method described above, and it was 100 ° C. The weight average molecular weight measured by the GPC method described above was 1.5 × 10 ⁴ .

[Chemical 32]

[Evaluation] A substrate having a copper layer was produced on a PET film having a thickness of 188 μm and having a thickness of 500 nm by a sputtering method.

<Evaluation of lamination suitability> The produced photosensitive transfer material 1, photosensitive transfer material 2 and photosensitive transfer material C1 were cut into 50 cm squares, the cover film was peeled off, and the laminating roll temperature was 90 ° C, Lamination conditions of a linear pressure of 0.6 MPa and a linear speed (laminating speed) of 3.6 m / min are laminated on a PET substrate with a copper layer. The area where the photosensitive resin layer was closely adhered to the copper layer was visually evaluated, and the area ratio of the adherence was determined based on "area to which the photosensitive resin layer is adhered / area of the cut transfer material" (%). Evaluation was based on A to C of the following standards. A: 95% or more B: 80% or more and less than 95% C: 80% or less

<Resolution evaluation> The prepared photosensitive transfer material 1 to photosensitive transfer material 6 and photosensitive transfer material C1 were laminated on a belt under a lamination condition of a linear pressure of 0.6 MPa and a linear velocity of 3.6 m / min. PET substrate with copper layer. In addition, when the lamination adaptability is B or less at a roll temperature of 90 ° C., the laminating roll temperature is increased until the lamination property becomes A judgment based on the evaluation criteria described above, and a sample is produced. In the photosensitive transfer materials of Examples 1 to 5 and C1, the temporary support was not peeled off, and was covered by a line and space pattern (duty ratio of 1: 1) with a line width of 3 μm to 20 μm. After exposure by an ultra-high pressure mercury lamp under a cover, the temporary support is peeled off and developed. Using a 1.0% sodium carbonate aqueous solution at 28 ° C., development was performed by spray development for 30 seconds. In the photosensitive transfer material of Example 6, the temporary support was peeled from the photosensitive layer, and then exposed in the same manner as in Example 1 through a mask and developed. Among the obtained line and space patterns, the pattern with the highest resolution was set as the reaching resolution, and evaluated according to the following criteria A to C. A: less than 7 μm B: 7 μm or more and less than 15 μm C: 15 μm or more The results are shown in Table 1 below.

[Table 1]

Either the lamination adaptability or the resolution evaluation of the photosensitive transfer material of the examples was good. On the other hand, the lamination adaptability of the photosensitive transfer material of Comparative Example 1 was poor.

[Example 7] On a 100-micron-thick PET substrate, ITO was formed as a second conductive layer by sputtering and a thickness of 150 nm, and the second conductive layer formed was vacuum-deposited. As a first conductive layer, copper was formed into a film with a thickness of 200 nm to form a circuit-forming substrate.

After peeling the cover film, the photosensitive transfer material 1 obtained in Example 1 was laminated (line pressure 0.6 MPa, line speed 3.6 m / min, roll temperature 100 ° C) on a copper layer. Without exposing the temporary support, a contact pattern exposure is performed using a photomask provided with a pattern A shown in FIG. 8 having a structure in which a conductive layer pad is connected in one direction (first exposure step). In the pattern A shown in FIG. 8, a solid line portion and a gray portion are light-shielding portions, a portion other than the light-shielding portion is an opening portion, and a dotted line portion imaginarily shows an aligned frame. The solid line portion is a thin line of 70 μm or less. Hereinafter, similar thin lines are formed in other examples and comparative examples.

Then, the temporary support was peeled off and developed using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution (first development step). After the first development step, water was washed to obtain a light-shielding region having a first pattern (pattern A). Shape pattern) shape of a positive photosensitive resin layer.

Next, the copper layer (first conductive layer) was etched using a copper etchant (manufactured by Kanto Chemical Co., Ltd., Cu-02), and then an ITO etchant (manufactured by Kanto Chemical Co., Ltd., ITO-02) was used. The ITO layer (the second conductive layer) is etched to obtain the copper layer (the first conductive layer) and the ITO layer (the second conductive layer). Each of the copper layers (the first conductive layer) and the ITO layer (the second conductive layer) is drawn with a first pattern (a pattern of the shape of the light-shielding region of the pattern A). Substrate (first etching step).

Then, in a state where the alignment is matched, in the pattern B shown in FIG. 9, the solid line portion and the gray portion also indicate the light shielding portion. Pattern exposure is performed using a mask provided with a light-shielding portion opening and a light-shielding portion according to the shape of the pattern B shown in FIG. 9 (second exposure step), and development is performed using a 2.38% TMAH aqueous solution (second development step). After the second development step, water-washing was performed to obtain a positive-type photosensitive resin layer having a shape of a second pattern (the pattern of the overlapping portion of the light-shielding portion of the pattern A and the light-shielding portion of the pattern B). In the pattern B shown in FIG. 9, as described above, the gray portion also indicates the light-shielding portion, the portion other than the light-shielding portion becomes an opening portion, and the dotted line portion virtually represents an aligned frame.

Then, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board. A circuit wiring board having a pattern C shown in FIG. 10 was obtained in the manner described above. In FIG. 10, the areas that are not solid lines (both white and gray areas) are in a state where the PET substrate is exposed. The solid line portion in the gray area in FIG. 10 is a state where the ITO wiring is exposed. The other solid line portions correspond to the peripheral wiring portion, and have a structure in which copper wiring is laminated on the ITO wiring to share the same circuit pattern.

Then, by using Cu-02, only the first conductive layer (copper layer) as a second pattern is provided in the region where the positive photosensitive resin layer is not provided (second etching step). Furthermore, using a peeling liquid (KP-301 manufactured by Kanto Chemical Co., Ltd.), the remaining photosensitive resin layer was peeled to obtain a circuit wiring board. Thereby, the circuit wiring board which has the wiring pattern C shown in FIG. 10 is obtained. In FIG. 10, a region other than a solid line is a state in which the PET substrate is exposed (both the openings indicated by white and the regions indicated by gray are both). The solid line portion in the gray area in FIG. 10 is a state where the ITO wiring (second conductive layer) is exposed. The other solid line portions correspond to peripheral wiring portions, and copper wiring (first conductive layer) is laminated on the ITO wiring to have a structure having a common circuit pattern. As a result of observing the circuit of the obtained circuit wiring board with a microscope, the pattern was free from peeling and defects, and was a high-definition and clear pattern.

[Example 8] On a 100-micron-thick PET substrate, ITO was formed into a film with a thickness of 150 nm as a second conductive layer by sputtering, and the second conductive layer was formed by vacuum evaporation. Copper was formed into a film with a thickness of 200 nm as a first conductive layer to form a circuit-forming substrate. A photosensitive transfer material 1 was laminated on a copper layer (a linear pressure of 0.6 MPa, a linear speed of 3.6 m / min, and a roller temperature of 100 ° C). Without exposing the temporary support, pattern exposure was performed using a photomask provided with a pattern A having a structure in which a conductive layer pad is connected in one direction. After exposure, the temporary support was peeled off, developed, and then washed with water to obtain a pattern A. Next, the copper layer was etched using a copper etchant (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer was etched using an ITO etchant (ITO-02 manufactured by Kanto Chemical Co., Ltd.), thereby obtaining Both copper and ITO are drawn with a pattern A.

Then, PET (A) was laminated again as a protective film on the remaining resist (positive-type photosensitive resin layer). In this state, in a state where the alignment is matched, pattern exposure is performed using a photomask provided with an opening portion of the pattern B, and PET (A) as a protective film is peeled off, followed by development and water washing. Then, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board. Thereby, the circuit wiring board of the pattern C is obtained. As a result of observing the circuit of the obtained circuit wiring board with a microscope, the pattern was free from peeling and defects, and was a high-definition and clear pattern.

1‧‧‧ substrate
2‧‧‧Mask layer
3‧‧‧ electrode pattern (first electrode pattern)
3a‧‧‧mat part
3b‧‧‧Connection section
4‧‧‧ transparent electrode pattern (second transparent electrode pattern)
5‧‧‧ Insulation
6‧‧‧ different conductive elements
7‧‧‧ transparent protective layer
10‧‧‧Capacitive input device
12‧‧‧ temporary support
14‧‧‧Positive photosensitive resin layer
14A‧‧‧The first pattern
14B‧‧‧Second Pattern
16‧‧‧ Covering film
20‧‧‧Circuit forming substrate
22‧‧‧ Substrate
24‧‧‧first conductive layer
24A‧‧‧First conductive layer (after the first etching step)
24B‧‧‧First conductive layer (after the second etching step)
26‧‧‧Second conductive layer
26A‧‧‧Second conductive layer (after the first etching step and the second etching step)
30, 40‧‧‧ Mask
100‧‧‧ photosensitive transfer material

FIG. 1 is a schematic diagram showing an example of a layer configuration of a photosensitive transfer material according to the present embodiment. FIG. 2 is a schematic view showing an example of a method for manufacturing a circuit wiring for a touch panel using the photosensitive transfer material of the embodiment. FIG. 3 is a schematic diagram of an example of a circuit wiring for a touch panel that can be manufactured by the circuit wiring manufacturing method of the present embodiment. FIG. 4 is a schematic diagram of an example of a circuit wiring for a touch panel that can be manufactured by the circuit wiring manufacturing method of the embodiment. FIG. 5 is a schematic diagram showing a configuration of an example of an input device having a circuit wiring formed by the manufacturing method of the embodiment. FIG. 6 is a schematic configuration diagram illustrating an example of an arrangement of pad portions and connection portions of a first electrode pattern, and a second electrode pattern. FIG. 7 is a schematic configuration diagram showing an example of an arrangement of pad portions and connection portions of a first electrode pattern, and a second electrode pattern. FIG. 8 is a schematic diagram showing a pattern A. FIG. FIG. 9 is a schematic diagram showing a pattern B. FIG. FIG. 10 is a schematic diagram showing a pattern C. FIG.

12‧‧‧ temporary support

14‧‧‧Positive photosensitive resin layer

16‧‧‧ Covering film

100‧‧‧ photosensitive transfer material

Claims (13)

A photosensitive transfer material comprising: a temporary support; and a positive-type photosensitive resin layer including a structural unit represented by the following general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 ° C. or lower. Polymers and photoacid generators,

In Formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, and 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 arylene group. The photosensitive transfer material according to item 1 of the scope of patent application, wherein the glass transition temperature of the polymer is -20 ° C or higher. The photosensitive transfer material according to item 1 of the scope of patent application, wherein the polymer contains 20% by mass or more of the structural unit represented by the general formula A with respect to the total solid content of the polymer. The photosensitive transfer material according to item 1 of the scope of patent application, wherein the polymer contains 0.1 to 20% by mass of the structural unit having an acid group with respect to the total solid content of the polymer. The photosensitive transfer material according to item 1 of the scope of patent application, wherein the structural unit in which R ³⁴ is a hydrogen atom in the general formula A is 20 with respect to the total amount of the structural units represented by the general formula A. Above mass%. The photosensitive transfer material according to item 2 of the scope of patent application, wherein the polymer contains 20% by mass or more of the structural unit represented by the general formula A with respect to the total solid content of the polymer. And contains 0.1 to 20% by mass of the structural unit having an acid group, and relative to the total amount of the structural unit represented by the general formula A, in the general formula A, R ³⁴ is a hydrogen atom. The constituent unit is 20% by mass or more. The photosensitive transfer material according to any one of claims 1 to 6, in which the photosensitive transfer material further includes a basic compound. The photosensitive transfer material according to item 7 of the scope of application, wherein the basic compound is a morpholine compound. The photosensitive transfer material according to item 7 of the scope of patent application, wherein the weight average molecular weight Mw of the polymer is 6.0 × 10 ⁴ or less. The photosensitive transfer material according to item 7 of the scope of patent application, wherein the temporary support has a light-transmitting property. A method for manufacturing a circuit wiring, which includes: (A) a bonding step, in which, for a substrate, the positive photosensitive resin layer of the photosensitive transfer material according to item 9 of the scope of patent application is applied to the substrate; The substrates are contacted and bonded; (B) an exposure step, which pattern-exposes the positive photosensitive resin layer of the photosensitive transfer material after the bonding step; (C) a developing step, which exposes The positive photosensitive resin layer after the step is developed to form a pattern; and (D) an etching step, in which an etching process is performed on the substrate in a region where the pattern is not arranged. A method for manufacturing a circuit wiring, which includes: (a) a bonding step, for a substrate, that is, a substrate including a plurality of conductive layers including a base material and a first conductive layer and a second conductive layer having different constituent materials from each other; and A substrate having the first conductive layer and the second conductive layer as the outermost layers is laminated on the surface of the substrate in an order away from the surface of the substrate, so that, as described in item 9 of the scope of patent application The positive-type photosensitive resin layer of the photosensitive transfer material is bonded with the first conductive layer in contact with the first conductive layer; (b) a first exposure step, wherein the photosensitive transfer layer is passed through the bonding step; Pattern exposure of the positive-type photosensitive resin layer by the temporary support of a printing material; (c) a first development step, peeling the positive-type photosensitive resin layer after the first exposure step; After temporarily supporting the substrate, developing the positive-type photosensitive resin layer after the first exposure step to form a first pattern; (d) a first etching step, in a region where the first pattern is not disposed, At least all of the plurality of conductive layers The first conductive layer and the second conductive layer are subjected to an etching treatment; (e) a second exposure step of patterning the first pattern after the first etching step in a pattern different from the first pattern; Exposure; (f) a second development step, which develops the first pattern after the second exposure step to form a second pattern; and (g) a second etching step, which does not configure the second pattern At least the first conductive layer of the plurality of conductive layers in the region is subjected to an etching process. The method for manufacturing circuit wiring according to item 12 of the scope of patent application, wherein after the first etching step and before the second exposure step, the method further includes attaching a light transmissive material on the first pattern. A protective film step, in the second exposure step, exposing the pattern to the first pattern via the protective film, and after the second exposure step, peeling off the first pattern from the first pattern After the protective film, the second etching step is performed.