TW201734637A - Positive photosensitive transfer materials and method for producing circuit wiring - Google Patents

Abstract

To provide a positive photosensitive transfer material having high adhesiveness to a substrate even when bonded at a low temperature and a high process speed, and allowing formation of a circuit wiring line with high resolution, and a method for manufacturing a circuit wiring line. A positive photosensitive transfer material 100 includes a temporary support and a positive photosensitive resin layer 14 which comprises: a polymer having a structural unit represented by formula A and having a weight average molecular weight of 1.0*10<SP>5</SP> or less; a plasticizer having a smaller weight average molecular weight than that of the polymer having the structural unit represented by formula A; and a photoacid generator. A method for manufacturing a circuit wiring line using the above material is also disclosed.

Description

Positive photosensitive transfer material and method of manufacturing circuit wiring

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

In a display device (an organic electroluminescent (EL) display device, a liquid crystal display device, or the like) including a touch panel such as a capacitive input device, an electrode pattern corresponding to a sensor of a visible portion, a peripheral wiring portion, and a take-out A conductive layer pattern such as wiring of the wiring portion is provided inside the touch panel. 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, partially cured, and 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 contains A polymer component having a polymer having the constituent unit a1 and a B photoacid generator having a group in which the acid group is protected by an acid-decomposable group, and the photosensitive resin composition does not have an ethylenic cross-linking structure.

Further, Patent Document 2 discloses a photosensitive transfer material comprising a support, a thermoplastic resin layer, and a photosensitive resin composition layer in this order, and a pattern forming method using the same. And the photosensitive resin composition layer contains a polymer component (A) including a polymer having a constituent unit (a1) and a photoacid generator (B) having an acid group-based acid-decomposable group Protected groups. [Prior Art Document] [Patent Literature]

[Patent Document 1] WO2015/093271 (Patent Document 2) WO2014/065220

[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 the wiring of the peripheral extraction portion (the peripheral wiring portion and the extraction wiring portion), and does not need to be bridged. Three-dimensional connections. Therefore, in the technical field of the method for manufacturing a circuit wiring for a touch panel, as in the case of using a pattern forming method of a conventional photosensitive resin composition, a resist is not formed for each desired pattern, and it is expected that the film is resistant once. The etchant is formed to form circuit wirings of the conductive layers including the plurality of patterns, thereby omitting the steps.

In addition, it is preferable that the substrate for forming a circuit wiring (hereinafter referred to as a "circuit for forming a circuit wiring") is used in the case of improving the resolution of the circuit wiring in which the pattern is formed, from the viewpoint of improving the productivity. The photosensitive transfer material is bonded to a photosensitive material at a low temperature while being conveyed at a high speed by a roll to roll, and exposed, developed, or the like.

In the photosensitive transfer material disclosed in Patent Document 1 and Patent Document 2, when the substrate is formed on the circuit wiring forming substrate at a low temperature and high speed, the adhesion is insufficient, and when the temporary support is peeled off, The photosensitive resin layer is also peeled off at the same time, or a part of the photosensitive resin composition layer is accidentally peeled off in the middle of the manufacturing process of the circuit wiring.

An object of the present invention is to provide a positive photosensitive transfer material and a circuit wiring manufacturing method, wherein the positive photosensitive transfer material has a low temperature and a high speed (for example, a roll temperature used for bonding is 130 ° C or lower, The transfer speed is 1 m/min or more. The circuit wiring forming substrate is bonded to each other, and also has high adhesion, and the circuit wiring can be formed with high resolution.

[Means for Solving the Problem] The inventors of the present invention conducted intensive studies and found that positively containing a specific polymer, a plasticizer, and a photoacid generator are included in the temporary support by the positive photosensitive transfer material. The photosensitive resin layer can achieve the object. That is, specific means for achieving the object of the present invention are as follows.

<1> A positive photosensitive transfer material comprising: a temporary support; and a positive photosensitive resin layer comprising a polymer having a structural unit represented by the following formula A and having a weight average molecular weight of 1.0 × 10 ⁵ or less a plasticizer having a weight average molecular weight smaller than a polymer having a constituent unit represented by Formula A, and a photoacid generator, and disposed on the temporary support, [Chemical Formula 1]

In the formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ represents an alkyl group or an aryl group, and R ³¹ Or 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 extended aryl group.

<2> The positive photosensitive transfer material according to <1>, wherein the plasticizer is a compound having an alkylene group in the molecule. <3> The positive photosensitive transfer material of the above-mentioned <1>, wherein the polymer and plasticization of the structural unit represented by Formula A with respect to the total solid content of the positive photosensitive resin layer. The total ratio of the agents is 70% by mass or more and 99% by mass or less. The positive photosensitive transfer material of any one of the above-mentioned positive photosensitive resin layers with respect to the polymer of the structural unit represented by Formula A, and The total amount of the plasticizers is such that the ratio of the polymer having the constituent unit represented by Formula A is 60% by mass or more and 90% by mass or less. The positive photosensitive material of any one of the above-mentioned positive photosensitive resin layers is 0.001 mass part with respect to 100 mass parts of the total solid content of the positive photosensitive resin layer. ～10 parts by mass of a nonionic surfactant. <6> The positive photosensitive transfer material according to <5>, wherein the nonionic surfactant is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography. 1.0×10 ³ or more and 1.0×10 ⁴ or less, and a copolymer of the structural unit A and the structural unit B represented by the following formula (I-1), (In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkyl group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon. An alkyl group having a number of 1 or more and 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are a mass percentage indicating a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less, q The numerical value is 20% by mass or more and 90% by mass or less, 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. The positive photosensitive transfer material according to any one of <1> to <6> wherein the temporary support has translucency.

<8> A method of manufacturing a circuit wiring, comprising: (a) a bonding step of, for a substrate, that is, including a substrate, and a plurality of conductive layers including a first conductive layer and a second conductive layer different in constituent materials from each other; a layer on the surface of the substrate, wherein a substrate having a first conductive layer and a second conductive layer as the outermost layer is laminated in order from the surface away from the substrate, and the positive photosensitive property as described in <7> is obtained. The positive photosensitive resin layer of the transfer material is in contact with the first conductive layer and is bonded; (b) the first exposure step, the positive support is positively supported by the temporary support of the positive photosensitive transfer material after the bonding step The resin layer is subjected to pattern exposure; (c) a first development step of developing the positive photosensitive resin layer after the first exposure step after peeling off the temporary support from the positive photosensitive resin layer after the first exposure step And forming a first pattern; (d) a first etching step of etching at least the first conductive layer and the second conductive layer of the plurality of conductive layers in the region where the first pattern is not disposed; (e) the second exposure Steps with the first a different pattern, patternwise exposing the first pattern after the first etching step; (f) a second developing step of developing the first pattern after the second exposing step to form a second pattern; and (g) And a second etching step of etching at least the first conductive layer of the plurality of conductive layers in the region where the second pattern is not disposed. <9> The method of manufacturing a circuit wiring according to <8>, wherein after the first etching step and before the second exposure step, the step of attaching a light-transmitting protective film to the first pattern is further included. In the second exposure step, the first pattern is subjected to pattern exposure via a protective film, and after the second exposure step, after the protective film is peeled off from the first pattern, a second etching step is performed.

[Effects of the Invention] According to the present invention, it is possible to provide a substrate for circuit wiring formation even at a low temperature and at a high speed (for example, a roll temperature of 130 ° C or lower for bonding, and a transfer speed of 1 m/min or more). The high-adhesiveness can form a positive photosensitive transfer material of a circuit wiring and a manufacturing method of a circuit wiring with high resolution.

In the following, the positive photosensitive transfer material and the method of manufacturing the circuit wiring of the present invention further include the circuit wiring and the input device according to the present invention, particularly an input device as a touch panel, and a display device using the input device. Description. In addition, the description will be made with reference to the accompanying drawings, but the description is omitted. In addition, the numerical range represented by the "-" in this specification is the range which has the numerical value of the [--- In the present specification, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, and "(meth)acrylate" means either or both of acrylate and methacrylate. .

[Positive Photosensitive Transfer Material] The positive photosensitive transfer material of the present invention includes a temporary support and a positive photosensitive resin layer, and the positive photosensitive resin layer includes the following formula A. The polymer having a weight average molecular weight of 1.0 × 10 ⁵ or less, a plasticizer having a weight average molecular weight smaller than that of the polymer having the structural unit represented by Formula A, and a photoacid generator are disposed on the temporary support.

[Chemical 2]

In the formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ represents an alkyl group or an aryl group, and R ³¹ Or 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 extended aryl group.

Fig. 1 schematically shows an example of a layer configuration of a positive photosensitive transfer material of the present invention. The positive photosensitive transfer material 100 shown in FIG. 1 is sequentially laminated with a temporary support 12, a positive photosensitive resin layer 14, and a cover film 16. The positive photosensitive resin layer 14 includes a polymer having a structural unit represented by Formula A and having a weight average molecular weight of 1.0×10 ⁵ or less, and a plasticizer having a weight average molecular weight smaller than that of the polymer having the structural unit represented by Formula A. And photoacid generators. Hereinafter, constituent materials and the like of the positive photosensitive transfer material of the present invention will be described. Further, the above-described configuration in the present invention may be referred to as follows in the present specification. The constituent unit represented by Formula A is sometimes referred to as "constituting unit (a)". A polymer having a structural unit represented by Formula A and having a weight average molecular weight of 1.0 × 10 ⁵ or less is sometimes referred to as a "specific polymer". The plasticizer having a weight average molecular weight smaller than the polymer having the constituent unit represented by Formula A may be simply referred to as a "plasticizer". The positive photosensitive resin layer may be referred to as a "photosensitive resin layer".

[Temporary Support] The temporary support 12 is a support that can support the positive photosensitive resin layer and can be peeled off from the positive photosensitive resin layer. In order to perform pattern exposure on the positive photosensitive resin layer, the positive photosensitive resin layer can be exposed via a temporary support, and the temporary support 12 used in the present invention preferably has light transmissivity. The light transmissive property means that the transmittance of the dominant wavelength of the pattern exposure is 50% or more, and the transmittance is preferably 60% or more, and more preferably 70% or more from the viewpoint of improving the sensitivity. Examples of the temporary support include a glass substrate, a resin film, and paper. From the viewpoint of strength and flexibility, a resin film is particularly preferred.

The thickness of the temporary support is not particularly limited, and as long as the strength of the support, the flexibility required for bonding the circuit wiring forming substrate, and the light transmittance required in the first exposure step, You can choose according to the material.

A preferred embodiment of the temporary support is described in [0017] to [0018] of JP-A-2014-85643, the contents of which are hereby incorporated by reference.

[Positive Photosensitive Resin Layer] The positive photosensitive resist material 100 of the present invention includes a positive photosensitive resin layer 14 disposed on the temporary support 12 . The positive photosensitive resin layer 14 of the present invention comprises a polymer (specific polymer) having a weight average molecular weight of 1.0 × 10 ⁵ or less and having a weight average molecular weight of less than a specific polymer. Plasticizer, and photoacid generator.

<Polymer component> (Specific polymer) The positive photosensitive resin layer of the present invention contains a specific polymer having a structural unit (a) represented by Formula A and having a weight average molecular weight (Mw) of 1.0 × 10 ⁵ or less. As a polymer component. The specific polymer is one of a polymer having a protective carboxyl group protected by an acid-decomposable group, but in the structural unit having a protective carboxyl group protected by an acid-decomposable group, from the viewpoint of improving sensitivity, a preferred formula is preferred. The constituent unit (a) indicated by A.

In the formula A, when R ³¹ or R ³² is an alkyl group, the number of carbon atoms is preferably an alkyl group of 1 to 10. In the case where 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 the formula A, R ³³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. In the formula A, R ³¹ or R ³² may be bonded to R ³³ to form a cyclic ether, preferably R ³¹ or R ³² , and is bonded to R ³³ to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, and is preferably 5 or 6, more preferably 5. In the formula A, R ³⁴ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In the formula A, X ⁰ represents a single bond or an extended aryl group, preferably a single bond.

In the structural unit (a) represented by the formula A, the structural unit represented by the following formula (A1) is more preferable from the viewpoint of further improving the sensitivity.

(A1) [Chem. 3]

In the formula (A1), R ¹²¹ represents a hydrogen atom or a methyl group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the formula (A1), R ^{121 is} preferably a hydrogen atom or a methyl group. In the formula (A1), R ¹²² to R ^{128 are} preferably a hydrogen atom.

A preferred specific example of the structural unit (a) having a protective carboxyl group protected by an acid-decomposable group represented by Formula A can be exemplified by the following structural unit. Further, R represents a hydrogen atom or a methyl group.

[Chemical 4]

The polymer component contained in the positive photosensitive resin layer may have another constituent unit (b) in addition to the structural unit (a) represented by Formula A. The polymer having the structural unit (a) represented by Formula A may also contain another constituent unit (b) as a copolymerization component. Further, unlike the polymer containing the constituent unit (a) represented by Formula A used in the polymer component, the polymer substantially not containing the constituent unit (a) represented by Formula A may have other constituent units ( b).

When the specific polymer is a copolymer, the copolymerization ratio of the structural unit (a) in the polymer having the structural unit (a) represented by Formula A is preferably 5 mol% with respect to the polymer. 90% by mole, more preferably 10% by mole to 80% by mole, particularly preferably 30% by mole to 70% by mole. In addition, after all the polymer components are decomposed into a constituent unit (monomer unit), a constituent unit of a protective carboxyl group having an acid group protected by an acid-decomposable group is provided with respect to the number of moles of all constituent units. The ratio is preferably from 0 mol% to 80 mol%, more preferably from 10 mol% to 70 mol%, particularly preferably from 15 mol% to 50 mol%.

The monomer to be another constituent unit (b) is not particularly limited, and examples thereof include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, and (meth)acrylic acid. Base ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid Acid, unsaturated dicarboxylic anhydride, and other unsaturated compounds. In addition, as described later, the polymer component contained in the positive photosensitive resin layer may have a constituent unit including an acid group as another constituent unit (b). The monomers which are other constituent units (b) may be used singly or in combination of two or more.

Specifically, the other constituent unit (b) includes constituent units derived from the following compounds: styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, and B. Nonyloxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid (3-methacryloxyloxy) Propyl)ester, (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 monoacetic acid acetate monomethyl ) Acrylate and the like. In addition, the compound described in Paragraph Nos. 0021 to 0024 of JP-A-2004-264623 is mentioned.

Further, from the viewpoint of electrical properties, the other constituent unit (b) is preferably a styrene group or a group having an aliphatic cyclic skeleton. Specific examples thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, and cyclohexyl (meth)acrylate. Ester, isobornyl (meth)acrylate, benzyl (meth)acrylate, and the like.

Further, from the viewpoint of adhesion, the other constituent unit (b) is preferably an alkyl (meth)acrylate. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. . In the constituent unit constituting the polymer comprising the structural unit (a) represented by the formula A, the content of the other constituent unit (b) is preferably 60 mol% or less, more preferably 50 mol% or less. It is 40% or less. The lower limit value may be 0 mol%, but may be, for example, 1 mol% or more, and may be 5 mol% or more. When it is in the above numerical range, the positive-type photosensitive transfer material is excellent in developability and resolution, and in particular, it is possible to obtain good developability and resolution in a weakly alkaline developing solution such as sodium carbonate.

The polymer component contained in the positive photosensitive resin layer preferably has a constituent unit containing an acid group as another constituent unit (b). By having a constituent unit containing an acid group, it is easily dissolved in an alkaline developing solution, and the development time can be shortened. The acid group in the present invention means a proton dissociative group having a pKa of 10 or less. The acid group is usually incorporated into the polymer as a constituent unit containing an acid group using a monomer capable of forming an acid group. When the constituent unit containing the acid group as described above is contained in the polymer, there is a tendency that the alkaline developing solution is easily dissolved. Examples of the acid group of the structural unit containing an acid group used in the other structural unit (b) include an acid group derived from a carboxylic acid group, an acid group derived from a sulfonylamino group, and a phosphonic acid group. An acid group, an acid group derived from a sulfonic acid group, an acid group derived from a phenolic hydroxyl group, a sulfonylamino group, a sulfonimide group, etc., preferably an acid group derived from a carboxylic acid group and/or An acid group derived from a phenolic hydroxyl group. The constituent unit containing an acid group used in the other constituent unit (b) is more preferably a constituent unit in which an acid group is substituted with a constituent unit derived from styrene or a constituent unit derived from a vinyl compound, and A constituent unit derived from (meth)acrylic acid.

Furthermore, from the viewpoint of optimizing the solubility of the developer and the physical physical properties of the film-type photosensitive resin layer, a constituent unit having an ester containing an acid group is also preferable.

In the present invention, from the viewpoint of sensitivity, the other constituent unit (b) is particularly preferably a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group.

The polymer having the structural unit (a) represented by the formula A preferably contains a constituent unit derived from a carboxylic acid group in another constituent unit (b) and/or an ester thereof as a copolymerization component, more preferably A constituent unit derived from (meth)acrylic acid, benzyl (meth)acrylate or 2-hydroxyethyl (meth)acrylate is included as a copolymerization component. In the case where the acid group is a phenolic acid group, the copolymerization ratio of the constituent unit including the acid group in the polymer including the constituent unit having the protective carboxyl group protected by the acid-decomposable group, with respect to the inclusion has an acid The polymer of the constituent unit of the carboxyl group protected by the decomposable group is preferably from 0 mol% to 40 mol%, more preferably from 0 mol% to 20 mol%. Further, in the case where the acid group is a carboxylic acid group, the copolymerization ratio of the constituent unit containing the acid group is preferably 0 with respect to the polymer including the constituent unit having a carboxyl group protected by the acid-decomposable group. Molar% to 30% by mole, more preferably 0% by mole to 20% by mole. The copolymerization ratio of the constituent unit of the acid group-containing ester in the polymer having the constituent unit protecting the carboxyl group protected by the acid-decomposable group, and the composition including the protective carboxyl group having the acid-decomposable group The polymer of the unit is preferably from 10 mol% to 80 mol%, more preferably from 15 mol% to 70 mol%, particularly preferably from 20 mol% to 60 mol%.

Among the polymer components contained in the positive photosensitive resin layer, the polymer having the structural unit (a) represented by Formula A may be one type or two or more types. The positive photosensitive resin layer contains, as a polymer component, a polymer comprising two or more constituent units including a group having an acid group protected by an acid-decomposable group, and may also contain a constituent unit represented by Formula A ( The polymer of a) acts as at least one polymer.

The molecular weight of the polymer (specific polymer) containing the structural unit (a) represented by Formula A contained in the positive photosensitive resin layer is 1.0 × 10 ⁵ or less in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight of the specific polymer contained in the positive photosensitive resin layer is 1.0 × 10 ⁵ or less, the melt viscosity of the positive photosensitive resin layer can be suppressed to a low value, and the substrate for circuit wiring can be formed. The bonding under low temperature (for example, 130 ° C or less) is achieved in the lamination (lamination). In addition, when the weight average molecular weight of the specific polymer is too small, it becomes too soft when the film is formed into a photosensitive resin layer on the temporary support, and is easily damaged during the treatment step, and there is excessive stickiness due to the addition. It becomes difficult to peel off the cover film. In view of the above, the weight average molecular weight of the specific polymer contained in the positive photosensitive resin layer is preferably from 2.0 × 10 ³ to 1.0 × 10 ⁵ , more preferably from 3.0 × 10 ³ to 5.0 × 10 ⁴ range. Further, the weight average molecular weight of each component contained in the positive photosensitive resin layer can be measured by gel permeation chromatography (GPC), and various commercially available devices can be used for the measurement device. And assay techniques are well known to those skilled in the art. Further, the ratio (dispersion) of the number average molecular weight to the weight average molecular weight of the specific polymer is preferably from 1.0 to 5.0, more preferably from 1.05 to 3.5.

(Manufacturing Method of Specific Polymer) The method for producing the specific polymer (synthesis method) is not particularly limited, and if an example is given, the polymerizable sheet including the constituent unit (a) represented by Formula A can be contained. The organic solvent in which the amount of the polymer and the polymerizable monomer of the other structural unit (b) are formed as needed, and polymerization is carried out by polymerization using a polymerization initiator. Further, it can also be synthesized by a so-called polymer reaction.

The positive photosensitive resin layer in the present invention preferably contains a polymer component in a proportion of 50 parts by mass to 99.9 parts by mass, more preferably 70 parts by mass to 98 parts by mass, based on 100 parts by mass of the total solid content. Contains polymer components.

In addition, the positive photosensitive material of the present invention preferably has a high adhesion even when the substrate for circuit wiring formation is bonded at a low temperature and a high speed, and is preferably positively sensitive. The total solid content of the resin layer is 70% by mass or more and 99% by mass or less based on the total ratio of the polymer having the constituent unit represented by Formula A to the plasticizer.

In addition, the positive photosensitive resin of the present invention is preferably a positive photosensitive resin from the viewpoint of exhibiting high adhesion even when the circuit wiring forming substrate is bonded at a low temperature and high speed. In the layer, the ratio of the polymer having the constituent unit represented by Formula A to the total amount of the polymer having the constituent unit represented by Formula A and the plasticizer is 60% by mass or more and 90% by mass or less.

(Other Polymer) The positive photosensitive resin layer in the present invention may contain a polymer (specific polymer) containing the structural unit (a) represented by Formula A as a polymer component, and may contain substantially no The structural unit (a) represented by Formula A has a polymer of another structural unit (a case called "other polymer"). In the case where the positive photosensitive resin layer of the present invention contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 30% by mass or less based on the total polymer component. 20% by mass or less.

The positive photosensitive resin layer may contain only one type of other polymer, or may contain two or more types, in addition to a specific polymer.

As the other polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer Co., Ltd.) can also be used. ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, East Asia Synthetic (manufactured)), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, BASF) Company manufacturing) and so on.

<Plasticizer> The positive photosensitive resin layer in the present invention contains a plasticizer. The plasticizer in the present invention is added for the purpose of improving the plasticity of the positive photosensitive resin layer. When the positive photosensitive resin layer contains a plasticizer in addition to the specific polymer, the melt viscosity is further lowered, and even if the positive photosensitive transfer material is bonded to the circuit wiring forming substrate at a low temperature and high speed, Get high adhesion.

From the viewpoint of imparting plasticity, the plasticizer preferably has a weight average molecular weight smaller than that of a specific polymer. The polymerization 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 particularly preferably 800 or more and less than 4,000, from the viewpoint of imparting plasticity. The plasticizer is not particularly limited as long as it is compatible with a specific polymer and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkylene group in the molecule. The alkylene oxide group contained in the plasticizer preferably has the following structure.

[Chemical 5]

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

Further, for example, even in the case of the compound having the alkyleneoxy group ("Compound X"), the compound X is specifically polymerized as compared with the positive photosensitive resin composition formed without the compound X. When the plasticity of the positive photosensitive resin composition obtained by mixing the body and the photoacid generator is not improved, the plasticizer in the present invention is not satisfied. For example, the arbitrarily added surfactant is used in an amount of less than 1% by weight of the usual solid content, and most of it is concentrated on the surface of the film without imparting plasticity to the composition, so even if the weight average molecular weight is smaller than the specific polymer, It is in accordance with the plasticizer in the present invention.

The plasticizer which can be used in the present invention is, for example, a compound having the following structure, but is not limited to these compounds.

[Chemical 6]

<Photoacid generator> The positive photosensitive resin layer in the present invention contains a photoacid generator. The photoacid generator used in the present invention is a compound which can generate an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X rays, or charged particle beams. The photoacid generator used in the present invention is preferably a compound which induces an acid to be irradiated with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but has no chemical structure. In addition, a photoacid generator which does not directly induce actinic rays having a wavelength of 300 nm or more is a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more by using a sensitizer 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 the irradiation of radiation is preferably 4.0 or less, and more preferably 3.0 or less. The lower limit 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 nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, sulfhydrazine sulfonate compounds, and oxime sulfonate compounds. Among these compounds, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of insulating properties. These photoacid generators may be used alone or in combination of two or more. Specific examples of the trichloromethyl-s-triazines and the diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494.

The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, is preferably exemplified by a compound containing an oxime sulfonate structure represented by the following formula (B1), which is incorporated in the specification of the present application.

[Chemistry 7]

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

Any group of the compound containing the oxime sulfonate structure represented by the formula (B1) may be substituted, and the alkyl group in R ²¹ may be linear, may be branched, or may be cyclic. The permitted substituents will be 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 a bridged type such as 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) An alicyclic group, preferably a bicycloalkyl group, is substituted. The aryl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may also be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

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

[化8]

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, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X ¹⁰ may be The same can be different.

The alkyl group of X ¹⁰ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group of 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), particularly preferably m4 is 1, ^X-10 is a methyl group, ^X-10 is substituted for the ortho position, R ⁴² is a C 1-4 straight chain alkyl group having 1 to 10, 7,7-dimethyl a compound of 2-oxo norbornylmethyl or p-tolylmethyl.

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

[Chemistry 9]

In the formula (B3), R ⁴³ has the same meaning as R ⁴² in the 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, or a cyano group. Or a nitro group, and n4 represents an integer of 0-5.

R ⁴³ in the formula (B3) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-positive Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl. X ^{1 is} preferably an alkoxy group having 1 to 5 carbon atoms, 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)benzylcarbonitrile, α-(ethylsulfonyloxyimino)benzylcarbonitrile, and α- (n-propylsulfonyloxyimido)benzylcarbonitrile, α-(n-butylsulfonyloxyimino)benzylcarbonitrile, α-(4-toluenesulfonyloxyimino)benzyl Nitrile, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4-methoxyphenyl] Acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino)-4-methoxybenzene Acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and the like, and may be used alone or in combination of two or more. The compound (i) to the compound (viii) can be obtained as a commercial product. In addition, it can also be used in combination with other types of photoacid generators.

[化10]

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

Formula (OS-1) [Chem. 11]

In the formula (OS-1), R ⁴¹¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group or an aryl group. Or a heteroaryl group. 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 an alkyl group or an aromatic group. base. 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, a decylamino group, a sulfo group or 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 or an alkyl group, and 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 them, from the viewpoint of sensitivity, it is preferred that R ⁴²¹ to R ⁴²⁴ are each a hydrogen atom. The functional groups described may each have a more substituent.

The compound represented by the formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

(OS-2) [Chemistry 12]

In the formula (OS-2), R ⁴⁰¹ , R ⁴⁰² and R ⁴²¹ to R ⁴²⁴ have the same meanings as those in the formula (OS-1), and the preferred examples are also the same. Among these, R ⁴⁰¹ in the formula (OS-1) and the formula (OS-2) is preferably a cyano group or an aryl group, and is preferably represented by the formula (OS-2) and R ⁴⁰¹ is The form of cyano, phenyl or naphthyl.

Further, in the oxime sulfonate compound, the steric structure (E, Z, etc.) of the hydrazine or the benzothiazole ring may be either one or a mixture.

Specific examples of the compound represented by the formula (OS-1) which can be suitably used in the present invention include the compounds described in Paragraph Nos. 0128 to 0132 of JP-A-2011-221494 (exemplified compounds b-1 to exemplified compounds). B-34), but the invention 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). An oxime sulfonate compound.

[Chemistry 13]

In the formulae (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. An atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represent an oxygen atom or a sulfur atom, and 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 formula (OS-3) to the formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent. In the formula (OS-3) to the formula (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Further, in the formulae (OS-3) to (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

Further, 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 the formula (OS-3) to the formula (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one ring which is a heteroaromatic ring, for example, the heteroaromatic ring and the benzene ring may be reduced. ring.

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, more preferably a hydrogen atom or an alkyl group. In the formula (OS-3) to the formula (OS-5), two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, and preferably one or two are an alkyl group, an aryl group or a halogen atom. More preferably, one is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the remainder is a hydrogen atom.

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

The aryl group in R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms in total 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 is preferably O. In the formula (OS-3) to the formula (OS-5), the ring including X ¹ to X ³ as a ring member is a 5-membered ring or a 6-membered ring. In the formulae (OS-3) to (OS-5), n ¹ to n ³ each independently represent 1 or 2. When X ¹ to X ³ are 0, n ¹ to n ³ are each independently preferably. In the case where X ¹ to X ³ are S, n ¹ to n ³ are each independently preferably 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 acid group, an aminosulfonyl group or an alkoxy group. Sulfosyl group. Wherein R ²⁴ , R ²⁷ and R ³⁰ are each independently preferably an alkyl group or an alkyloxy group. The alkyl group, the alkyloxy group, the sulfonic acid group, the aminosulfonyl group and the alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent. In the formula (OS-3) to the formula (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

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

Further, in the formulae (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, particularly preferably Is 0. In addition, each of the substituents of the formula (OS-3) to the formula (OS-5) is (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of JP-A-2011-221494. The preferred range of substituents is also preferred.

In addition, 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).

[Chemistry 14]

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, and R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ and 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 range of the formula (OS-6) to the formula (OS-11) is compared with (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of JP-A-2011-221494. The best range is the same.

Specific examples of the oxime sulfonate compound represented by the formula (OS-3) to the formula (OS-5) include the compounds described in Paragraph Nos. 0114 to 0120 of JP-A-2011-221494, but the present invention It is not limited to these compounds.

In the positive photosensitive resin layer, the nonionic photoacid generator is preferably 100 parts by mass based on the total resin component (preferably the total solid content, more preferably the total of the polymer) in the positive photosensitive resin layer. It is more preferably used in an amount of from 0.1 part by mass to 10 parts by mass, even more preferably from 0.5 part by mass to 10 parts by mass. It is also possible to use two or more types together.

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

The triarylsulfonium salt used as the ionic photoacid generator is represented by the following formula (1).

[化15]

In the 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, may be bonded to each other to form a ring; X ^- represents a conjugated salt group. .

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. The alkyl group as described above may, for example, be methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl or the like. Among them, a methyl group, an ethyl group or a tert-butyl group is preferred. Further, in the case where two or more of R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ are an alkyl group, it is preferred that the two or more alkyl groups are bonded to each other to form a ring, and the ring form as described above contains a sulfur atom. The form is preferably a 5-membered ring (thiolane) and a 6-membered ring (thiamethylene). 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 as described above include a phenyl group, a naphthyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-tert-butylphenyl group, and a 4-phenylsulfuric acid. Phenylphenyl, 2,4,6-trimethylphenyl, 4-methoxy-1-naphthyl, or 4-(4'-diphenylmercaptophenylthio)phenyl. Further, the ionic photoacid generator represented by the formula (1) may be bonded by any of R ⁵⁰⁵ to R ⁵⁰⁷ to form a polymer 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 preferably an aromatic group, and particularly preferably a phenyl group, a 4-methoxyphenyl group or a 4-chlorophenyl group. 4-(4'-Diphenylmercaptophenylthio)phenyl. These substituents may also be further substituted with a substituent.

The conjugated salt group in X ^- is preferably a conjugated salt group of an alkyl sulfonic acid, a conjugated salt group of an aryl sulfonic acid, BY ₄ ^- (Y represents a halogen atom; the same applies hereinafter), PY ₆ ^- , AsY ₆ ^- , SbY ₆ ^- or a monovalent anion represented by the following formula (3) or (4), particularly preferably a conjugated salt of an alkylsulfonic acid, a conjugated salt of an arylsulfonic acid, PY ₆ ^- or a monovalent anion represented by the formula (3).

The conjugated salt group of the alkylsulfonic acid and the arylsulfonic acid is preferably a conjugated salt of an alkylsulfonic acid having 1 to 7 carbon atoms, more preferably a conjugated alkylsulfonic acid having 1 to 4 carbon atoms. The salt group, if expressed in the form of an acid, is particularly preferably methanesulfonic acid, trifluoromethanesulfonic acid, n-propanesulfonic acid, and heptanesulfonic acid. The conjugated salt group of the arylsulfonic acid is represented by an acid, and examples thereof include benzenesulfonic acid, chlorobenzenesulfonic acid, and p-toluenesulfonic acid.

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.

[Chemistry 16]

In the 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 of 1 to 10 carbon atoms, or R ^{521 .} A ring in which R ^{522 is} bonded to each other by an alkylene group having 2 to 6 carbon atoms or an alkylene group having a fluorine atom having 2 to 6 carbon atoms.

In the formula (3) and the formula (4), examples of the alkyl group having 1 to 10 carbon atoms in R ⁵²¹ , R ⁵²² and R ⁵²³ include a methyl group, an ethyl group, a butyl group, a tert-butyl group and a cyclohexyl group. , 辛基, etc. Further, examples of the alkyl group having a fluorine atom having 1 to 10 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, a perfluorooctyl group, and the like. . In these groups, R ⁵²¹ , R ⁵²² and R ^{523 are} preferably an alkyl group having a fluorine atom having 1 to 10 carbon atoms, particularly preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms. In the formula (3) and the formula (4), in the case where R ⁵²¹ and R ⁵²² are bonded to each other to form a ring, the alkylene group having 2 to 6 carbon atoms may be exemplified by an exoethyl group, a propyl group and a butyl group. Base, pentyl group, and hexyl group. Further, examples of the alkylene group having a fluorine atom having 2 to 6 carbon atoms include a tetrafluoroextension ethyl group, a hexafluoroextension propyl group, an octafluorobutylene butyl group, a decafluoropentyl group, and an undecafluorohexyl group. In 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 a fluorine atom of 2 to 6 carbon atoms, particularly preferably a carbon atom. A number of 2 to 4 alkyl groups having a fluorine atom are bonded.

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

[化17]

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 conjugated salt group.

The alkyl group and the aromatic group in R ⁵¹⁰ , R ⁵¹¹ , R ⁵¹² and R ⁵¹³ have the same meanings as the alkyl group and the aromatic group represented by R ⁵⁰⁵ , R ⁵⁰⁶ and R ^{507 of} the formula (1), and the preferred embodiment is also the same. In addition, the substituents which may be present are also the same.

The conjugated salt group in X ^1- and X ^2- has the same meaning as the conjugated salt group represented by X ^{- in} the formula (1), and the preferred embodiment is also the same.

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

Specific examples of the triarylsulfonium salt used as the ionic photoacid generator include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, and 4-methoxyphenyldiphenyl. Based on trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-phenylthiophenyldiphenylphosphonium 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 Co., Ltd.); GSID-26-1, Cyracure UVI-6976 (above, BASF).

The diarylsulfonium salt used as the ionic photoacid generator is represented by the formula of the following formula (2).

[化18]

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

In the formula (2), the aromatic group in R ⁵⁰⁸ and R ⁵⁰⁹ has the same meaning as the aromatic group represented by R ⁵⁰⁵ , R ⁵⁰⁶ and R ^{507 in} the formula (1), and the preferred embodiment is also the same. In the formula (2), the conjugated salt group in X ^1- has the same meaning as the conjugated salt group represented by X ^{- in} the formula (1), and the preferred embodiment is also the same. Further, the photoacid generator represented by the formula (2) may be bonded to R ⁵⁰⁸ to R ⁵⁰⁹ to form a polymer 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 diarylsulfonium salt used as the ionic photoacid generator include diphenylsulfonium trifluoroacetate, diphenylsulfonium trifluoromethanesulfonate, and 4-methoxyphenylbenzene. Base trifluoromethanesulfonate, 4-methoxyphenylphenylphosphonium trifluoroacetate, phenyl, 4-(2'-hydroxy-1'-tetradecyloxy)phenylfluorene trifluoromethyl Sulfonate, 4-(2'-hydroxy-1'-tetradecyloxy)phenylphosphonium hexafluoroantimonate, phenyl, 4-(2'-hydroxy-1'-tetradecyloxy) Phenylhydrazine-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 salt used as the ionic photoacid generator include tetramethylammonium butyl tris(2,6-difluorophenyl)borate and tetramethylammonium hexyltris(p-chlorochloride). Phenyl)borate, tetramethylammonium hexyltris(3-trifluoromethylphenyl)borate, benzyldimethylphenylammonium butyl tris(2,6-difluorophenyl)borate, benzyl Dimethylphenylammonium hexyltris(p-chlorophenyl)borate, benzyldimethylphenylammonium hexyltris(3-trifluoromethylphenyl)borate, and the like.

Specific examples of the photoacid generator include the following compounds, but the photoacid generator used in the present invention is not limited to these compounds. [Chemistry 19]

[Chemistry 20]

[Chem. 21]

The content of the photoacid generator in the positive photosensitive resin layer is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 5 parts by mass, per 100 parts by mass of the polymer component. When the content of the photo-acid generator is 0.1 part by mass or more, the desired sensitivity (high sensitivity) is easily obtained, and when it is 10 parts by mass or less, the transparency of the coating film is easily ensured.

<Solvent> A positive photosensitive resin composition for forming a positive photosensitive resin layer (hereinafter referred to as a "photosensitive resin composition") is preferably prepared to form a positive photosensitive resin layer. A solution of the component dissolved in a solvent. A known solvent can be used as the solvent used for the positive photosensitive resin composition for forming the positive photosensitive resin layer, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol. Alcohol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ethers Acetate, dipropylene glycol monoalkyl ether, dipropylene glycol dialkyl ether, dipropylene glycol monoalkyl ether acetate, esters, ketones, guanamines, lactones, and the like. Further, a specific example of the solvent used in the positive photosensitive resin composition for forming the positive photosensitive resin layer is a solvent described in paragraphs 0174 to 0178 of JP-A-2011-221494. These are incorporated in this specification.

In addition, it may be further added to the solvents as needed: benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and different Buddha Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , Ethyl carbonate, propyl carbonate and other solvents. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used singly or in combination of two or more. More preferably, it is preferably propylene glycol monoalkyl ether acetate or propylene glycol dialkyl ether or propylene glycol diacetate. It is used in combination with diethylene glycol dialkyl ether or butanediol alkyl ether acetate.

Further, the solvent is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture of such solvents. The solvent having a boiling point of 130 ° C or more and less than 160 ° C can be exemplified by 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). The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ethyl ether (boiling point: 176 ° C), and 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 II Acetate (boiling point 232 ° C).

The content of the solvent in the positive photosensitive resin composition for forming the positive photosensitive resin layer is preferably 50 parts by mass to 95 parts by mass, based on 100 parts by mass of the total resin component in the photosensitive resin composition. It is preferably 60 parts by mass to 90 parts by mass.

<Sensitizer> The positive photosensitive resin layer in the present invention preferably further contains a sensitizer. In order to promote decomposition of the positive photosensitive resin layer in combination with a photoacid generator, it is preferable to contain a sensitizer, and in particular, when a nonionic photoacid generator is used, it is preferable to contain a sensitizer. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. Thereby, the photoacid generator chemically changes and decomposes to form an acid. When the sensitizing agent is contained, the exposure sensitivity is further improved, and when a nonionic photoacid generator having low absorption efficiency of visible light is used, it is particularly effective when the exposure light source is a g or h-ray mixing line.

The sensitizer is preferably an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a basic styryl derivative, a distyrylbenzene derivative, more preferably ruthenium. derivative. The anthracene derivative is preferably: ruthenium, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9 - bromine, 9-chloropurine, 9,10-dibromofluorene, 2-ethylhydrazine, 9,10-dimethoxyfluorene. The acridone derivative is preferably: acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone, N-ethyl-2-methyl Oxyacridone. The thioxanthone derivative is preferably thiazinone, diethyl thiazinone, 1-chloro-4-propoxythiaxanone or 2-chlorothiazinone. The coumarin derivative is preferably: coumarin-1, coumarin-6H, coumarin-110, coumarin-102. Examples of the basic styryl derivative include 2-(4-dimethylaminostyryl)benzoxazole, 2-(4-dimethylaminostyryl)benzothiazole, 2-( 4-Dimethylaminostyryl)naphthylthiazole. The distyrylbenzene derivative may, for example, be distyrylbenzene, bis(4-methoxystyryl)benzene or bis(3,4,5-trimethoxystyryl)benzene.

Specific examples of the sensitizer include the following, but the present invention is not limited thereto. Further, in the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

[化22]

The content of the sensitizer in the positive photosensitive resin layer is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 5 parts by mass, per 100 parts by mass of the polymerizable component. By setting the content of the sensitizer to 0.1 part by mass or more, it is easy to obtain the desired sensitivity, and by setting it to 10 parts by mass or less, it is easy to ensure the transparency of the coating film.

<Basic Compound> The positive photosensitive resin layer in the present invention preferably further contains a basic compound. The basic compound can be arbitrarily selected from the basic compounds used in the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of such a compound include the compounds described in Paragraph Nos. 0204 to 0207 of JP-A-2011-221494, the contents of which are incorporated herein by reference.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, and tri-positive. 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, nicotinic acid decylamine, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, hydrazine, pyrrolidine, piperidine, piperazine, morpholino compound, 4-methyl? Porphyrin, 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.3.0]-7-undecene, and the like. 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 the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds which can be used in the present invention 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 part by mass to 5 parts by mass, more preferably 0.005 part by mass to 3 parts by mass per 100 parts by mass of the total solid content of the positive photosensitive resin layer. Share.

<Heterocyclic Compound> The positive photosensitive resin layer in the present invention preferably contains a compound containing a heterocyclic compound. By adding a heterocyclic compound, the cured film obtained from the positive photosensitive resin layer can be made into a stronger film. The heterocyclic compound is not particularly limited as long as the polymer component is removed. For example, a compound having an epoxy group or an oxetanyl group or a heterocyclic compound containing an alkoxymethyl group in the molecule described below may be added, and other cyclic ethers and cyclic esters may be added. An oxygen-containing compound such as a (lactone), a nitrogen-containing compound such as a cyclic amine or an oxazoline, or a heterocyclic compound such as ruthenium, sulfur or phosphorus having d electrons may be added.

The amount of the heterocyclic compound added to the positive photosensitive resin layer is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass per 100 parts by mass of the total solid content of the positive photosensitive resin layer. The mass part is particularly preferably from 1 part by mass to 5 parts by mass. When it is added in this range, a cured film excellent in mechanical strength is obtained, and a cured film excellent in chemical resistance is obtained. A plurality of heterocyclic compounds may be used in combination. In this case, the total content of the heterocyclic compounds is calculated in total.

Specific examples of the compound having an epoxy group in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an aliphatic ring. Oxygen resin, etc.

These compounds are available as commercial products. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the market described in paragraph No. 0189 of JP-A-2011-221494 Sales, etc. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, Adeco resin (ADEKA) RESIN)EP-4011S (above, manufactured by ADEKA); NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, Addico ( ADEKA) (manufacturer); 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, Nippon Steel & Sumitomo Chemical Manufacturing); Cyrusde ( Celloxide) 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Celvenus B0134, B0177 (Daicel). These may be used alone or in combination of two or more.

Among these compounds, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and an aliphatic epoxy resin are more preferable, and an aliphatic epoxy resin is especially preferable.

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, East Asia Synthetic (Stock) manufacturing).

Further, the compound containing an oxetanyl group is preferably used singly or in combination with a compound containing an epoxy group.

Among these compounds, the positive photosensitive resin layer in the present invention preferably has a heterocyclic compound as a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

Further, a compound having both an alkoxydecane structure and a heterocyclic structure in the molecule can also be suitably used. For example, γ-glycidoxypropyl trialkoxy decane, γ-glycidoxypropyl alkyl dialkoxy decane, β-(3,4-epoxycyclohexyl)ethyl three Alkoxydecane. Among these compounds, more preferred is γ-glycidoxypropyl trialkoxydecane. These compounds may be used alone or in combination of two or more.

<Interacting Agent> The positive photosensitive resin layer in the present invention may further contain a surfactant. The surfactant may be any of an anionic, cationic, nonionic or amphoteric, but a preferred surfactant is a nonionic surfactant. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, anthrone series, and fluorine interface. Active agent. In addition, the following trade names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Eftop (electronic development of Mitsubishi Materials ( JEMCO)), Megafac (made by DiCai (DIC)), Fluorad (made by Sumitomo 3M), Asahi Guard, Shafulong ( Surflon) (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), and SH-8400 (Toray Dow Corning Silicone). Further, as the surfactant, a copolymer comprising a constituent unit A represented by the following formula (I-1) and a constituent unit B, and tetrahydrofuran (THF) is exemplified. The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography in the case of a solvent is 1.0 × 10 ³ or more and 1.0 × 10 ⁴ or less.

Formula (I-1) [Chem. 23]

In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number of 1 or more. And an alkyl group of 4 or less, L represents an alkylene group having 3 or more carbon atoms and 6 or less, p and q are mass percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20 mass%. A numerical value of % or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.

L is preferably a branched alkyl group represented by the following formula (I-2). R ⁴⁰⁵ in the formula (I-2) represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and preferably has a carbon number of 1 or more and 3 in terms of compatibility and wettability to a surface to be coated. The alkyl group below 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) [Chem. 24]

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 surfactants described in paragraphs [0017] of JP-A-4502784, and paragraphs [0060] to [0071] of JP-A-2009-237362 may be used.

These surfactants may be used alone or in combination of two or more. The amount of the surfactant added to the positive photosensitive resin layer is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, per 100 parts by mass of the total solid content in the positive photosensitive resin layer. It is particularly preferably from 0.01 part by mass to 3 parts by mass.

<Radiation Absorber> The positive photosensitive resin layer in the present invention preferably further contains a radiation absorber. The radiation absorbing agent is preferably an ultraviolet absorber, and particularly preferably a radiation absorber which exhibits so-called photofading property by reducing absorbance by ultraviolet light absorption. Specific examples thereof include a photodecolorizable material such as a naphthoquinone diazide derivative, a nitroxide or a diazonium salt (for example, Japanese Patent Publication No. Sho 62-40697, M. Sasano). The compound described in "Society of Photo-Optical Instrumentation Engineers (SPIE Symp. Proc.)", 631, 321 (1986). These materials are used for the purpose of averaging the light intensity distribution in the photosensitive resin layer by the radiation absorbing agent, and are obtained by a so-called Contrast Enhancement Lithography (CEL) effect. The effect of rectangular patterning and edge roughness improvement (see "Semiconductor Process Materials and Chemicals", edited by Sakamoto Masahiro, CMC Publishing (2006)).

<Other components> In the positive photosensitive resin layer of the present invention, metal oxide particles, a crosslinking agent other than the heterocyclic compound, an alkoxydecane compound, an antioxidant, a dispersing agent, and an acid proliferating agent may be further added. A known additive such as a development accelerator, a conductive fiber, a colorant, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a tackifier, and an organic or inorganic precipitation preventive agent. A preferred embodiment of the other components is described in each of [0165] to [0184] of JP-A-2014-85643, the contents of which are hereby incorporated by reference.

<Thickness of Positive Photosensitive Resin Layer> The thickness of the positive photosensitive resin layer is preferably 0.5 μm to 10 μm. When the thickness of the positive photosensitive resin layer is 10 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 from 0.8 μm to 5 μm, particularly preferably from 1.0 μm to 3.0 μm.

<Method of Forming Positive Photosensitive Resin Layer> The positive photosensitive resin composition for forming a positive photosensitive resin layer can be prepared by mixing and mixing the components in a predetermined ratio by any method. For example, each component may be previously formed into a solution dissolved in a solvent, and then the solutions may be mixed at a predetermined ratio to prepare a composition solution. The composition solution 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.

By applying the composition solution to the surface of the temporary support and drying it, the positive photosensitive resin material of the present invention in which the positive photosensitive resin layer is formed on the temporary support can be obtained (positive photosensitive transfer) Printed material).

<Contrast Enhancement Layer> The positive photosensitive transfer material of the present invention preferably further includes a positive photosensitive resin layer and a contrast enhancement layer. A Contrast Enhancement Layer Method (CEL method) using a Contrast Enhancement Layer (CEL) will be described. The method was published in 1983 by Griffing of General Electric Company (GE) (BF Griffing, PR West, "Electrical and Electronic Engineers" "Instrument of Electrical and Electronic Engineers (Electron Device Letters)", Vol ED 1-4, 14, 1983), as disclosed in U.S. Patent No. 4,702,996, Japanese Patent Publication No. Sho 62-40697, The aryl nitrone compound and the polymer bonding agent, which are substances which are discolored by light, are mainly formed on the positive photosensitive resin layer film to form the photochromic compound film, according to the procedure of the conventional method. Form a pattern. Generally, the portion of the light that is shielded by the reticle during exposure is also exposed to a plurality of weak light due to the interference effect, and the portion is blocked by the photo fading film (CEL) to achieve contrast between the exposed portion and the unexposed portion. The enhancement helps the resolution and depth of focus increase. It is also preferable to form an intermediate layer on the positive photosensitive resin layer and form a contrast enhancement layer (hereinafter referred to as "CEL" or "CE layer") on the intermediate layer. The intermediate layer is provided to prevent mixing of the CEL and the positive photosensitive resin layer. As disclosed in Japanese Laid-Open Patent Publication No. Hei 2-212851, CEL is a layer containing a material (referred to as a photochromic dye component) which absorbs the exposure wavelength before exposure, but with exposure The absorption is gradually reduced, that is, the transmittance of light is increased. As the photochromic dye component, a diazonium salt, a styrlbazolium salt, or an aryl nitroso salt is known. A phenol resin or the like is used as the film forming component. In addition, the contrast enhancement layer can be used as follows: [0004] to [0051] of JP-A-6-97065, and [0012] to [0055] of Japanese Patent Laid-Open No. Hei 6-332167; (photopolymer handbook), photopolymer symposium, industrial survey (1989); photopolymer technology (Photopolymer Technology), Yamaoka, Yongsong, and Nikkan Kogyo Shimbun (1988).

<Other Layers> The positive photosensitive transfer material of the present invention preferably further includes, for example, a temporary support, a thermoplastic resin layer, and a positive photosensitive resin layer, and may further include another layer such as a cover film. The preferred embodiment of the thermoplastic resin layer is described in [0189] to [0193] of JP-A-2014-85643, and the preferred embodiment of the other layer is [0194] of JP-A-2014-85643. [0196] The contents of this publication are incorporated in the present specification.

In the case where the positive photosensitive transfer material of the present invention includes another layer such as a thermoplastic resin layer, the photosensitive transfer material described in paragraphs [0094] to [0098] of JP-A-2006-259138 can be used. The production method is to make. For example, in the case of producing a positive photosensitive transfer material of the present invention comprising a thermoplastic resin layer and an intermediate layer, a solution (thermoplastic) in which an additive is dissolved together with a thermoplastic organic polymer is applied to a temporary support. After the thermoplastic resin layer is provided by drying the coating liquid for a resin layer, a preparation liquid prepared by adding a resin and an additive to a solvent in which the thermoplastic resin layer is not dissolved is applied to the thermoplastic resin layer (application for intermediate layer) Liquid), dry it to build an intermediate layer. Further, the coating liquid for a positive photosensitive resin layer prepared by dissolving a solvent which does not dissolve the intermediate layer is applied to the intermediate layer, and dried to laminate a positive photosensitive resin layer, whereby the present invention can be suitably produced. Positive photosensitive transfer material.

[Manufacturing Method of Circuit Wiring] The method of manufacturing the circuit wiring of the present invention is a method of manufacturing a circuit wiring, which includes, in order: (a) a bonding step, in which a substrate, that is, a substrate, and a constituent material are different from each other a conductive layer and a plurality of conductive layers of the second conductive layer, and a substrate on which the first conductive layer and the second conductive layer are the outermost layer are laminated on the surface of the substrate from the surface away from the substrate. The positive photosensitive resin layer of the positive photosensitive transfer material of the present invention is brought into contact with the first conductive layer and bonded; (b) the first exposure step, the positive photosensitive conversion after the bonding step a temporary support of the printing material, patterning the positive photosensitive resin layer; (c) a first developing step, after peeling off the temporary support from the positive photosensitive resin layer after the first exposure step, the first exposure The positive photosensitive resin layer after the step is developed to form a first pattern; (d) a first etching step of at least the first conductive layer and the second conductive of the plurality of conductive layers in the region where the first pattern is not disposed Floor a row etching process; (e) a second exposing step of patternwise exposing the first pattern after the first etching step in a pattern different from the first pattern; (f) a second developing step, after the second exposing step The first pattern is developed to form a second pattern; and (g) a second etching step of etching at least the first conductive layer of the plurality of conductive layers in the region where the second pattern is not disposed.

Conventionally, the photosensitive resin composition is classified into a negative type that remains as an image when irradiated to the actinic ray, and a positive type that remains as an image of a portion that is not irradiated with the actinic ray. . In the positive type, by irradiating an actinic ray, for example, a sensitizer which generates an acid by irradiation with an actinic ray, or the like, the solubility of the exposed portion is improved. Therefore, the exposed portion and the unexposed portion are not hardened during pattern exposure. When the pattern shape is defective, the substrate can be reused (rework) by full exposure or the like. Therefore, from the viewpoint of excellent secondary workability, it is preferably positive. Further, only the positive photosensitive resin layer can realize the technique of re-exposing the remaining photosensitive resin layer to produce different patterns.

According to the method of manufacturing a circuit wiring of the present invention, even when a positive photosensitive transfer material is bonded to a circuit wiring forming substrate at a low temperature and a high speed, high adhesion can be ensured. In the method of manufacturing the circuit wiring of the present invention, the circuit wiring including the conductive layers of the plurality of patterns can be formed by lamination (lamination) of the method for manufacturing the circuit wiring of the present invention, and therefore, the manufacturing efficiency is excellent, and The alignment of the conductive layers of multiple patterns is not required and is therefore suitable for use as an input device, particularly for touch panels.

Hereinafter, preferred embodiments of the method of manufacturing the circuit wiring of the present invention will be described. FIG. 2 schematically shows an example of a method of manufacturing a circuit wiring for a touch panel which is one embodiment of the present invention. Here, a case will be described in which a circuit wiring substrate including a conductive layer of two patterns including a substrate 22 and one surface away from the substrate 22 is manufactured using the circuit-forming substrate 20 The first conductive layer 24 and the second conductive layer 26 are sequentially arranged.

A case where the positive-type photosensitive resin layer in the positive photosensitive transfer material of the present invention is used as an etch resist (etching pattern) to obtain a conductive layer pattern of the capacitance type input device will be described. Further, the capacitance type input device includes a substrate (front plate or film substrate) and elements including at least the following (2) to (5) on the non-contact side of the substrate, and is preferably manufactured using the circuit wiring of the present invention. The method forms at least one of (2), (3), and (5). (2) the plurality of first electrode patterns (3) formed by the plurality of pad portions extending in the first direction via the connection portion are electrically insulated from the first electrode patterns and include the extension formed in a direction crossing the first direction The plurality of second electrode patterns (4) of the plurality of pad portions electrically connect the insulating layer (5) electrically insulated from the first electrode pattern and the second electrode pattern to at least one of the first electrode pattern and the second electrode pattern The details of the respective steps will be described below with respect to other conductive elements different from the first electrode pattern and the second electrode pattern.

(a) bonding step first, in the bonding step, for the substrate 20, that is, including the substrate 22, and a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 having different constituent materials, and On the surface of the substrate 22, a substrate (circuit wiring forming substrate) 20 in which the first conductive layer 24 and the second conductive layer 26 as the outermost layer are laminated in this order from the surface away from the substrate 22 is provided. The positive photosensitive resin layer 14 of the positive photosensitive transfer material 100 of the present invention is in contact with the first conductive layer 24 and bonded thereto. In addition, the bonding of the circuit wiring forming substrate and the positive photosensitive transfer material as described above is referred to as "transfer" or "lamination".

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

(Substrate) The substrate on which a plurality of conductive layers are laminated on the substrate is preferably a glass substrate or a film substrate, more preferably a film substrate. In the case of the circuit wiring for a touch panel, the method of manufacturing the circuit wiring of the present invention is particularly preferably a substrate-like resin composition. In addition, the substrate is preferably transparent. The refractive index of the substrate is particularly preferably from 1.5 to 1.52. The substrate may also include a light-transmitting substrate such as a glass substrate, and tempered glass represented by Corning's Gorilla Glass may be used. Further, as the transparent substrate, a material used in Japanese Patent Laid-Open Publication No. 2010-86684, Japanese Patent Laid-Open No. 2010-152809, and Japanese Patent Laid-Open No. 2010-257492 can be preferably used. When a film substrate is used as the substrate, it is more preferable to use a substrate having no optical strain and a substrate having high transparency, and specific examples of the raw material include polyethylene terephthalate (polyethylene terephthalate). Terephthalate, PET), polyethylene naphthalate, polycarbonate, triethyl fluorenyl cellulose, cyclic olefin polymer.

(Conductive Layer) The plurality of conductive layers formed on the substrate may be any of the common circuit layers or any of the conductive layers used in the touch panel wiring. The material of the conductive layer may, for example, be a metal or a metal oxide.

In the method of manufacturing a circuit wiring of the present invention, it is preferable that at least one of the plurality of conductive layers contains a metal oxide. Examples of the metal oxide used in the conductive layer include a metal oxide film such as indium tin oxide (ITO), indium zinc oxide (Indium Zinc Oxide, IZO), and SiO ₂ . The conductive layer is preferably a first electrode pattern, a second electrode pattern, and other conductive elements used in the capacitance type input device described later. Preferred embodiments of the other conductive layers will be described later in the description of the capacitance type input device.

(b) First Exposure Step In the first exposure step, the positive photosensitive resin layer 14 is subjected to pattern exposure through the temporary support 12 of the positive photosensitive transfer material after the bonding step.

As an example of the exposure step, the development step, and the other steps in the present invention, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 can also be suitably used in the present invention.

For example, a mask 30 having a predetermined pattern is disposed above the positive photosensitive material 100 disposed on the first conductive layer 24 (on the side opposite to the side in contact with the first conductive layer 24), Then, a method of performing exposure from the top of the mask via the mask 30 or the like is performed. In the present invention, the detailed arrangement of the patterns and the specific dimensions 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 the circuit wiring manufactured by the present invention, and at least to reduce the area occupied by the extraction wiring, at least a part of the pattern (especially touch The electrode pattern of the control panel and the portion from which the wiring is taken out are preferably thin wires of 100 μm or less, and particularly preferably 70 μm or less. Here, if the light source used for the exposure can be irradiated with light in a wavelength range (for example, 365 nm, 405 nm, etc.) in which the exposed portion of the positive photosensitive material can be dissolved in the developer, the light source can be appropriately selected and used. The light source. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure amount is usually from about 5 mJ/cm ² to about 200 mJ/cm ² , preferably from about 10 mJ/cm ² to about 100 mJ/cm ² . Further, for the purpose of improving the rectangularity and linearity of the pattern after the exposure, it is also preferred to carry out heat treatment before development. By the so-called "Post Exposure Bake" (PEB) step, the roughness of the pattern edge caused by the standing wave generated in the photosensitive resin layer at the time of exposure can be alleviated.

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

(c) First development step In the first development 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 subjected to Development is performed to form the first pattern 14A.

The first developing step is a step of forming a first pattern by developing the pattern-exposed positive photosensitive resin layer. The development of the pattern-exposed positive photosensitive resin layer can be carried out using a developing solution. The developing solution is not particularly limited as long as the exposed portion of the positive photosensitive resin layer is removed. For example, a known developing solution such as a developing solution described in JP-A-5-72724 can be used. Further, the developer is preferably a developer in which the exposure portion of the positive photosensitive resin layer performs a dissolution type development operation. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L is preferably used, and a small amount of an organic solvent miscible with water may be further added. Examples of the organic solvent which is miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono- N-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphorus Guanidine, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone, and the like. The concentration of the organic solvent in the developer is preferably from 0.1% by mass to 30% by mass. A known surfactant can be further added to the developer. The concentration of the surfactant in the developer is preferably from 0.01% by mass to 10% by mass.

The development method may be any one of liquid coating development, shower development, shower and rotation development, immersion development, and the like. Here, when the shower development is described, the developer can be blown onto the exposed positive photosensitive resin layer by spraying to remove the exposed portion. In addition, when a thermoplastic resin layer, an intermediate layer, or a CE layer or the like is provided, it is also preferred to spray a washing liquid having a low solubility of the positive photosensitive resin layer by spraying or the like before development. The thermoplastic resin layer, the intermediate layer, the CE layer, and the like are removed in advance. Moreover, it is preferable to remove the development residue while wiping off with a brush or the like by spraying the detergent or the like after the development. The liquid temperature of the developer is preferably from 20 ° C to 40 ° C, and the pH of the developer is preferably from 8 to 13.

Further, a post-baking step of heat-treating the pattern containing the positive photosensitive resin layer obtained by development may be included. The post-baking heating is preferably carried out in an environment of 0.08 atm to 1.2 atm, more preferably in an environment of 0.5 atm or more. On the other hand, it is preferably carried out in an environment of 1.1 atm or less, and particularly preferably in an environment of 1.0 atm or less. Further, it is particularly preferably carried out in an environment of about 1 atm (atmospheric pressure) from the viewpoint of not reducing the production cost without using a special pressure reducing device. The post-baking temperature is preferably from 110 ° C to 170 ° C, more preferably from 120 ° C to 160 ° C, particularly preferably from 130 ° C to 150 ° C. The post-baking time is preferably from 1 minute to 30 minutes, more preferably from 2 minutes to 10 minutes, and particularly preferably from 2 minutes to 4 minutes. The post-baking can be carried out in an air atmosphere or in a nitrogen-substituted environment, but it is preferably carried out in an air environment from the viewpoint of not reducing the production cost without using a special pressure-reducing device.

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 of the plurality of conductive layers 24, 26 in the region where the first pattern 14A is not disposed are subjected to an etching treatment. The first conductive layer 24A and the second conductive layer 26A having the same pattern are formed by etching.

The etching of the conductive layer can be applied by a known method such as the method described in paragraphs [0048] to [0054] of JP-A-2010-152155, and the like.

For example, a method of etching can be exemplified by a wet etching method which is usually performed by immersing in an etching liquid. The etching liquid used in the wet etching may be appropriately selected from an acid type or an alkaline type etching liquid depending on the object to be etched. The acid type etching liquid may, for example, be an aqueous solution having a single acidic component such as hydrochloric acid, sulfuric acid, hydrofluoric acid or phosphoric acid, or a mixed aqueous solution of an acidic component with a salt such as ferric chloride, ammonium fluoride or potassium permanganate. As the acidic component, a component obtained by combining a plurality of acidic components can also be used. The alkaline type etching liquid can be exemplified by a single aqueous solution of a basic component such as a salt of an organic amine such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine or tetramethylammonium hydroxide, and an alkaline component and permanganic acid. A mixed aqueous solution of a salt such as potassium. As the alkaline component, a component obtained by combining a plurality of basic components can also be used.

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

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

(e) Second Exposure Step After the first etching step, the first pattern 14A after the first etching step is subjected to pattern exposure 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 at least a portion corresponding to the portion of the first conductive layer to be removed in the second development step to be described later. The pattern exposure in the second exposure step may be applied in the same manner 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 Developing Step In the second developing step, the first pattern 14A after the second exposure step is developed to form the second pattern 14B. The exposed portion of the first pattern in the second exposure step is removed by development. Further, in the second developing step, the same method as the development in the first developing step can be applied.

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

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

(h) Positive Photosensitive Resin Layer Removal Step After the second etching step is completed, the second pattern 14B remains in a portion of the first conductive layer 24B. If the positive photosensitive resin layer is not required, all of the remaining positive photosensitive resin layers 14B may be removed.

The method of removing the remaining positive photosensitive resin layer is not particularly limited, and a method of removing it by chemical treatment can be mentioned. For the method of removing the positive photosensitive resin layer, for example, a peeling liquid in which a substrate having a positive photosensitive resin layer or the like is stirred at 30 to 80 ° C, preferably 50 to 80 ° C, is used. Immerse for 5 minutes to 30 minutes. The positive photosensitive resin layer used as an etching mask may be a resin layer which exhibits excellent resistance to liquidity at 45 ° C or lower, but preferably exhibits alkalinity if the temperature of the chemical liquid reaches 50 ° C or higher. The nature of the peeling liquid and the swelling. According to the above properties, when the peeling step is performed using a peeling liquid of 50° C. to 80° C., the step time is shortened, and the peeling residue of the positive photosensitive resin layer is reduced. In other words, the positive photosensitive resin layer serving as an etching mask exhibits good resistance in the etching step by setting a difference in the temperature of the chemical solution between the etching step and the step of removing the remaining positive photosensitive resin layer. The liquid chemical property, on the other hand, exhibits good peeling property in the removal step, and can simultaneously satisfy the two opposite characteristics of the drug resistance liquidity and the peeling property.

Examples of the peeling liquid include an inorganic alkaline component such as sodium hydroxide or potassium hydroxide, or an organic alkaline component such as a tertiary amine or a quaternary ammonium salt, and are dissolved in water, dimethyl hydrazine, and N-methylpyrrole. A retort or a stripping solution obtained by mixing the solutions. The peeling liquid can also be used and peeled off by a spray method, a shower method, a liquid coating method, or the like.

The method of manufacturing the circuit wiring of the present invention may also include any other steps. For example, the steps described below can be cited, but are not limited to the steps.

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

<Step of Decreasing Visible Light Reflectance> The method of manufacturing a circuit wiring of the present invention may include a step of performing a process of reducing a visible light reflectance of a part or all of a plurality of conductive layers on a substrate. The treatment for lowering the reflectance of visible light can be exemplified by oxidation treatment or the like. For example, copper oxide is formed by oxidizing copper to be blackened, whereby the visible light reflectance can be lowered. A preferred embodiment of the process for reducing the reflectance of the visible light is [0017] to [0025] of JP-A-2014-150118, and [0041], [0042] of JP-A-2013-206315. It is described in [0048] and [0058], and the contents of this publication are incorporated in the present specification.

<Step of Forming New Conductive Layer on Insulating Film> The method of manufacturing the circuit wiring of the present invention preferably further includes the steps of forming an insulating film on the formed circuit wiring, and forming a new conductive layer on the insulating film A step of. According to 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 of forming a permanent film can be mentioned. Further, an insulating film having a desired pattern may be formed by a photolithography method using an insulating photosensitive material. The step of forming a new conductive layer on the insulating film is not particularly limited. It is also possible to use a photosensitive photosensitive material to form a new conductive layer of a desired pattern by photolithography.

In addition, in the description with reference to FIG. 2, a case has been described in which a circuit wiring having two different patterns is formed on a circuit wiring forming substrate including two conductive layers, but the circuit of the present invention is applied. The number of the conductive layers of the substrate in the method of manufacturing the wiring is not limited to two, and the substrate for forming a circuit wiring in which three or more conductive layers are laminated may be used, and the exposure step, development step, and etching step may be performed. The combination is performed three times or more, thereby forming three or more conductive layers into different circuit wiring patterns.

In addition, although not shown in FIG. 2, the manufacturing method of the circuit wiring of the present invention is also preferably: the substrate includes a plurality of conductive layers on both side surfaces, and the conductive layers formed on both side surfaces of the substrate are successively applied. Or form a circuit at the same time. According to the configuration described above, the circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface can be formed. Further, it is also preferable that the circuit wiring for the touch panel having the above configuration is formed from both surfaces of the substrate by a roll-to-roller.

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

FIG. 3 shows an example of a circuit wiring for a touch panel, and is one of the embodiments of the circuit wiring that can be manufactured by the method of manufacturing the circuit wiring of the present invention. In FIG. 3, the first electrode pattern 3 is formed on the substrate 1, and other conductive elements 6 are formed on the first electrode pattern. The circuit wiring for a touch panel shown in FIG. 3 is a circuit wiring including a conductive layer of the following two patterns: a conductive layered body in which another conductive element different from the first electrode pattern 3 is formed, and only the first electrode Conductive layer of pattern 3. When the circuit wiring for the touch panel of FIG. 3 is observed from the obliquely upward direction, it is as shown in FIG. In an example of the circuit wiring for a touch panel shown in FIG. 4, the broken line portion in FIG. 4 is a conductive layered body in which other conductive elements different from the first electrode pattern 3 are formed, and the portion in which the quadrilateral of FIG. 4 is connected is only A conductive layer having the first electrode pattern 3. As described above, in the method of manufacturing the circuit wiring of the present invention, it is preferable that the conductive layer having a different type of pattern included in the circuit wiring includes two or more layers in which the conductive layers having at least one pattern share the same circuit pattern. Conductive layer laminate.

[Input Device and Display Device] An input device is exemplified as a device including the circuit wiring manufactured by the method of manufacturing the circuit wiring of the present invention. The input device in the present invention is preferably an electrostatic capacitance type touch panel. The display device of the present invention includes the input device of the present invention. The display device in the present invention is preferably an image display device.

<Image display device including a capacitive input device and a capacitive input device> A capacitive input device that is a preferred embodiment of the input device and the display device of the present invention, and a capacitive input device The image display device of the components can be applied: "The Latest Touch Panel Technology" (released on July 6, 2009, Techno Times), and "Technology and Development of Touch Panels" edited by Mitani Yuji , CMC Publishing (2004, 12); 2009 International Flat Panel Display Forum (FPD (Flat Panel Display) International 2009 Forum) T-11 lecture materials, Cypress Semiconductor Corporation (Cypress Semiconductor Corporation) application notes AN2292 and other disclosures .

First, the configuration of the capacitance type input device will be described. Fig. 5 is a cross-sectional view showing the configuration of a capacitance type input device. In FIG. 5, the capacitance type input device 10 includes a substrate 1, a mask layer 2, a first electrode pattern 3, a second transparent electrode pattern 4, an insulating layer 5, other 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 represented by Corning's Gorilla Glass can be used. In addition, in FIG. 5, the side of the front layer 1 in which each element is provided is called 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 to be input. In this specification, the front panel is referred to as a "substrate".

Further, a mask layer 2 is provided on the non-contact surface of the substrate 1. The mask layer 2 is a frame-like pattern around the display region formed on the non-contact side of the front panel of the touch panel, and is formed in order to prevent the lead wiring or the like from being seen. The mask layer 2 may be provided on the capacitance type input device 10 so as to cover a part of the substrate 1. Further, on the substrate 1, an opening portion may be provided in a part. A mechanical switch by squeezing may be provided at the opening.

Forming a contact surface of the substrate 1 with a plurality of first electrode patterns 3 formed by extending a plurality of pad portions in a first direction via the connection portion, electrically insulated from the first electrode patterns 3, and included in the first direction A plurality of second transparent electrode patterns 4 of a plurality of pad portions formed to extend in a crossing direction, and an insulating layer 5 electrically insulating the first electrode patterns 3 from the second transparent electrode patterns 4. The first electrode pattern 3, the second transparent electrode pattern 4, and other conductive elements 6 to be described later can be made of, for example, indium tin oxide (ITO) or indium zinc oxide (Indium Zinc Oxide, IZO). Conductive metal oxide film is produced. Examples of the metal film as described above include an ITO film; a metal film of Al, Zn, Cu, Fe, Ni, Cr, Mo, or the like; a metal oxide film of SiO ₂ or the like. In this case, the film thickness of each element can be set to 10 nm to 200 nm. Further, since the amorphous ITO film is formed into a polycrystalline ITO film by firing, the electric resistance can also be reduced. Further, the first electrode pattern 3 and the second transparent electrode pattern 4 are preferably formed using an positive photosensitive resin layer as an etch resist (etching pattern). In the formation of the second electrode layer for forming the second transparent electrode pattern, a known method can be used in addition to the photolithography method using a resist typified by the positive photosensitive resin layer used in the present invention. Alternatively, it may be produced by using a photosensitive transfer material containing a photosensitive resin composition using conductive fibers. In the case where the first conductive pattern or the like is formed by using ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to.

Further, 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 both side regions of the surface of the mask layer 2 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 both side regions of the surface of the mask layer 2 opposite to the substrate 1.

The first electrode pattern 3 and the second electrode pattern 4 will be described with reference to FIGS. 6 and 7 . 6 and 7 are explanatory views showing an example of the first electrode pattern and the second electrode pattern. As shown in FIGS. 6 and 7, the pad portion 3a of the first electrode pattern 3 is formed to extend in the first direction via the connection portion 3b. In addition, the second electrode pattern 4 is electrically insulated from the first electrode pattern by the insulating layer 5, and includes a plurality of pad portions extending in a direction crossing the first direction (the second direction in FIG. 3). Here, in the case where the first electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be integrally formed, or only the connection portion 3b may be formed, and the pad portion 3a and the second transparent electrode pattern 4 may be formed (pattern Into one. When the pad portion 3a and the second transparent electrode pattern 4 are formed (patterned) integrally, 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 Each layer is formed in such a manner that the first electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated from each other.

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

In addition, in FIG. 5, the transparent protective layer 7 is provided so that it may cover all the components. The transparent protective layer 7 may be configured to cover 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 material constituting the insulating layer 5 and the transparent protective layer 7 is preferably a material having high surface hardness and heat resistance, and a known photosensitive siloxane resin material, acrylic resin material or the like is used, and such materials are well known to those skilled in the art. In addition to the photolithography method, a known method such as inkjet or screen printing may be used for the patterning method of the insulating layer.

In the method of manufacturing the capacitance type input device, at least one of the first electrode pattern 3, the second transparent electrode pattern 4, and the other conductive elements 6 preferably uses a positive photosensitive resin layer as an etch resist (etching The pattern is formed by performing an etching process. Further, it is preferable that at least one element of the black mask layer 2, the insulating layer 5, and the optional transparent protective layer 7 also uses a photosensitive film including a temporary support, a thermoplastic resin layer, and a photocurable resin layer in this order. To form.

At least one of the first electrode pattern 3, the second transparent electrode pattern 4, and the other conductive elements 6 is preferably formed by performing an etching treatment using an positive photosensitive resin layer as an etch resist (etching pattern). When the first electrode pattern 3, the second transparent electrode pattern 4, and other conductive elements 6 are formed by etching, first on the non-contact surface of the substrate 1 on which the black mask layer 2 or the like is 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 substrate 1 or the inorganic insulating layer by sputtering. Then, a positive photosensitive resin layer having an etching photocurable resin layer as a photocurable resin layer on the transparent electrode layer is 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.

In the case where the first electrode pattern 3, the second transparent electrode pattern 4, and other conductive elements 6 are formed using a photosensitive film having a conductive photocurable resin layer, by being on the surface of the substrate 1, 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 transferred onto the non-contact surface of the substrate 1 or the inorganic insulating layer.

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

The present invention will be further specifically described below by way of examples. The materials, the amounts, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.

[Example 1] A positive photosensitive resin composition was produced in the following formulation.・Polymer component (polymer A1 having the following structural unit, weight average molecular weight: 5.0 × 10 ³ ): 7.73 parts, plasticizer (Compound B below, weight average molecular weight: 1,216): 1.93 parts • Photoacid generation The following compound A-1 described in paragraph 0227 of JP-A-2013-047765: 0.25 parts, surfactant (the following surfactant C): 0.01 part, additive (the following compound D): 0.08 Parts propylene glycol monomethyl ether acetate: 90.00 parts

Polymer A1: Polymer having the following constituent units [Chem. 25]

Compound B [Chem. 26]

Compound A-1 described in paragraph 0227 of Japanese Patent Laid-Open No. 2013-047765 [Chem. 27]

Surfactant C: Perfluoroalkyl-containing nonionic surfactant (F-554, manufactured by Di Ai Sheng (DIC) Co., Ltd.)

Compound D: a basic compound of the following structure (manufacturer: manufactured by Toyo Chemical Co., Ltd., product number: CMTU) [Chem. 28]

The positive photosensitive resin composition produced was applied to a polyethylene terephthalate film having a thickness of 50 μm as a temporary support by using a slit nozzle so that the dry film thickness was 2.5 μm (hereinafter Called "PET (A)"). Then, it was dried by a convection oven at 100 ° C for 2 minutes, and finally a polyethylene film (manufactured by Tredegar Co., Ltd., OSM-N) was pressure-bonded to form a positive photosensitive transfer material 1 as a cover film.

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

[Example 2] A positive photosensitive transfer material 2 was produced in the same manner as in Example 1 except that the amount of the polymer component and the plasticizer used was changed to the following.・Polymer component (polymer A1): 8.21 parts ・Plasticizer (Compound B): 1.45 parts

[Example 3] A positive photosensitive transfer material 3 was produced in the same manner as in Example 1 except that the amount of the polymer component and the plasticizer used was changed to the following.・Polymer component (polymer A1): 7.25 parts ・Plasticizer (Compound B): 2.41 parts

[Comparative Example 1] A positive photosensitive resin composition was produced in the following formulation.・Polymer component (1-ethoxyethyl protecting agent/p-hydroxystyrene copolymer of p-hydroxystyrene, 30 mol%/70 mol%, molecular weight: 1.1×10 ⁴ ): 9.58 parts • photoacid Producer (a compound of the following structure synthesized according to the method described in Paragraph No. 0108 of JP-A-2002-528451; in addition, in the following structure, Ts represents p-toluenesulfonyl): 0.2 part

[化29]

・Sensitizer (9,10-dibutoxyanthracene): 0.2 parts ・Interfacial surfactant (surfactant C): 0.01 parts ・Additive (Compound D): 0.01 parts ・ Propylene glycol monomethyl ether acetate: 90.00 Share

In the same manner as in Example 1, the photosensitive resin composition was applied onto PET (A) and dried to prepare a positive photosensitive transfer material 4.

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

<Layerability evaluation> The positive photosensitive photosensitive material 1 to the positive photosensitive transfer material 4 were cut into 50 cm squares, and the cover film was peeled off to have a linear pressure of 0.6 MPa and a linear velocity (layer). Lamination conditions of a press speed of 1.0 m/min or 3.6 m/min. were laminated on a PET substrate with a copper layer. The laminate roll was changed in temperature and laminated, and the area where the photosensitive resin layer was adhered to the copper layer at each temperature was visually evaluated, and the area to which the photosensitive resin layer was adhered/the transferred transfer material was The area "%" is used to find the area ratio of the adhesion. It is evaluated according to the following criteria A to C. A: 95% or more B: 90% or more and less than 95% C: less than 90%

<Identification of the resolution> The positive photosensitive photosensitive material 1 to the positive photosensitive transfer material 4 produced were laminated at the lowest laminating roll temperature at which the lamination adaptability was A (the linear pressure was 0.6). MPa, linear velocity: 3.6 m/min.) On a PET substrate with a copper layer, the temporary support was not peeled off, and exposed by an ultrahigh pressure mercury lamp through a line and space pattern with a line width of 20 μm. The support is temporarily supported for development. Development was carried out for 30 seconds by spray development using a 2.38% aqueous solution of 2.38% tetramethylammonium hydroxide (TMAH) at 23 °C. The exposure amount at which a line and space pattern of 20 μm can be formed was obtained in the above manner as the optimum exposure amount. Then, through various line width line and space pattern masks, exposure is performed in the same manner with an optimal exposure amount, and when developing in the same manner, the line and space which are the same line width as the mask can be resolved least. The pattern size is used as the resolution. The results are shown in Table 1 below.

[Table 1]

Even if the positive photosensitive transfer material of the example has the same resolution, it can be transferred at a lower temperature than the photosensitive transfer material of the comparative example, and a wide process margin can be obtained.

[Example 10] On a 100 μm thick PET substrate, ITO was formed by sputtering and a thickness of 150 nm as a second conductive layer, on which vacuum evaporation method was used and at a thickness of 200 nm Copper is formed into a film to form a circuit for forming a circuit as a first conductive layer.

A positive photosensitive transfer material 1 was laminated on the copper layer (linear pressure of 0.6 MPa, linear velocity of 3.6 m/min, and roll temperature of 100 ° C). The contact pattern exposure (first exposure step) is performed by using a photomask provided with the pattern A shown in FIG. 8 having a configuration in which a conductive layer pad is connected in one direction without peeling off the temporary support. The solid line portion and the ash portion of the pattern A shown in FIG. 8 are light blocking portions, and the other portions are openings, and the broken line portions imaginarily show aligned frames. Further, the solid line portion is set to a thin line of 70 μm or less. Hereinafter, the same thin lines are formed in the other examples and comparative examples.

Then, the temporary support was peeled off, and development was carried out using 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) (first development step), followed by washing with water to obtain a pattern having the shape of the first pattern (the pattern of the light-shielding portion of the pattern A). A positive photosensitive resin layer of a shape.

Then, using a copper etching solution (manufactured by Kanto Chemical Co., Ltd., Cu-02), the copper layer (first conductive layer) was etched, and then an ITO etching solution (manufactured by Kanto Chemical Co., Ltd., ITO-02) was used. The ITO layer (second conductive layer) is etched, whereby the copper layer (first conductive layer) and the ITO layer (second conductive layer) are each depicted in a first pattern (a pattern of the shape of the light shielding portion region of the pattern A) Substrate (first etching step).

Then, in a state where the alignment is matched, pattern exposure is performed using a mask provided with the opening of the pattern B and the light-shielding portion shown in FIG. 9 (second exposure step), and development is performed using 2.38% of an aqueous solution of TMAH (No. The second development step) is followed by water washing to obtain a positive photosensitive resin layer having a shape of a second pattern (a pattern of a light-shielding portion of the pattern A and a pattern of overlapping portions of the light-shielding portions of the pattern B). The ash portion of the pattern B shown in FIG. 9 is a light shielding portion, the other portion is an opening portion, and the broken line portion imaginarily indicates an aligned frame.

Then, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling liquid (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board. Thereby, the circuit wiring board of the pattern C shown in FIG. 10 is obtained. In FIG. 10, the area which is not a solid line is a state in which the PET substrate is exposed (both white and gray areas). The solid line portion in the ash region of Fig. 10 is in a state in which the ITO wiring is exposed. The solid line portion other than the solid line portion corresponds to the peripheral wiring portion, and the copper wiring is laminated on the ITO wiring, and has a configuration in which the same circuit pattern is shared.

Then, by using Cu-02, only the first conductive layer (copper layer) which is a region of the second pattern in which the positive photosensitive resin layer is not provided is etched (second etching step). Further, a peeling liquid (KP-301 manufactured by Kanto Chemical Co., Ltd.) was used, and the remaining photosensitive resin layer was peeled off to obtain a circuit wiring board. Thereby, a circuit wiring board having the wiring pattern C shown in FIG. 10 is obtained. In FIG. 10, the area which is not a solid line is a state in which the PET substrate is exposed (both white and gray areas). The solid line portion in the ash region of FIG. 10 is in a state in which the ITO wiring (second conductive layer) is exposed. The other solid line portion corresponds to the peripheral wiring portion, and a copper wiring (first conductive layer) is laminated on the ITO wiring to have a structure in which the same circuit pattern is shared. As a result of observing the circuit of the obtained circuit wiring board by a microscope, the pattern was free from peeling or chipping, and was a high-definition clear pattern.

[Example 20] On a 100 μm thick PET substrate, ITO was formed by sputtering and a thickness of 150 nm as a second conductive layer, on which vacuum evaporation method was used and thickness was 200 nm. Copper is formed into a film to form a circuit for forming a circuit as a first conductive layer. A positive photosensitive transfer material 1 was laminated on a copper layer (linear pressure of 0.6 MPa, linear velocity of 3.6 m/min, and roll temperature of 100 ° C). Pattern exposure is performed by using a mask provided with a pattern A having a structure in which a conductive layer pad is connected in one direction without peeling off the temporary support. Then, the temporary support was peeled off, developed, and then washed with water to obtain pattern A. Then, the copper layer was etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer was etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which both copper and ITO are depicted in pattern A.

Then, PET (A) was laminated again as a protective film on the remaining resist (positive type photosensitive resin layer). In this state, pattern exposure is performed using a mask provided with an opening of the pattern B in a state where the alignment is matched, and the cover film is peeled off, and development and water washing are performed. Then, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling liquid (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 by a microscope, the pattern was free from peeling or chipping, and was a high-definition clear pattern.

1‧‧‧Substrate
2‧‧‧mask layer
3‧‧‧electrode pattern
3a‧‧‧Piece part
3b‧‧‧Connected section
4‧‧‧Transparent electrode pattern
5‧‧‧Insulation
6‧‧‧Other conductive elements
7‧‧‧Transparent protective layer
10‧‧‧Electrostatic type input device
12‧‧‧ temporary support
14‧‧‧ Positive photosensitive resin layer
14A‧‧‧first pattern
14B‧‧‧second pattern
16‧‧‧ Cover film
20‧‧‧Substrate for circuit formation
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‧‧‧ mask
40‧‧‧ mask
100‧‧‧正 type photosensitive transfer material

FIG. 1 is a schematic view showing an example of a layer configuration of a positive photosensitive transfer material of the present invention. FIG. 2 is a schematic view showing an example of a method of manufacturing a circuit wiring for a touch panel using the positive photosensitive transfer material of the present invention. 3 is a schematic view showing an example of a circuit wiring for a touch panel which can be manufactured by the method for manufacturing a circuit wiring of the present invention. 4 is a schematic view showing an example of a circuit wiring for a touch panel which can be manufactured by the method for manufacturing a circuit wiring of the present invention. Fig. 5 is a schematic view showing a configuration of an example of an input device of the present invention. FIG. 6 is a schematic configuration diagram showing an example of the arrangement of the pad portion, the connection portion, and the second electrode pattern of the first electrode pattern. FIG. 7 is a schematic perspective view showing an example of the arrangement of the pad portion, the connection portion, and the second electrode pattern of the first electrode pattern. FIG. 8 is a schematic view showing a pattern A. FIG. 9 is a schematic view showing a pattern B. FIG. 10 is a schematic view showing a pattern C.

12‧‧‧ temporary support

14‧‧‧ Positive photosensitive resin layer

16‧‧‧ Cover film

100‧‧‧正 type photosensitive transfer material

Claims (11)

A positive photosensitive transfer material comprising: a temporary support; and a positive photosensitive resin layer comprising a polymer having a weight average molecular weight of 1.0 × 10 ⁵ or less and having a structural unit represented by the following formula A; a plasticizer having an average molecular weight smaller than a polymer having the constituent unit represented by the formula A, and a photoacid generator, and disposed on the temporary support; In the formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ represents an alkyl group or an aryl group, and R ³¹ Or 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 extended aryl group. The positive photosensitive transfer material according to claim 1, wherein the plasticizer is a compound having an alkylene group in the molecule. The positive photosensitive transfer material according to claim 1, wherein the polymer having the constituent unit represented by the formula A is the same as the total solid content of the positive photosensitive resin layer. The total ratio of the plasticizer is 70% by mass or more and 99% by mass or less. The positive photosensitive photosensitive material according to claim 1, wherein the positive photosensitive resin layer is polymerized with respect to the polymer having the constituent unit represented by the formula A and the plasticizing The ratio of the polymer having the constituent unit represented by the above formula A is 60% by mass or more and 90% by mass or less. The positive photosensitive transfer material according to the second aspect of the invention, wherein the polymer having the constituent unit represented by the formula A and the total solid content of the positive photosensitive resin layer The total ratio of the plasticizer is 70% by mass or more and 99% by mass or less, and is represented by the formula A with respect to the total amount of the polymer having the constituent unit represented by the formula A and the plasticizer. The ratio of the polymer of the constituent unit is 60% by mass or more and 90% by mass or less. The positive photosensitive transfer material according to any one of the first to fifth aspects of the present invention, further comprising 0.001 parts by mass based on 100 parts by mass of the total solid content of the positive photosensitive resin layer. ～10 parts by mass of a nonionic surfactant. The positive photosensitive photosensitive material according to claim 6, wherein the nonionic surfactant is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography. 1.0×10 ³ or more and 1.0×10 ⁴ or less, and a copolymer of the structural unit A and the structural unit B represented by the following formula (I-1), In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number. 1 or more and 4 or less alkyl groups, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less, and q is a value. A numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less. The positive photosensitive transfer material according to any one of the items 1 to 5, wherein the temporary support has a light transmissive property. The positive photosensitive transfer material according to claim 6, wherein the temporary support has light transmissivity. A method of manufacturing a circuit wiring, comprising: (a) a bonding step for a substrate, that is, including a substrate, and a plurality of conductive layers including a first conductive layer and a second conductive layer different in composition materials, and On the surface of the substrate, a substrate of the first conductive layer and the second conductive layer as a frontmost layer is laminated in this order from the surface away from the substrate, so as to be ninth as claimed in the patent application. The positive photosensitive resin layer of the positive photosensitive transfer material according to the item is in contact with the first conductive layer and bonded; (b) a first exposure step, after the bonding step The temporary support of the positive photosensitive transfer material, the pattern exposure of the positive photosensitive resin layer; (c) the first development step, the positive photosensitive resin layer after the first exposure step After the temporary support is peeled off, the positive photosensitive resin layer after the first exposure step is developed to form a first pattern; (d) a first etching step for the region where the first pattern is not disposed Among the plurality of conductive layers Between the first conductive layer and the second conductive layer being etched; (e) a second exposure step, in a pattern different from the first pattern, the first after the first etching step The pattern is subjected to pattern exposure; (f) a second developing step of developing the first pattern after the second exposing step to form a second pattern; and (g) a second etching step, At least the first one of the plurality of conductive layers in the region of the two patterns is subjected to an etching process. The method of manufacturing a circuit wiring according to claim 10, wherein after the first etching step and before the second exposure step, further comprising attaching the light transmissive to the first pattern a step of protecting the film, in the second exposing step, performing the pattern exposure on the first pattern via the protective film, and peeling off from the first pattern after the second exposing step After the protective film, the second etching step is performed.