JP6968273B2 - Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method. - Google Patents

Description

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

In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the wiring of the take-out wiring part are wired. The conductive layer pattern such as is provided inside the touch panel.
Generally, in forming a patterned layer, the number of steps for obtaining the required pattern shape is small, so a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is used. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

Further, as a conventional photosensitive resin composition, those described in Patent Document 1 or 2 are known.
As a conventional method, for example, in Patent Document 1, (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2), and (1) (a-1) acid groups are acids. A polymer having a structural unit having a group protected by a degradable group and (a-2) a structural unit having a crosslinkable group, and (2) (a-1) an acid group are protected by an acid-degradable group. A polymer having a structural unit having a group, (a-2) a polymer having a structural unit having a crosslinkable group, (B) a photoacid generator, (C) a solvent, and (S) a general formula (1). ) And the polymer having the structural unit represented by the general formula (2), and the polymer (S) is the general formula in all the repeating units of the polymer (S). The molar ratio of the structural unit represented by (2) is 0.3 to 5 times the molar ratio of the structural unit represented by the general formula (1) in all the repeating units of the polymer (S). The photosensitive resin composition is disclosed.

In formulas (1) and (2), R ¹⁰ and R ¹¹ independently represent a hydrogen atom or a methyl group, and L ¹ and L ² independently represent a single bond or a divalent linkage, respectively. Represents a group, R ^{1 to} R 4 independently represent an alkyl group having 1 to 12 carbon atoms or an alkoxy group ^{having 1 to 12 carbon atoms, and R 5} is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkyl group. Represents an alkoxy group having 1 to 12 carbon atoms.

Further, in Patent Document 2, at least one of the repeating unit a having a carboxyl group substituted with an acid unstable group and the repeating units b1 and b2 having a sulfonium salt represented by the following general formula (1). As described above, a resist material characterized by containing a polymer compound having a repeating unit c having an amino group is disclosed.

(In the formula, R ¹ , R ³ , R ⁸ , and R ¹² each independently represent a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ² represents an acid unstable group. X represents a simple acid group. bond, phenylene, or naphthylene group, or ester group, .R ⁴ is a linking group having 1 to 12 carbon atoms having a lactone ring is an alkylene group having 1 to 10 carbon atoms, or number 6-10 carbon It is an arylene group and may have a fluorine atom, a trifluoromethyl group, an ester group, an ether group, and a lactone ring. R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , and R ¹¹ are the same or may have. It is a different kind of linear, branched or cyclic alkyl group having 1 to 12 carbon atoms and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms and 7 carbon atoms. It represents an aralkyl group or a thiophenyl group of about 20 and has an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxycarbonyl group, a carbonate group, and a halogen atom, a cyano group, a hydroxyl group and a carboxyl group as substituents. also a good .Y represents a single bond, a methylene group, a fluorine atom or arylene group substituted with a trifluoromethyl group, or ^{-C (= O) -O-R} 17 - a is ^{.R 17} is fluorine atom or trifluoromethyl a substituted arylene group group .R ¹³ is a single bond or a straight, branched or cyclic alkylene group, R ^14, R ¹⁵ are each independently a hydrogen atom, the number of carbon atoms 1 to 20 Linear, branched or cyclic alkyl groups, t-butoxycarbonyl groups, or t-allyloxycarbonyl groups with ether bonds, thioether bonds, hydroxyl groups, formyl groups, acetoxy groups, cyano groups, aromatics. It may have a group, and R ¹³ and R ¹⁴ , R ¹³ and R ¹⁵ , and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. R ¹⁶ may be bonded to a hydrogen atom or R 15. Z may be a single bond, a methylene group, an arylene group, -O-, -C (= O) -O- or -C (= O) -OR ^18- C (=). O) -O-, R ¹⁸ is a single-bonded or linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. 0 <a <1.0, 0 ≦ b1 ≦ 0. 3, 0 ≦ b2 ≦ 0.3, 0 <b1 + b2 ≦ 0.3, 0 <c ≦ 0.5)

Further, as a conventional photosensitive transfer material, those described in Patent Document 3 are known.
Patent Document 3 includes a temporary support, a polymer represented by the following general formula A and a structural unit having an acid group, and a glass transition temperature of 90 ° C. or lower, and a photoacid generator. A photosensitive transfer material having a positive photosensitive resin layer containing the above is disclosed.

In the general formula A, R ³¹ and R ³² 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 is an alkyl group. Alternatively, it represents an aryl group, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether. R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group.

Patent Document 1: Japanese Patent Application Laid-Open No. 2015-187634 Patent Document 2: Japanese Patent Application Laid-Open No. 2011-39266 Patent Document 3: Japanese Patent Application Laid-Open No. 2017-156735

An object to be solved by one embodiment of the present invention is to provide a photosensitive transfer material having excellent laminating suitability and resolvability.
Another object to be solved by another embodiment of the present invention is to provide a method for manufacturing a resin pattern using the photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel. ..

The means for solving the above problems include the following aspects.
<1> The polymer component having a temporary support and a photosensitive resin layer, and the photosensitive resin layer containing at least one of the following a1 and a2, and a photoacid generator, is contained in the polymer component. A photosensitive transfer material having a glass transition temperature of 90 ° C. or lower.
a1: Polymer component containing a structural unit having an acid group protected by an acid-degradable group and a polymer having a structural unit having a pKaH of 3 or more a2: An acid group protected by an acid-degradable group Polymer component containing a polymer having a structural unit having a pKaH and a polymer having a structural unit having a pKaH of 3 or more <2> All groups having a pKaH of 3 or more contained in the photosensitive resin layer. The photosensitive transfer material according to <1>, wherein the proportion of groups having a pKaH of 3 or more contained in the polymer component is 30 mol% or more.
<3> Of all the groups having a pKaH of 3 or more contained in the photosensitive resin layer, the ratio of the groups having a pKaH of 3 or more contained in the polymer component is 50 mol% or more <1> or The photosensitive transfer material according to <2>.
<4> The polymer in the polymer component further has a structural unit having an acid group protected by an acid-degradable group and a structural unit other than the structural unit having a group having 3 or more pKaH <1> to <3. > The photosensitive transfer material according to any one of.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the structural unit having three or more groups of pKaH is the structural unit represented by the following formula I or formula II.

In formulas I and II, R ₁ represents a hydrogen atom or a methyl group, Z is a single bond, a methylene group, an arylene group, -O-, -C (= O) -NH- or -C (= O)-. Representing O-, R ₂ is a carbon which may have at least one group selected from the group consisting of a single bond or an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of number 1-10, where R ₃ and R ₄ are independently hydrogen atoms or ether bonds, thioether bonds, hydroxy groups, formyl groups, acetoxy groups, cyano. A linear, branched group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond and an aromatic group. Representing a cyclic or cyclic alkyl group, R ₂ and R ₃ , R ₂ and R ₄ , or R ₃ and R ₄ may be bonded to each other to form a ring, and Q ₁ has a nitrogen atom. Represents an aromatic group or a nitrogen-containing heteroaromatic group.

<6> The photosensitive transfer material according to <5>, wherein the structural unit having a group having 3 or more pKaH is the structural unit represented by the above formula I.
<7> The photosensitive transfer material according to any one of <1> to <6>, wherein the structural unit having an acid group protected by the acid-degradable group is a structural unit represented by the following formula A. ..

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

<8> A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate and sticking them together, and a step of pattern-exposing the photosensitive resin layer. A method for producing a resin pattern, comprising the steps of developing the exposed photosensitive resin layer to form a pattern, and the above-mentioned step of forming a pattern.
<9> The step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer. A circuit wiring including a step of pattern exposure, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not arranged. Production method.
<10> The method for manufacturing a circuit wiring according to <9>, wherein the conductive layer is a layer containing copper.
<11> The step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer. Manufacture of a touch panel including a step of pattern exposure, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not arranged. Method.

According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material having excellent laminating suitability and resolution.
Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.

It is a schematic diagram which shows an example of the layer structure of the photosensitive transfer material which concerns on this disclosure. It is a schematic diagram which shows the pattern A. It is a schematic diagram which shows the pattern B.

Hereinafter, the contents of the present disclosure will be described. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
Further, the numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition when a plurality of the substances corresponding to each component are present in the composition, unless otherwise specified. Means quantity.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams (active energy rays) are used. Can be mentioned.
Further, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, for the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) are used. It is a molecular weight converted by using a gel permeation chromatography (GPC) analyzer, a solvent THF (tetrahydrogen), and a differential refractometer, and using polystyrene as a standard substance.

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of the following a1 and a2, a polymer component, and a photoacid generator. The glass transition temperature (Tg) of the polymer component is 90 ° C. or lower.
a1: Polymer component containing a structural unit having an acid group protected by an acid-degradable group and a polymer having a structural unit having a pKaH of 3 or more a2: Acid group protected by an acid-degradable group In addition, the photosensitive transfer material according to the present disclosure is a positive photosensitive transfer material. ..

A low molecular weight basic compound (also referred to as "quencher") may be added to the conventional positive photosensitive transfer material for the purpose of capturing the generated acid and stopping the decomposition reaction of the acid-degradable group. rice field. However, in the conventional photosensitive transfer material to which the small molecule basic compound is added, the small molecule basic compound is likely to be unevenly distributed on the substrate side or the like to which the small molecule basic compound is transferred, and the uneven distribution causes hemming at the lower part of the resist pattern during development. The present inventors have found that the resolution may be poor. This problem is a problem peculiar to a photosensitive transfer material containing an acid-decomposable polymer having a Tg of 90 ° C. or lower and a photoacid generator, and has a high Tg of a non-transferable Tg of more than 90 ° C. such as a coating type. This was a problem not found in conventional resist compositions using polymers.
As a result of diligent studies, the present inventors have found that the photosensitive transfer material having the above-mentioned structure is excellent in laminating suitability and resolution.
Although the detailed mechanism for expressing the above effects is unknown, by containing a polymer having a structural unit in which pKaH has 3 or more groups, groups having 3 or more pKaH as a base component are fixed to the polymer. It is considered that the structural units having pKaH as a base component having 3 or more groups were suppressed from being unevenly distributed on the substrate side, and the deterioration of resolution due to the tailing of the resist pattern during development could be improved. There is. Therefore, even if a polymer component having a Tg of 90 ° C. or lower, which is considered to be easy for small molecule components to move, can be used, the decrease in resolution due to the tailing of the resist pattern during development can be improved, and the Tg can be increased. Since it is a polymer component at 90 ° C. or lower, it has excellent laminating suitability.

Further, since the photosensitive transfer material according to the present disclosure has the above configuration, it is possible to suppress the excessive diffusion of the acid generated by the photoacid generator, and a certain amount of time has passed after the photosensitive transfer material was exposed. It is possible to suppress the thinning of the line width of the obtained resin pattern even when the development is performed after the process (also referred to as "retention time dependence inhibitory property").

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

FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, a photosensitive resin layer 12, and a cover film 14 are laminated in this order.
The photosensitive resin layer 12 contains a polymer component satisfying at least one of a1 and a2 and a photoacid generator, and the glass transition temperature of the polymer component is 90 ° C. or lower.
Hereinafter, the constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described.

<Temporary support>
The temporary support is a support that supports the photosensitive resin layer and can be peeled off.
The temporary support used in the present disclosure is preferably light-transmitting from the viewpoint of being able to expose the photosensitive resin layer via the temporary support when pattern-exposing the photosensitive resin layer.
In the present disclosure, having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is exposure. From the viewpoint of improving sensitivity, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method for measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like. Of these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, and is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm in terms of ease of handling and versatility.
The thickness of the temporary support should be selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a wiring forming substrate, light transmission required in the first exposure process, and the like. Just do it.

Preferred embodiments of the provisional support are described in, for example, paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of this publication are incorporated in the present specification.

<Photosensitive resin layer>
The photosensitive transfer material according to the present disclosure has at least a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of a1 and a2, and a polymer component and photoacid generation. The glass transition temperature (Tg) of the polymer component containing the agent is 90 ° C. or lower.
The photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.
In the photoacid generators such as onium salts and oxime sulfonate compounds described later, the acid generated in response to active light is deprotection of the protected acid group in the binder having the acid group protected by acid decomposition. Since it acts as a catalyst for, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, which is a large value such as the power of 10. High sensitivity is obtained as a result of so-called chemical amplification.
On the other hand, when a quinonediazide compound (NQD) is used as a photoacid generator that is sensitive to active light, a carboxy group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less, and the chemically amplified type is suitable. Not applicable.

<< Polymer component >>
The polymer component contained in the photosensitive resin layer satisfies at least one of the following a1 and a2. The glass transition temperature of the polymer component is 90 ° C. or lower.
a1: Polymer component containing a structural unit having an acid group protected by an acid-degradable group and a polymer having a structural unit having a pKaH of 3 or more a2: Acid group protected by an acid-degradable group A polymer component having a structural unit having a pKaH of 3 or more and a polymer having a structural unit having a pKaH of 3 or more.

The polymer component preferably satisfies the above a1 from the viewpoint of developability, and preferably satisfies the above a2 from the viewpoint of ease of adjusting the physical properties.
In addition, at least one structural unit selected from the group consisting of a structural unit having an acid group protected by an acid-degradable group and a structural unit having an acid group, each of which is contained in the polymer component. It is preferable that it is a polymer having.
Each of the polymers shown in a1 and a2 may contain only one kind or two or more kinds.
Further, the polymer component may further contain a polymer other than the polymers shown in a1 and a2.
Unless otherwise specified, the polymer component in the present disclosure is meant to include other polymers added as necessary in addition to the above-mentioned aspects a1 and a2.

The polymer in the polymer component is preferably an addition polymerization type resin, and is derived from a structural unit derived from (meth) acrylic acid and / or an ester thereof, and / or a styrene compound and / or a vinyl naphthalene compound. It is more preferable that the polymer contains a structural unit thereof, and it is further preferable that the polymer contains a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, it may have a structural unit other than the above, for example, a structural unit derived from a vinyl compound or the like.

-Glass transition temperature (Tg) of polymer component-
The glass transition temperature (Tg) of the polymer component in the present disclosure is 90 ° C. or lower, preferably 60 ° C. or lower, and more preferably 50 ° C. or lower. Within the above range, the photosensitive resin layer has high adhesion and excellent transferability.
The lower limit of Tg is not particularly limited, but is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, further preferably 10 ° C. or higher, and particularly preferably 25 ° C. or higher. When the Tg of the polymer component is −20 ° C. or higher, good pattern forming property is maintained, and for example, when a cover film is used, peeling failure when peeling the cover film is suppressed.
Further, a structural unit having an acid group protected by an acid-degradable group in the present disclosure, a polymer having a structural unit having a pKaH of 3 or more, and a structure having an acid group protected by an acid-degradable group. The glass transition temperature (Tg) of the polymer having a unit or the polymer having a structural unit having a pKaH of 3 or more is preferably 90 ° C. or lower independently from the viewpoint of transferability. It is more preferably 20 ° C. or higher and 70 ° C. or lower, further preferably 10 ° C. or higher and 60 ° C. or lower, and particularly preferably 25 ° C. or higher and 50 ° C. or lower.

The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
The specific measurement method is carried out according to the method described in JIS K 7121 (1987). As the glass transition temperature in the present specification, the extrapolated glass transition start temperature (hereinafter, may be referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after holding the device at a temperature about 50 ° C. lower than the expected polymer Tg until the apparatus stabilizes, the heating rate is 20 ° C./min, which is about 30 ° C. than the temperature at which the glass transition is completed. ℃ Heat to a high temperature to draw a DTA curve or DSC curve.
The extra glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification is a straight line extending the baseline on the low temperature side of the DTA curve or the DSC curve to the high temperature side, and the stepwise change portion of the glass transition. It is calculated as the temperature at the intersection with the tangent line drawn at the point where the slope of the curve becomes maximum.

As a method for adjusting the Tg of the polymer to the above-mentioned preferable range, for example, the FOX formula is used as a guideline from the Tg of the homopolymer of each structural unit of the target polymer and the mass ratio of each structural unit. , It is possible to control the Tg of the target polymer.
About the FOX formula The Tg of the homopolymer of the first constituent unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constituent unit is W1, and the Tg of the homopolymer of the second constituent unit is Tg1. Is Tg2, and when the mass fraction in the copolymer of the second constituent unit is W2, the Tg0 (K) of the copolymer containing the first constituent unit and the second constituent unit is as follows. It is possible to estimate according to the equation.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
Using the FOX formula described above, the type and mass fraction of each structural unit contained in the copolymer can be adjusted to obtain a copolymer having a desired Tg.
It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.

Further, the glass transition temperature of the polymer component in the present disclosure is measured or calculated by measuring or calculating the glass transition temperature of each polymer contained in the polymer component, and is a weighted average, that is, the glass transition temperature of each polymer and the entire polymer component. It shall be obtained by adding the product with the mass ratio to.
Polymer component Tg = Tg of polymer 1 x content ratio of polymer 1 + Tg of polymer 2 x content ratio of polymer 2 + ...

-Weight average molecular weight (Mw) of polymer-
The weight average molecular weight (Mw) of the polymer is preferably 60,000 or less, more preferably 2,000 to 60,000, and more preferably 2,000 to 60,000, in terms of polystyrene-equivalent weight average molecular weight, from the viewpoint of laminating suitability. It is more preferably 000 to 50,000, and particularly preferably 15,000 to 50,000.
The weight average molecular weight and the number average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. , The measurement technique is known to those skilled in the art.
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) is used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) is used as a column. .6 mm ID x 15 cm, manufactured by Tosoh Corporation, Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, one each manufactured by Tosoh Corporation, connected in series, and THF (tetratetra) can be used as the eluent.
The measurement conditions are a sample concentration of 0.2% by mass, a flow velocity of 0.35 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and a differential refractive index (RI) detector. be able to.
The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", " It can be prepared by using at least two or more samples of any one of the seven samples of "A-2500" and "A-1000".

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

-A structural unit in which pKaH has 3 or more groups-
The polymer component includes a polymer having at least a structural unit having pKaH having 3 or more groups.
Specifically, for example, a polymer having a structural unit having an acid group protected by an acid-degradable group and a polymer having a structural unit having a pKaH of 3 or more, or an acid protected by an acid-degradable group. Examples thereof include polymers having no structural unit having a group and having a structural unit having a pKaH of 3 or more.
In the present disclosure, pKaH is pKa of a conjugate acid, and a group having a pKaH of 3 or more represents a group having a pKa of the conjugate acid of the group of 3 or more. For example, the value of pKaH of -NH ₂ is the value of _-NH ^{3 +} of pKa.
Further, in the present disclosure, pKaH is a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).
Specifically, the chemical structure of the structural unit having a specific functional group is calculated using the above ACD / ChemSketch, and the pKaH value of the specific functional group is calculated.

The group having a pKaH of 3 or more is preferably a group having a pKaH of 4 or more, more preferably a group having a pKaH of 5 or more, and a pKaH of 5 or more, from the viewpoint of resolution and retention time dependence inhibitory property. It is more preferable that the group is 5 or more and 15 or less, and it is particularly preferable that the pKaH is 6 or more and 10 or less.
In other words, the polymer component preferably contains a polymer having at least a structural unit having a group having a pKaH of 4 or more, and a pKaH of 5 or more, from the viewpoint of resolution and retention time dependence inhibitory property. It is more preferable to include a polymer having at least a structural unit having a group of 5 or more, further preferably to contain a polymer having at least a structural unit having a group having a pKaH of 5 or more and 15 or less, and a group having a pKaH of 6 or more and 10 or less. It is particularly preferable to include a polymer having at least a structural unit having the above.

The group having a pKaH of 3 or more is preferably a group having a nitrogen atom from the viewpoint of resolution and retention time dependence inhibitory property, and is preferably an aliphatic amino group, an aromatic amino group, or a nitrogen-containing complex. It is more preferably an aromatic ring group, further preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution and retention time dependence inhibitory property, it is the first. It is preferably a secondary amino group or a tertiary amino group.
The aromatic amino group is preferably an anilino group, a monoalkylanilino group, or a dialkylanilino group, and more preferably a monoalkylanilino group or a dialkylanilino group.
The nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic ring group is preferably a pyridine ring, an imidazole ring, or a triazole ring, more preferably a pyridine ring or an imidazole ring, and is a pyridine ring. Is particularly preferable.
Further, the nitrogen-containing heteroaromatic ring group may further have a substituent on the nitrogen-containing heteroaromatic ring. The substituent is not particularly limited, but is preferably an alkyl group, more preferably a methyl group.

Further, the group having a pKaH of 3 or more is particularly preferably a group having an alkylamine structure from the viewpoint of resolution and retention time dependence inhibitory property.
Examples of the alkylamine structure include dialkylamine and trialkylamine, and specifically, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, 1,2,2,6,6-penta. Examples thereof include an alkyl-4-piperidyl group and a 2,2,6,6-tetraalkyl-4-piperidyl group.

The structural unit having three or more groups of pKaH is preferably a structural unit represented by the following formula I or formula II from the viewpoint of resolution and retention time dependence inhibitory property, and is represented by the following formula I. It is more preferable that it is a structural unit to be formed.

In formulas I and II, R ₁ represents a hydrogen atom or a methyl group, Z is a single bond, a methylene group, an arylene group, -O-, -C (= O) -NH- or -C (= O)-. Representing O-, R ₂ is a carbon which may have at least one group selected from the group consisting of a single bond or an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of number 1-10, where R ₃ and R ₄ are independently hydrogen atoms or ether bonds, thioether bonds, hydroxy groups, formyl groups, acetoxy groups, cyano. A linear chain having 1 to 20 carbon atoms, which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond, and an aromatic group. Representing a branched or cyclic alkyl group, R ₂ and R ₃ , R ₂ and R ₄ , or R ₃ and R ₄ may be bonded to form a ring, respectively, and Q ₁ represents a nitrogen atom. Represents an aromatic group or a nitrogen-containing heteroaromatic group.

Z in the formula I is a single bond, an arylene group, -C (= O) -NH- or -C (= O) -O- from the viewpoint of resolution, retention time dependence inhibitory property and easiness of synthesis. It is preferably an arylene group, more preferably -C (= O) -NH- or -C (= O) -O-, and more preferably -C (= O) -NH- or -C (= O). -O- is particularly preferable.
Z in Formula II is preferably a single bond, an arylene group or —C (= O) —O— from the viewpoint of resolution, retention time dependence inhibitory property and ease of synthesis, and is preferably a single bond. Is more preferable.
_{R 2} in the formula I has at least one group selected from the group consisting of an ether bond, a urethane bond and a urea bond from the viewpoints of resolution, retention time dependence inhibitory property and easiness of synthesis. It is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has at least one group selected from the group consisting of an ether bond, a urethane bond and a urea bond. It is more preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, and particularly preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms.
_{R 2} in Formula II is preferably a single bond from the viewpoint of resolution, retention time dependence inhibitory property, and ease of synthesis.

_{R 3} and R ₄ in the formula I are independently each having 1 to 20 carbon atoms which may have a hydrogen atom or an ether bond from the viewpoints of resolution, retention time dependence inhibitory property and easiness of synthesis. It is preferably a linear, branched or cyclic alkyl group, and more preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
Further, in the formula I, from the viewpoint of resolution and retention time dependence inhibitory property, _{it is preferable that R 2} , R ₃ and R ₄ in the formula I are bonded to form a nitrogen-containing aliphatic ring. The embodiment in which the piperidine ring is formed is more preferable.
_{Q 1} in Formula II is preferably a nitrogen-containing heteroaromatic group from the viewpoint of resolution, retention time dependence inhibitory property, and easiness of synthesis, and is preferably a pyridyl group, a methylpyridyl group, an imidazoyl group, or a methylimidazole group. It is more preferably a group or a triazolyl group, further preferably a pyridyl group, and particularly preferably a 4-pyridyl group.

Specific examples of the monomer forming a structural unit in which pKaH has 3 or more groups include the following monomers.
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2 methacrylic acid , 6,6-Tetramethyl-4-piperidyl, Acrylic acid 2,2,6,6-Tetramethyl-4-piperidyl, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, Acrylic acid 2- (diethylamino) ethyl, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) acrylate ) Propyl, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl] acrylamide, allylamine, 4-aminostyrene, 4-vinyl Pyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-vinyl-1,2,4-triazole

In the above-mentioned monomer, R ¹² represents a hydrogen atom or a methyl group.

Further, the monomers having an amino group or a nitrogen-containing heterocyclic group described in JP-A-2015-187634 or JP-A-2011-39266 can also be mentioned.

A resin having at least a structural unit in which pKaH has 3 or more groups (for example, a structural unit having an acid group protected by an acid-degradable group, and a polymer having a structural unit in which pKaH has 3 or more groups. Alternatively, the content of the structural unit having a pKaH of 3 or more in the polymer having a structural unit having a pKaH of 3 or more is determined from the viewpoint of resolution and retention time dependence inhibitory property. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, and 0.1% by mass or more and 10% by mass or less with respect to the total mass of the coalescence. It is more preferably 0.4% by mass or more and 4% by mass or less, and most preferably 0.5% by mass or more and 2% by mass or less.
Further, the content of the structural unit having a group of 3 or more pKaH in the polymerizable component is 0.01 with respect to the total mass of the polymer component from the viewpoint of resolution and retention time dependence inhibitory property. It is preferably 0% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 8% by mass or less, further preferably 0.1% by mass or more and 5% by mass or less, and 0.4% by mass or less. It is particularly preferably 5% by mass or more and 4% by mass or less, and most preferably 0.5% by mass or more and 2% by mass or less.

Further, as will be described later, the photosensitive resin layer may contain a basic compound or the like having a group having a pKaH of 3 or more in addition to the group having a pKaH of 3 or more in the polymer.
From the viewpoint of resolution and retention time dependence suppression, the proportion of all groups containing 3 or more pKaH contained in the photosensitive resin layer is 3 or more groups containing 3 or more pKaH contained in the polymer component. , 30 mol% or more, more preferably 50 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more and 100 mol% or less.
The content (content ratio: mass ratio) of the structural unit having a group having a pKaH of 3 or more in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-NMR measurement.} ..

-A building block having an acid group protected by an acid-degradable group-
The polymer component includes a polymer having at least a structural unit having an acid group protected by an acid-degradable group.
Specifically, for example, a structural unit having an acid group protected by an acid-degradable group, a polymer having a structural unit having a pKaH of 3 or more, or a configuration having a pKaH of 3 or more. Examples thereof include polymers having no unit and having a structural unit having an acid group protected by an acid-degradable group.
By including the polymer having a structural unit having an acid group protected by an acid-degradable group in the polymer component, an extremely sensitive chemically amplified positive type photosensitive resin layer can be obtained.
As the "acid group protected by an acid-degradable group" in the present disclosure, known acid groups and acid-degradable groups can be used, and the present invention is not particularly limited. Specific examples of the acid group include a carboxy group and a phenolic hydroxyl group. Further, as the acid group protected by the acid-degradable group, a group relatively easily decomposed by an acid (for example, an ester group protected by a group represented by the formula A, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester). Use an acetal-based functional group such as a group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Can be done.
Among these, the acid-degradable group is preferably a group having a structure in which the acid is protected in the form of acetal from the viewpoint of sensitivity and resolution.

The structural unit having an acid group protected by the acid-degradable group is preferably a structural unit represented by the following formula A from the viewpoint of sensitivity and resolution.

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

In the formula A, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferable. R ³¹ and R ³² are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
In the formula A, R ³³ represents an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
Further, the alkyl group and the aryl group in ^{R 31 to} R ^{33 may have a substituent.}
In the formula A, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and it is preferable that ^{R 31} or R ³² and R ^{33 are linked to form a cyclic ether.} The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the formula A, X ⁰ represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
The structural unit represented by the above formula A is a structural unit having a carboxy group protected by an acid-degradable group. Since the polymer contains a structural unit represented by the formula A, it is excellent in sensitivity at the time of pattern formation and is superior in resolution.

In the formula A, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer can be lowered.
^{More specifically, the structural unit in which R 34} is a hydrogen atom in the formula A is preferably 20% by mass or more with respect to the total amount of the structural units represented by the formula A contained in the polymer.
The content (content ratio: mass ratio) of the structural unit in which ^R34 is a hydrogen atom in the formula A among the structural units having an acid group protected by the acid-degradable group ^{is 13} C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from the spectrum (NMR) measurement.

Among the structural units represented by the formula A, the structural unit represented by the following formula A2 is more preferable from the viewpoint of further increasing the sensitivity at the time of pattern formation.

In formula A2, R ³⁴ represents a hydrogen atom or a methyl group, and R ^{35 to} R ⁴¹ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A2, R ³⁴ is preferably a hydrogen atom.
In the formula A2, R ^{35 to} R ⁴¹ are preferably hydrogen atoms.

The following structural units can be exemplified as a preferable specific example of the structural unit having a carboxy group protected by an acid-degradable group represented by the formula A. In addition, R ³⁴ represents a hydrogen atom or a methyl group.

Further, as the structural unit having an acid group protected by the acid-degradable group, the structural unit represented by the following formula A3 is preferable from the viewpoint of suppressing deformation of the pattern shape.

In formula A3, ^RB1 and ^RB2 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of ^RB1 and ^RB2 is an alkyl group or an aryl group, and ^RB3 is an alkyl group or an aryl group. represents an aryl group, and R ^B1 or R ^B2, may be linked and the R ^B3 to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, X ^B represents a single bond or a divalent linking group , R ^B12 represents a substituent, and n represents an integer from 0 to 4.

In the formula A3, when ^RB1 or ^RB2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When ^RB1 or ^RB2 is an aryl group, a phenyl group is preferable. ^RB1 and ^RB2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A3, ^RB3 represents an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
^The alkyl group and the aryl group in R B1 ^{to R B3} may have a substituent.
In the formula A3, ^RB1 or ^RB2 and ^RB3 may be linked to form a cyclic ether, and it is preferable that ^RB1 or ^RB2 and ^{RB3 are linked to form a cyclic ether.} The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the formula A3, ^{X B} represents a single bond or a divalent linking group, a single bond or an alkylene group, -C (= O) O - , - C (= O) NR N -, - O- , or a combination thereof Is preferable, and a single bond is more preferable. The alkylene group may be linear, has a branch, may have a cyclic structure, or may have a substituent. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. When X ^B contains −C (= O) O−, it is preferable that the carbon atom contained in −C (= O) O− and the carbon atom to which ^RB4 is bonded are directly bonded. When ^{containing, -C (= O) NR N} - - is ^{X B -C (= O) NR} N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In Formula ^A3, the group containing R B1 ^{to R B3,} The ^{X B,} it is preferably bonded at para positions.
In the formula A3, ^RB12 represents a substituent, and an alkyl group or a halogen atom is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In the formula A3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula A3, ^RB4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer can be lowered.
^{More specifically, the structural unit in which RB4} is a hydrogen atom in the formula A3 is 20% by mass or more with respect to the total content of the structural unit having an acid group protected by the acid-degradable group contained in the polymer. Is preferable.
The content (content ratio: mass ratio) of the structural unit in which ^RB4 is a hydrogen atom in the formula A3 among the structural units having an acid group protected by the acid-degradable group ^{is 13} C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from the spectrum (NMR) measurement.

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

In the formula ^{A4, R B4} represents a hydrogen atom or a methyl ^group, are each R ^{B5 to R B11} independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon ^{atoms, R B12} represents a substituent, n represents 0 Represents an integer of ~ 4.
In the formula A4, ^RB4 is preferably a hydrogen atom.
In the formula ^A4, R ^{B5 to R B11} is a hydrogen atom is preferable.
In the formula A4, ^RB12 represents a substituent, and an alkyl group or a halogen atom is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In the formula A4, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

As a preferable specific example of the structural unit A4 represented by the formula A4, the following structural unit can be exemplified. In addition, ^RB4 represents a hydrogen atom or a methyl group.

The structural unit having an acid group protected by the acid-degradable group contained in the polymer may be one kind or two or more kinds.
The content of the structural unit having an acid group protected by the acid-degradable group in the polymer is preferably 10% by mass or more, preferably 10% by mass to 90% by mass, based on the total mass of the polymer. It is more preferably 20% by mass to 70% by mass.
The content (content ratio: mass ratio) of the structural unit having an acid group protected by the acid-degradable group in the polymer is confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-NMR measurement.} be able to.
Further, after decomposing all the polymer components into constituent units (monomer units), the content ratio of the constituent units having the acid groups protected by the acid-degradable groups in the polymer components is the total mass of the polymer components. It is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass with respect to the mass.

The mass ratio of the content mass ratio M _B of structural units containing a mass ratio M _A and pKaH constituent units having protected acid groups in the acid-decomposable group in the polymer component having three or more groups (M _A / M _B), from the viewpoint of resolution and the holding time period dependent inhibitory preferably from 5 to 200, more preferably from 10 to 150, more preferably 20 to 100.

From the viewpoint of developability and resolvability, the polymer in the polymer component is a structural unit other than a structural unit having an acid group protected by an acid-degradable group and a structural unit having a group having a pKaH of 3 or more (for example,). , A structural unit having an acid group, which will be described later, and other structural units).

-Constituent unit having an acid group-
The polymer in the polymer component may independently contain a structural unit having an acid group from the viewpoint of developability and resolvability.
A structural unit having an acid group is a protective group, for example, an acid group not protected by an acid-degradable group, that is, a structural unit having an acid group having no protecting group. By including the polymer having a structural unit having an acid group in the polymer component, the sensitivity at the time of pattern formation becomes good, and it becomes easy to dissolve in an alkaline developer in the developing process after pattern exposure, and the developing time is shortened. Can be planned.
The acid group in the present specification means a proton dissociative group having a pKa of 12 or less. The acid group is usually incorporated into a polymer as a structural unit having an acid group using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Further, the pKa of the acid group is preferably −5 or more.

By having at least one of the polymers in the polymer component having a structural unit having an acid group that is not protected by an acid-degradable group and setting the glass transition temperature of the polymer component to 90 ° C. or lower, the polymer can be prepared. The positive photosensitive resin layer contained has better resolution and sensitivity at the time of pattern formation while maintaining transferability and releasability from the temporary support at a good level.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonylimide group and the like. Of these, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
The introduction of the structural unit having an acid group into the polymer can be carried out by copolymerizing the monomer having an acid group.
The structural unit having an acid group may be a structural unit derived from styrene, a structural unit derived from a vinyl compound in which an acid group is substituted, or a structural unit derived from (meth) acrylic acid. preferable.

As the structural unit having an acid group, a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint of improving the sensitivity at the time of pattern formation.
The monomer having an acid group capable of forming a structural unit having an acid group is not limited to the above-mentioned example.

The structural unit having an acid group contained in the polymer may be only one kind or two or more kinds.
When the polymer has a structural unit having an acid group, the polymer having a structural unit having an acid group contains 0.1% by mass to 20% by mass of the structural unit having an acid group with respect to the total mass of the polymer. %, More preferably 0.5% by mass to 15% by mass, still more preferably 1% by mass to 10% by mass. Within the above range, the pattern forming property becomes better.
The content (content ratio: mass ratio) of the structural unit having an acid group in the polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ^{13 C-NMR measurement.}
Further, after decomposing all the polymer components into constituent units (monomer units), the content ratio of the constituent units having an acid group in the polymer components is 0.1 with respect to the total mass of the polymer components. It is preferably from% by mass to 20% by mass, more preferably from 0.5% by mass to 15% by mass, and particularly preferably from 1% by mass to 10% by mass.

-Other building blocks-
The polymer contains other structural units other than the above-mentioned structural unit having an acid group protected by an acid-degradable group, the structural unit having a group having a pKaH of 3 or more, and the structural unit having an acid group. , The photosensitive transfer material according to the present disclosure may be included as long as the effect is not impaired.
The monomer forming other constituent units is not particularly limited, and is, for example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid. Diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups with an aliphatic cyclic skeleton, and others. Unsaturated compounds can be mentioned.
Various properties of the polymer can be adjusted by adjusting at least one of the type and the content by using other structural units. In particular, by appropriately using other structural units, the Tg of the polymer component can be easily adjusted to 90 ° C. or lower.
The polymer may contain only one type of other structural unit, or may contain two or more types.

Other constituent units are specifically styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth). ) Methyl acrylate, (meth) ethyl acrylate, (meth) n-propyl acrylate, (meth) isopropyl acrylate, (meth) 2-hydroxyethyl acrylate, (meth) 2-hydroxypropyl acrylate, (meth) ) A structural unit formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetate acetate mono (meth) acrylate can be mentioned. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-246623 can be mentioned.

Further, as the other structural units, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical properties of the obtained transfer material. Specific examples of the monomers forming these constituent units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. And benzyl (meth) acrylate and the like. Among them, a structural unit derived from cyclohexyl (meth) acrylate is preferably mentioned.

Further, as the monomer forming other structural units, for example, (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Of these, a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The content of the other structural units is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, based on the total mass of the polymer. The lower limit value may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.

Above all, it is preferable that each of the polymers contained in the polymer component independently contains a structural unit having a carboxylic acid ester structure from the viewpoint of laminating suitability and resolvability. The structural units having a carboxylic acid ester structure include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and cyclohexyl (meth) acrylate from the viewpoint of laminating suitability and resolution. , 2-Ethylhexyl (meth) acrylate or benzyl (meth) acrylate is preferred, preferably methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate. The structural unit of origin is more preferred.
Further, the polymer shown in a1 or a2 is derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate from the viewpoint of laminating suitability and resolution. It is preferable to have two or more structural units derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate.

Further, each polymer contained in the polymer component may independently contain a structural unit represented by the following formula C as a structural unit having the carboxylic acid ester structure from the viewpoint of laminating suitability and resolvability. preferable.

Wherein ^{C, R C1} represents a hydrogen atom or a methyl ^{group, R C2} is a straight, branched or cyclic alkyl group, or an aralkyl group having 7 to 20 carbon atoms ..

R ^C2 in formula C, in view of the laminate suitability and resolution, a straight, branched or cyclic alkyl group, or, to be an aralkyl group 7-16 carbon atoms preferably , A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or a benzyl group is more preferable, and a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is particularly preferable.

Further, the polymer shown in a1 or a2 preferably contains a structural unit having a carboxylic acid ester structure in an amount of 30% by mass or more based on the total mass of the polymer from the viewpoint of laminating suitability and resolution. It is more preferably contained in an amount of mass% or more, more preferably 50% by mass to 80% by mass, and particularly preferably 60% by mass to 75% by mass.
Further, after decomposing all the polymer components into structural units (monomer units), the content ratio of the structural units having the carboxylic acid ester structure in the polymer components is 30 with respect to the total mass of the polymer components. It is preferably 5% by mass or more, more preferably 50% by mass or more, and particularly preferably 50% by mass to 80% by mass.

-Polymer manufacturing method-
The method for producing the polymer (synthesis method) is not particularly limited, but for example, the pKaH, which is a polymerizable monomer for forming a structural unit having an acid group protected by an acid-degradable group, is 3 or more. A polymerization initiator is contained in an organic solvent containing a polymerizable monomer for forming a structural unit having a group and, if necessary, a polymerizable monomer for forming a structural unit represented by the formula C. It can be synthesized by using and polymerizing. It can also be synthesized from other polymers by a so-called polymer reaction.

From the viewpoint of exhibiting good adhesion, the photosensitive resin layer in the present disclosure may contain the polymer component in a ratio of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer. It is preferably contained in a proportion of 70% by mass to 98% by mass, more preferably.

-Other polymers-
In addition to the polymer shown in a1 or a2, the photosensitive resin layer contains an acid group protected by an acid-degradable group as a polymer component as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired. It may further contain a polymer having a structural unit and a polymer having no structural unit having a pKaH of 3 or more (sometimes referred to as “another polymer”). When the photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total polymer components. It is more preferably 20% by mass or less.

In addition to the polymer shown in a1 or a2, the photosensitive resin layer may contain only one type of other polymer, or may contain two or more types.
As another polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all manufactured by Sartmer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all manufactured by Toa Synthetic Co., Ltd.), and Joncryl 690, Jonc. , Joncryl 67, Joncryl 586 (above, manufactured by BASF) and the like can also be used.

<< Photoacid generator >>
The photosensitive resin layer contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiating with active rays such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
As the photoacid generator used in the present disclosure, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm and generates an acid is preferable, but its chemical structure is not limited. In addition, a photoacid generator that is not directly sensitive to active light with a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
As the photoacid generator used in the present disclosure, a photoacid generator that generates an acid having a pKa of 4 or less is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator having a pKa of 2 or less is more preferable. A photoacid generator that generates the acid of the above is particularly preferable. The lower limit of pKa is not particularly determined, but is preferably -10.0 or more, for example.

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

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

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

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

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

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

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

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

The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution, and is 0. It is more preferably 5.5% by mass to 5% by mass.

<< Basic compound >>
The photosensitive resin layer may further contain a basic compound.
The molecular weight of the basic compound in the present disclosure is less than 2,000, preferably less than 1,000.
As the basic compound, any of the basic compounds used in the chemically amplified positive resist can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-221494, the contents of which are incorporated in the present specification.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine and tri. Examples thereof include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
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 amide, quinoline, 8-oxyquinolin, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholin, 4-methylmorpholin, 1,5-diazabicyclo [4.3.0] -5-nonen, and 1,8-diazabicyclo [5.3.0] -7-Undesen and the like can be mentioned.
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 above basic compounds may be used alone or in combination of two or more.
The photosensitive resin layer preferably does not contain a basic compound, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less with respect to the total mass of the photosensitive resin layer. It does not contain a basic compound, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less with respect to the total mass of the photosensitive resin layer, and does not contain the basic compound. The content of the basic compound is more preferably more than 0% by mass and 1.2% by mass or less with respect to the total mass of the photosensitive resin layer, and it is particularly preferable that the basic compound is not contained.

<< Other additives >>
The photosensitive resin layer in the present disclosure may contain known additives in addition to the above components, if necessary.

-Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic) or amphoteric surfactants can be used, but the preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based and fluorine-based surfactants. .. In addition, under the following product names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop (manufactured by JEMCO), Megafuck (manufactured by DIC Co., Ltd.), Florard (manufactured by Sumitomo 3M) Series such as Asahi Guard (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.) can be mentioned.
Further, as the surfactant, the constituent unit A and the constituent unit B represented by the following formula I-1 are contained, and the polystyrene-equivalent weight average measured by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent. A copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

In formula (I-1), R ⁴⁰¹ and R ⁴⁰³ independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less ^{carbon atoms, and R 404} represents a hydrogen atom or carbon. An alkyl group having a number of 1 to 4 is represented, L is an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less. , Q represents 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, s represents an integer of 1 or more and 10 or less, and * represents a bonding site with another structure. show.

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

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

In addition, the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362 can also be used.

The surfactant may be used alone or in combination of two or more.
The amount of the surfactant added is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably% to 3% by mass.

-Polymerization inhibitor-
The photosensitive resin layer may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, preferably 0.01% by mass, based on the total mass of the photosensitive resin layer. % To 1% by mass is more preferable, and 0.01% by mass to 0.8% by mass is further preferable.

− Solvent −
The photosensitive resin layer may contain a solvent.
Further, in the photosensitive resin composition forming the photosensitive resin layer, in order to easily form the photosensitive resin layer, the photosensitive resin composition is once contained with a solvent to adjust the viscosity of the photosensitive resin composition, and the photosensitive resin composition contains the solvent. The photosensitive resin layer can be suitably formed by applying and drying the sex resin composition.
As the solvent used in the present disclosure, a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, and diethylene glycol dialkyl ethers. , Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like can be exemplified. Further, specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and these contents are incorporated in the present specification.

Further, in addition to the above-mentioned solvent, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, capric acid, 1-octanol, 1 -Solvents such as nonar, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate can also be added.
Only one type of solvent may be used, or two or more types may be used.
The solvent that can be used in the present disclosure may be used alone or in combination of two. When two or more solvents are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers are used in combination, diacetates and diethylene glycol dialkyl ethers are used in combination, or esters and butylene glycol alkyl ether acetates are used in combination. It is preferable to use it in combination with the like.

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

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

-Plasticizer-
The photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a smaller weight average molecular weight than the polymer represented by a1 or a2.
From the viewpoint of imparting plasticity, the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and further preferably 800 or more and less than 4,000.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

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

For example, even a compound having an alkyleneoxy group having the above structure (referred to as “Compound X”) is chemically amplified positive photosensitive obtained by mixing Compound X, the above polymer, and a photoacid generator. If the resin composition does not have improved plasticity as compared with the chemically amplified positive photosensitive resin composition formed without containing compound X, it does not fall under the plastic agent in the present disclosure. For example, the arbitrarily added surfactant is not generally used in an amount that causes plasticity in the photosensitive resin composition, and therefore does not fall under the plasticizer in the present specification.

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

From the viewpoint of adhesion, the content of the plasticizer is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 20% by mass, based on the total mass of the photosensitive resin layer. preferable.
The photosensitive resin layer may contain only one type of plasticizer, or may contain two or more types of plasticizer.

-Sensitizer-
The photosensitive resin layer may further contain a sensitizer.
The sensitizer absorbs the active light beam and becomes an electronically excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the photoacid generator undergoes a chemical change and decomposes to produce an acid.
By containing a sensitizer, the exposure sensitivity can be improved.

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

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

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

-Heterocyclic compound-
The photosensitive resin layer in the present disclosure may contain a heterocyclic compound.
The heterocyclic compound in the present disclosure is not particularly limited. For example, compounds having an epoxy group or an oxetanyl group in the molecules described below, heterocyclic compounds containing an alkoxymethyl group, various cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones), silicon, sulfur, phosphorus and the like. A heterocyclic monomer having d-electrons of the above can be added.

When the heterocyclic compound is added, the amount of the heterocyclic compound added in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. The above range is preferable from the viewpoint of adhesion and etching resistance. Only one kind of heterocyclic compound may be used, or two or more kinds may be used in combination.

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

Compounds having an epoxy group in the molecule are available as commercial products. For example, commercial products described in paragraph 0189 of JP2011-221494A such as JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-. 1000, EPPN-501, EPPN-502 (all manufactured by ADEKA CORPORATION), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC- 203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (above Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Eporide GT400, Serviners B0134, B0177 (manufactured by Daicel Corporation) and the like can be mentioned.
The compound having an epoxy group in the molecule may be used alone or in combination of two or more.

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

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

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

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

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

-Other ingredients-
The photosensitive resin layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorption. Further known additives such as agents, thickeners, crosslinkers, and organic or inorganic antiprecipitants can be added.
Preferred embodiments of other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated in the present specification.

<< Average film thickness of photosensitive resin layer >>
The average film thickness of the photosensitive resin layer is preferably 1.0 μm or more, more preferably 2.0 μm or more, from the viewpoint of transferability (laminatability). The average film thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 15 μm or less, from the viewpoint of manufacturing suitability.

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

By applying the photosensitive resin composition on a temporary support or an intermediate layer described later and drying it, the photosensitive transfer material according to the present disclosure having a photosensitive resin layer on the temporary support can be obtained.
The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
It is also possible to apply the photosensitive resin layer on the intermediate layer on which the other layers described below are formed.

<Middle layer>
The photosensitive transfer material according to the present disclosure is the temporary support and the photosensitive resin layer from the viewpoints of resolution, retention time dependence inhibitory property, adhesion between the intermediate layer and the photosensitive resin layer, and pattern formation property. It is preferable to have an intermediate layer between the and. Further, the intermediate layer preferably contains a binder.

<< Binder >>
The binder is preferably a water-soluble or alkali-soluble binder, and more preferably a water-soluble or alkali-soluble polymer.
In the present disclosure, "water-soluble" means that the solubility of pH 7.0 in water at 25 ° C is 0.1% by mass or more, and "alkali-soluble" means pH 8. It means that the solubility in an alkaline aqueous solution of 5 or more is 0.1% by mass or more.
Further, the above-mentioned "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or may be water-soluble and alkali-soluble.

Examples of the binder include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, and phenol / cresol (m-, p-, or m- / p-mixed). Novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, homopolymer or copolymer of hydroxyalkyl (meth) acrylate), Steels, glycogens, chitins, agaroses, carrageenans, purulans, arabic gum, soya gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, polyurethane resin, polyvinyl alcohol, polyvinylformal, polyamide resin, Examples thereof include polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol and the like.

Among these, the binder is at least one selected from the group consisting of novolak resin, modified cellulose resin, and acrylic resin having a hydroxy group from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern forming property. It is preferably a resin, more preferably at least one resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxy group, and even more preferably a modified cellulose resin.
Further, as the modified cellulose resin, hydroxyalkylated cellulose is preferable from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern forming property.
Preferred examples of the hydroxyalkylated cellulose include hydroxymethyl cellulose, hydroxyethyl cellulose, polyhydroxyethylated cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, glioxalized hydroxypropylmethyl cellulose, hydroxypropylmethylcellulose phthalate and the like.
Above all, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation property, at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is preferable, and hydroxypropyl methyl cellulose is preferable. Is more preferable.
The binder is preferably at least one resin selected from the group consisting of polyvinyl alcohol and polyvinyl formal from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and is preferably polyvinyl alcohol. Is more preferable.

The weight average molecular weight of the binder is preferably 1,000 or more from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation property, solubility in a developing solution after exposure, and transferability. It is preferably 000 to 100,000, more preferably 10,000 to 50,000.

The intermediate layer may contain one kind of binder alone or two or more kinds of the binder.
The content of the binder in the intermediate layer is adjusted with respect to the total mass of the intermediate layer from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer, pattern forming property, solubility in a developing solution after exposure, and transferability. It is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, further preferably 40% by mass or more and 100% by mass or less, and 65% by mass or more and 85% by mass. % Or less is particularly preferable.

<< Other additives >>
The intermediate layer in the present disclosure may contain a known additive, if necessary, in addition to the binder.
As other additives, other additives used for the photosensitive resin layer are preferably mentioned.

<< Particles >>
The intermediate layer preferably contains particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
The particles are preferably metal oxide particles or organic particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and oxidation of an element selected from the group consisting of Si, Ti and Zr. More preferably, it is a physical particle or an organic particle.
The metal of the metal oxide particles in the present disclosure also includes metalloids such as B, Si, Ge, As, Sb, and Te.
Examples of the metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, and B. , Al, Si, Ge, Sn, Pb, Sb, Bi, Te and the like, and oxide particles containing atoms are preferable, and silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or , Antimon / tin oxide is more preferred, silica, titanium oxide, titanium composite oxide, or zirconium oxide is even more preferred, and silica, titanium oxide, or zirconium oxide is particularly preferred.
Preferred examples of the organic particles include organic resin particles.
Examples of the organic resin particles include homopolymers and copolymers of acrylic acid-based monomers such as acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester, and cellulose-based polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate. , Polyethylene, Polypropylene, Polystyrene, Vinyl Chloride Copolymer, Vinyl Chloride-Vinyl Acetate Copolymer, Polyvinylpyrrolidone, Polyvinylbutyral, Polypolymers of Vinyl Polymers and Vinyl Compounds, Polyester, Polyurethane, Polypolymer Condensation polymers such as, rubber-based thermoplastic polymers such as butadiene-styrene copolymers, polymers obtained by polymerizing and cross-linking photopolymerizable or thermopolymerizable compounds such as epoxy compounds, melamine compounds and the like. can.
Among these, as the organic particles, acrylic resin particles are preferably mentioned, and polymethylmethacrylate particles are more preferably mentioned.
In addition, the surface of these particles can be treated with an organic material or an inorganic material in order to impart dispersion stability. The particles preferably have a hydrophilic surface. For example, the surface of particles having a hydrophobic surface may be hydrophilized.

The arithmetic mean particle size of the particles is preferably 400 nm or less, more preferably 250 nm or less, still more preferably 150 nm or less, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer. It is particularly preferably 10 nm to 200 nm.
The method for measuring the arithmetic average particle size of particles in the present disclosure is to measure the particle size of 200 arbitrary particles with an electron microscope and refer to the arithmetic mean. If the shape of the particles is not spherical, the maximum diameter is taken as the diameter.

The volume fraction of the particles in the intermediate layer (volume fraction occupied by the particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 15% to 70%, and particularly preferably 20% to 60%.

<< Average film thickness of intermediate layer >>
The average film thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and more preferably 0.3 μm, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation property. ~ 2 μm is particularly preferable.
The method for measuring the average film thickness of each layer in the present disclosure is not particularly limited, and a known method can be used. Further, it is preferable to measure and calculate the average value at 10 points or more.
Specific examples thereof include surface shape measurement, cross-sectional observation with an optical microscope or an electron microscope, and the like. Further, for the surface shape measurement, the Dektak series manufactured by Bruker can be preferably used. Further, a scanning electron microscope (SEM) can be preferably used for cross-section observation.
Further, the thickness of the intermediate layer is preferably thinner than the thickness of the photosensitive resin layer.

<< Method of forming the intermediate layer >>
The method for forming the intermediate layer is not particularly limited, but for forming the intermediate layer by mixing each component and a solvent (preferably an aqueous solvent) at a predetermined ratio and by any method and stirring and dissolving. A composition for forming an intermediate layer can be prepared. For example, it is also possible to prepare a composition by preparing a solution in which each component is previously dissolved in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can also be used after being filtered using a filter having a pore size of 5 μm or the like.
Examples of the water-based solvent include water and water-soluble solvents such as alcohols.

By applying the composition for forming an intermediate layer to the temporary support and drying it, the intermediate layer can be easily formed on the temporary support.
The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
It is also possible to apply an intermediate layer on the temporary support on which another layer described later (for example, a thermoplastic resin layer or the like) is formed.

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

-Thermoplastic resin layer, cover film, etc.-
From the viewpoint of transferability, the photosensitive transfer material according to the present disclosure preferably further has a thermoplastic resin layer between the temporary support and the photosensitive resin layer or the intermediate layer.
Further, the photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive resin layer.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-85643, and preferred embodiments of other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of this publication are incorporated herein.
Above all, from the viewpoint of transferability, it is preferable that the thermoplastic resin layer contains at least one thermoplastic resin selected from the group consisting of an acrylic resin and a styrene / acrylic copolymer.

When the photosensitive transfer material according to the present disclosure has another layer such as a thermoplastic resin layer, it is produced according to the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
For example, in the case of producing the photosensitive transfer material according to the present disclosure having a thermoplastic resin layer, a solution (for a thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support is used. (Coating liquid) is applied and dried to provide a thermoplastic resin layer, and then a preparation liquid (intermediate) prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer. The layer composition) is applied and dried to laminate the intermediate layer. The photosensitive transfer material according to the present disclosure is obtained by further applying a photosensitive resin composition prepared by using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, drying the mixture, and laminating the photosensitive resin layer. Can be suitably produced.

-Contrast enhancement layer-
The photosensitive transfer material according to the present disclosure may have a contrast enhancement layer in addition to the above-mentioned photosensitive resin layer.
The contrast enhancement layer (CEL) absorbs a large amount of light with respect to the exposure wavelength before exposure, but the absorption gradually decreases with exposure, that is, a material having high light transmittance (light extinction). It is a layer containing) (referred to as a sex pigment component). Diazonium salts, stillvazolium salts, arylnitroso salts and the like are known as photochromic dye components. As the film-forming component, a phenol-based resin or the like is used.
In addition, as the contrast enhancement layer, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to paragraph 0055 of JP-A-6-332167, Photopolymer Handbook, Photopolymer Social gathering edition, Industrial Research Council ( 1989), Photopolymer Technology, Yamaoka, Nagamatsu ed., Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

(Manufacturing method of resin pattern and manufacturing method of circuit wiring)
The method for producing the resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the above-mentioned photosensitive resin in the photosensitive transfer material according to the present disclosure is not particularly limited. The substrate includes a step of bringing the layers into contact with the substrate and bonding them together, a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a pattern. It is preferable to include a step of peeling off the temporary support after the step of bonding to and before the step of forming the pattern.
The method for manufacturing the circuit wiring according to the present disclosure is not particularly limited as long as it is a method for manufacturing the circuit wiring using the photosensitive transfer material according to the present disclosure, but the above-mentioned photosensitive in the photosensitive transfer material according to the present disclosure is not particularly limited. A step of bringing the sex resin layer into contact with a substrate having a conductive layer and sticking them together, a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a pattern. The step of etching the conductive layer in the region where the pattern is not arranged is included in this order, and the temporary support is peeled off after the step of bonding to the substrate and before the step of forming the pattern. It is preferable to include a step.
Further, the substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface.

Conventionally, the photosensitive resin composition is divided into a negative type in which a portion irradiated with active light remains as an image and a positive type in which a portion not irradiated with active light remains as an image, depending on the difference in the photosensitive system. In the positive type, by irradiating with active light rays, for example, in order to improve the solubility of the exposed part by using a photosensitive agent that generates acid by being irradiated with active light rays, both the exposed part and the unexposed part are exposed at the time of pattern exposure. If the pattern is not cured and the obtained pattern shape is defective, the substrate can be reused (reworked) by full exposure or the like. Therefore, from the viewpoint of excellent so-called reworkability, the positive type is preferable. Further, since the technique of re-exposing the remaining photosensitive resin layer to produce a different pattern can be realized only by the photosensitive resin layer, the method for manufacturing the resin pattern according to the present disclosure or the circuit according to the present disclosure. In the method of manufacturing wiring, an embodiment in which exposure is performed twice or more is preferably mentioned.

<Lasting process>
In the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, the photosensitive resin layer in the photosensitive transfer material according to the present disclosure is brought into contact with a substrate, preferably a substrate having a conductive layer. It is preferable to include a step of forming and bonding (bonding step).
Further, in the bonding step, it is preferable that the conductive layer and the photosensitive resin layer are pressure-bonded so as to be in contact with each other. In the above aspect, the photosensitive resin layer on which the pattern is formed after exposure and development can be suitably used as an etching resist when etching the conductive layer.
The method for pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and a known transfer method or laminating method can be used.
Specifically, for example, it is preferable to stack the photosensitive resin layer side of the photosensitive transfer material on the substrate and pressurize it with a roll or the like, or pressurize and heat it. For bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
The crimping pressure and temperature in the bonding step are not particularly limited, and depend on the surface material of the substrate to be bonded, for example, the material of the conductive layer, the material of the photosensitive resin layer, the transport speed, the crimping machine to be used, and the like. , Can be set as appropriate. When the cover film is provided on the photosensitive resin layer of the photosensitive transfer material, the cover film may be removed from the photosensitive resin layer and then pressure-bonded.
When the base material is a resin film, crimping may be performed by roll-to-roll.

The substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of the base material. Wiring is formed by patterning the conductive layer. Further, in the present disclosure, it is preferable that a film base material such as polyethylene terephthalate is provided with a plurality of conductive layers such as metal oxides and metals.
Further, the substrate used in the present disclosure is preferably a substrate containing copper from the viewpoint of further exerting the effect in the present disclosure. Further, from the viewpoint of further exerting the effect in the present disclosure, the conductive layer is preferably a layer containing copper.

Further, the substrate is preferably a substrate in which a plurality of conductive layers are laminated on a support.
In the substrate in which a plurality of conductive layers are laminated on the support, the support is preferably a glass base material or a film base material, and more preferably a film base material. In the circuit wiring manufacturing method according to the present disclosure, when the circuit wiring for a touch panel is used, it is particularly preferable that the support is a sheet-shaped resin composition.
Further, the support is preferably transparent.
The refractive index of the support is preferably 1.50 to 1.52.
The support may be made of a translucent base material such as a glass base material, and tempered glass typified by Corning's gorilla glass can be used. Further, as the above-mentioned transparent base material, the materials used in JP-A-2010-86684A, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
When a film base material is used as the base material, it is more preferable to use a base material that is not optically distorted and a base material having high transparency, and specific materials include polyethylene terephthalate (PET). Examples thereof include polyethylene terephthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

Examples of the conductive layer include any conductive layer used for general wiring or touch panel wiring.
Examples of the material of the conductive layer include metals and metal oxides.
Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), SiO _{2 and the} like. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo and the like.

In the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.
As the conductive layer, it is preferable that the electrode pattern corresponds to the sensor of the visual recognition portion used in the capacitive touch panel or the wiring of the peripheral extraction portion.

<Exposure process>
It is preferable that the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
In the exposure step, it is preferable to irradiate the photosensitive resin layer with active light rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate acid. By the catalytic action of the generated acid, the acid-degradable group contained in the coating film component is hydrolyzed to generate an acid group, for example, a carboxy group or a phenolic hydroxyl group.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit board manufactured in the present disclosure and to make the area occupied by the take-out wiring as small as possible, at least a part of the pattern (particularly a touch panel) is desired. The electrode pattern and the portion of the take-out wiring) are preferably thin wires of 100 μm or less, and more preferably 70 μm or less.
Further, the exposure in the exposure step may be an exposure through a mask or a digital exposure using a laser or the like, but an exposure via an exposure mask is preferable.
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure is a step of bringing the photosensitive transfer material into contact with an exposure mask between the bonding step and the exposure step. It is preferable to include. In the above aspect, the resolution of the obtained pattern is more excellent.

Examples of the active light include visible light, ultraviolet light, and electron beam, but visible light or ultraviolet light is preferable, and ultraviolet light is particularly preferable.
As an exposure light source using active light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a light-emitting diode (LED) light source, an excima laser generator, or the like can be used, and g-line (436 nm) and i-line (365 nm) can be used. , H line (405 nm) and other active rays having a wavelength of 300 nm or more and 450 nm or less can be preferably used. Further, if necessary, the irradiation light can be adjusted through a spectroscopic filter such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
Exposure dose, depending on the photosensitive resin layer to be used may be appropriately ^selected, but is preferably from ^{5mJ / cm 2 ~200mJ / cm 2} , more preferably 10mJ / cm ² ~100mJ / cm 2 ..
Further, it is also preferable to perform heat treatment before development for the purpose of improving the rectangularness and linearity of the pattern after exposure. By the so-called PEB (Post Exposure Bake) process, it is possible to reduce the roughness of the pattern edge due to the standing wave generated in the photosensitive resin layer during exposure.

Even if the pattern exposure is performed after the temporary support is peeled off from the photosensitive resin layer, the temporary support is exposed through the temporary support before the temporary support is peeled off, and then the temporary support is peeled off. May be good. The pattern exposure may be an exposure through a mask or a digital exposure using a laser or the like.

<Development process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure is a step of developing the exposed photosensitive resin layer to form a pattern after the exposure step (development step). It is preferable to include.
When the photosensitive transfer material has an intermediate layer, the intermediate layer of the exposed portion is also removed together with the exposed photosensitive resin layer in the developing step.
Further, in the developing step, the intermediate layer of the unexposed portion may also be removed in a form of being dissolved or dispersed in the developing solution.
The exposed photosensitive resin layer can be developed by using a developing solution in the developing step.
The developing solution is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed, and a known developing solution such as the developing solution described in JP-A-5-72724 can be used. .. The developer is preferably a developer in which the exposed portion of the photosensitive resin layer has a dissolution-type development behavior. As the developing solution, an alkaline aqueous solution is preferable, and for example, an alkaline aqueous solution containing a compound having pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is more preferable. The developer may further contain an organic solvent miscible with water, a surfactant and the like. Examples of the developer preferably used in the present disclosure include the developer described in paragraph 0194 of International Publication No. 2015/093271.

The development method is not particularly limited and may be any of paddle development, shower development, shower and spin development, dip development and the like. Here, the shower development will be described. By spraying the developer on the photosensitive resin layer after exposure with a shower, the exposed portion can be removed. Further, after the development, it is preferable to spray a cleaning agent or the like with a shower and rub it with a brush or the like to remove the development residue. The liquid temperature of the developer is preferably 20 ° C to 40 ° C.
Further, the longer the time from exposure to development is, the more effective the effect of suppressing the deformation of the pattern shape in the present disclosure is exhibited. Development may be performed immediately after exposure, but in an embodiment in which development is performed after the time from exposure to development is preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 6 hours or more. , The effect of suppressing the deformation of the pattern shape in the present disclosure is more exhibited.
Further, the method for manufacturing a resin pattern according to the present disclosure, or the method for manufacturing a circuit wiring according to the present disclosure, is known such as a step of cleaning with water or the like after development, a step of drying a substrate having the obtained pattern, and the like. May include the steps of.

Further, it may have a post-baking step of heat-treating the pattern obtained by developing.
The post-bake heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably performed in an environment of 50.66 kPa or more. On the other hand, it is more preferably performed in an environment of 111.46 kPa or less, and particularly preferably performed in an environment of 101.3 kPa or less.
The temperature of the post-bake is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
Post-baking may be performed in an air environment or a nitrogen substitution environment.

The transport speed of the support at each step in the method for manufacturing the resin pattern according to the present disclosure or the method for manufacturing the circuit wiring according to the present disclosure is not particularly limited, but is 0.5 m / m / except for the time of exposure. It is preferably min to 10 m / min, and more preferably 2.0 m / min to 8.0 m / min except during exposure.

<Peeling process>
In the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, the temporary support is peeled off after the step of attaching to the substrate and before the step of forming the pattern. It is preferable to include a step (peeling step).
Since the above-mentioned photosensitive transfer material is used in the method for manufacturing the resin pattern according to the present disclosure or the method for manufacturing the circuit wiring according to the present disclosure, provisionally at any timing after the photosensitive transfer material is bonded and before development. Even if the support is peeled off, the adhesion to the photosensitive resin layer is excellent, so that it is possible to suppress the occurrence of defects such as partial peeling, and the pattern can be formed satisfactorily.
Further, in the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, from the viewpoint of pattern formability and resolution, the photosensitive resin layer is formed after the step of bonding to the substrate. It is more preferable to include a step of peeling off the temporary support before the step of pattern exposure. Further, in the above aspect, when the mask is brought into contact with the pattern to be exposed, the photosensitive resin layer and the mask do not come into direct contact with each other, so that the pattern formability and the resolution are excellent.
The method for peeling the temporary support in the peeling step is not particularly limited, and the temporary support may be peeled by a known method.

<Etching process>
The method for manufacturing a circuit wiring according to the present disclosure preferably includes a step (etching step) of etching a conductive layer in a region where the pattern is not arranged.
In the etching step, the pattern formed from the photosensitive resin layer by the developing step is used as an etching resist, and the conductive layer is etched.
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 method by dry etching such as known plasma etching.
For example, as an etching method, a commonly used wet etching method of immersing in an etching solution can be mentioned. As the etching solution used for wet etching, an acidic type or alkaline type etching solution may be appropriately selected according to the etching target.
As the acidic type etching solution, an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or phosphoric acid, an acidic component and ferric chloride, ammonium fluoride, or permanganese Examples thereof include a mixed aqueous solution of a salt such as potassium acid. As the acidic component, a component in which a plurality of acidic components are combined may be used.
The alkaline type etching solution includes an aqueous solution of an alkaline component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or a salt of an organic amine such as tetramethylammonium hydroxide, an alkaline component and potassium permanganate. A mixed aqueous solution of salts such as, etc. is exemplified. As the alkaline component, a component in which a plurality of alkaline components are combined may be used.

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

After the etching step, in order to prevent contamination of the process line, a step of cleaning the etched substrate (cleaning step) and a step of drying the etched substrate (drying step) are performed as necessary. It is also good. Examples of the cleaning step include cleaning the substrate with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.). For the drying step, for example using the air blowing may be performed dried by appropriately adjusting the air blow pressure ^{(0.1kg / cm 2 ~5kg / cm} 2 or so).

<Etching resist peeling process>
The method for manufacturing a circuit wiring according to the present disclosure preferably includes a step of peeling the photosensitive resin layer with a peeling liquid (etching resist peeling step) after the etching step.
After the completion of the etching step, the patterned photosensitive resin layer remains. If the photosensitive resin layer is unnecessary, all the remaining photosensitive resin layers may be removed.
As a method of peeling using a stripping solution, for example, a substrate having the above-mentioned photosensitive resin layer or the like is added to the stripping solution being stirred at preferably at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 5 minutes. Examples thereof include a method of immersing for about 30 minutes.
As the stripping solution, for example, 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 may be used as water, dimethylsulfoxide, N-methylpyrrolidone, or. , A stripping solution dissolved in a mixed solution of these. A stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.

Further, in the circuit wiring manufacturing method according to the present disclosure, the exposure step, the developing step and the etching step may be repeated twice or more, if necessary.
As an example of the exposure step, the developing step and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure may include any other step. For example, the following steps can be mentioned, but the steps are not limited to these steps.

<Step to reduce visible light reflectance>
The method for manufacturing a circuit wiring according to the present disclosure can include a step of reducing the visible light reflectance on the surface of the conductive layer, for example, a part or all of the surface of the conductive layer on the substrate. ..
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, by oxidizing copper to copper oxide, it is possible to reduce the visible light reflectance by blackening the copper.
Preferable embodiments of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Laid-Open No. 2013-206315. There is a description and the contents of this publication are incorporated herein by reference.

<Step of forming an insulating film on the etched substrate and step of forming a new conductive layer on the insulating film>
The method for manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on the above-mentioned substrate, for example, a formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film. It is also preferable to include.
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 photolithography using a photosensitive material having an insulating property.
The process of forming a new conductive layer on the insulating film is not particularly limited. A photosensitive material having conductivity may be used to form a new conductive layer of a desired pattern by photolithography.

Further, in the method for manufacturing the circuit wiring according to the present disclosure, the new conductive layer may be etched by forming an etching resist by the same method as described above, or may be separately etched by a known method. ..
The substrate having the circuit wiring obtained by the method for manufacturing the circuit wiring according to the present disclosure may have only one layer of wiring on the substrate or may have two or more layers of wiring.

Further, in the method for manufacturing a circuit wiring according to the present disclosure, the substrate may have a plurality of conductive layers on both surfaces thereof, and the circuit may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate. preferable. With such a configuration, wiring in which a first conductive pattern (first wiring) is formed on one surface of the substrate and a second conductive pattern (second wiring) is formed on the other surface, preferably wiring for a touch panel. Can be formed.

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

(Input device and display device)
An input device is mentioned as a device provided with the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure.
The input device according to the present disclosure may be any input device having at least the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure, and is preferably a capacitive touch panel.
The display device according to the present disclosure preferably includes an input device according to the present disclosure. The display device according to the present disclosure is preferably an organic EL display device and an image display device such as a liquid crystal display device.

(Touch panel and touch panel display device)
The touch panel according to the present disclosure is a touch panel having at least the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure. Further, the touch panel according to the present disclosure preferably has at least a transparent substrate, electrodes, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure, and is preferably a touch panel display device having the touch panel according to the present disclosure.
The method for manufacturing the touch panel according to the present disclosure is not particularly limited as long as it is a method for manufacturing a touch panel using the photosensitive transfer material according to the present disclosure, but the above-mentioned photosensitive resin for the photosensitive transfer material according to the present disclosure is not particularly limited. A step of bringing the layers into contact with a substrate having a conductive layer and sticking them together, a step of pattern-exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and the above-mentioned pattern. It is preferable to include a step of etching the conductive layer in the region where the is not arranged, in this order.
As the detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Above all, the capacitance method is preferable.

The touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-51751), and a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125). The one described in FIG. 19 of the publication, the one described in FIGS. 1 and 5 of Japanese Patent Application Laid-Open No. 2012-89102), OGS (One Glass Solution) type, TOR (Touch-on-Lens) type (for example, Japanese Patent Application Laid-Open No. 2012-89102). (The one described in FIG. 2 of Japanese Patent Application Laid-Open No. 2013-5472), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.) can be mentioned.

As the touch panel related to this disclosure and the touch panel display device related to this disclosure, "Latest Touch Panel Technology" (July 6, 2009, published by Techno Times Co., Ltd.), supervised by Yuji Mitani, "Touch Panel Technology and Development" ( CMC Publishing, December 2004), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiment of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Polymer component>
In the following synthetic examples, the following abbreviations represent the following compounds, respectively.
ATH F: 2-tetrahydrofuranyl acrylate (synthetic product)
MATTH: 2-Tetrahydrofuranyl methacrylate (synthetic product)
TBA: tert-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
EA: Ethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
CHA: Cyclohexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
BMA: Benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
PMPMA: Methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl (manufactured by Wako Pure Chemical Industries, Ltd.)
DMAPAA: N- [3- (dimethylamino) propyl] acrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
DMAEMA: 2- (dimethylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
DEAEMA: 2- (diethylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
DPAEMA: 2- (diisopropylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MEMA: 2-morpholinoethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
VP: Vinyl pyridine (manufactured by Wako Pure Chemical Industries, Ltd.)
VI: 1-Vinylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
VT: 1-vinyl-1,2,4-triazole (manufactured by Sigma-Aldrich)
NVP: N-vinylpyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
DMAA: Dimethylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)
MANa: Sodium methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
V-601: Dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of ATHF>
Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to the three-necked flask and cooled to 20 ° C. After dropping camphorsulfonic acid (0.0070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 mol equivalent), 1. within the range of 20 ° C ± 2 ° C. After stirring for 5 hours, the temperature was raised to 35 ° C. and the mixture was stirred for 2 hours. After spreading Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite powder, manufactured by Kyowa Chemical Industry Co., Ltd.) on Nutche in this order. The reaction solution was filtered to obtain a filtrate. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts by mass) was added to the obtained filtrate, and then concentrated under reduced pressure at 40 ° C. to make 140.8 parts by mass of tetrahydrofuran-2-yl acrylate (ATHF) colorless oil. Obtained as a product (yield 99.0%).

<Synthesis of MATTH>
Acrylic acid was changed to methacrylic acid, but the ratio was the same as that of ATHF.

<Example of synthesis of polymer A-1>
PGMEA (75.0 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. ATHF (30.0 parts by mass), PMPMA (1.0 parts by mass), ethyl acrylate (EA, 35.0 parts by mass), methyl methacrylate (MMA, 34.0 parts by mass), V-601 (4. The solution containing 0 part by mass) and PGMEA (75.0 part by mass) was added dropwise to the three-necked flask solution maintained at 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropping, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain polymer A-1 (solid content concentration 40.0%).

<Synthesis Examples of Polymer A-2 to Polymer A-23>
The types of monomers and the like were changed as shown in Table 1 below, and the other conditions were the same as for the polymer A-1. The solid content concentration of the polymer was 40% by mass. The unit of the amount of each monomer used in Table 1 is mass%.

<Photoacid generator>
B-1: Compound having the structure shown below (compound according to paragraph 0227 of JP2013-47765A, synthesized according to the method described in paragraph 0227).

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

B-3: A compound having the structure shown below (synthesized according to the method described in paragraph 0210 of JP-A-2014-197155).

In the above compounds, Ts represents a tosyl group.

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

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

<Basic compound>
D-1: Compound with the structure shown below

D-2: 2-Phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: Trioctylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Preparation of photosensitive transfer material>
In Examples 1 to 17 and Comparative Examples 1 to 5, the polymer component, the photoacid generator, the basic compound, and the surfactant were added to PGMEA so as to have the solid content ratio (mass ratio) shown in Table 2 below. The mixture was dissolved and mixed so as to have a solid content concentration of 10% by mass, and filtered through a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a photosensitive resin composition.
In each Example and Comparative Example, the obtained photosensitive resin composition was placed on a polyethylene terephthalate film (hereinafter, also referred to as PET (A)) having a thickness of 30 μm as a temporary support using a slit-shaped nozzle. The film was applied so that the dry film thickness was 3.0 μm and the coating width was 1.0 m. Then, it is passed through a drying zone at 80 ° C. for 40 seconds, a polyethylene film (OSM-N manufactured by Tredegar) is pressure-bonded as a cover film to prepare a photosensitive transfer material, and the photosensitive transfer material is wound up and rolled. Made into a form.

<Performance evaluation>
A PET substrate with a copper layer was used, in which copper was deposited to a thickness of 200 nm by a vacuum vapor deposition method on a PET film having a thickness of 100 μm.

-Laminating aptitude evaluation-
The prepared photosensitive transfer material was cut into 50 cm squares, the cover film was peeled off, the roll temperature was 90 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 4.0 m / min. It was laminated on the PET substrate with a copper layer under the above-mentioned laminating conditions. Visually discriminate the portion where the intermediate layer and the photosensitive resin layer are attached to the copper layer, and use oil-based magic from above the temporary support at the portion where the intermediate layer and the photosensitive resin layer are attached to the copper layer. Mark the entire PET substrate, and use image analysis software (ImageJ (manufactured by National Institute of Health, USA)) to cover the area where the intermediate layer and photosensitive resin layer are attached to the copper layer and the entire sample piece. Was calculated respectively. Then, the area ratio was calculated from the following formula and evaluated according to the following evaluation criteria.
Area ratio (%) = Area to which the intermediate layer and photosensitive resin layer are attached / Area of the entire sample piece x 100
5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: 80% or less

-Sensitivity evaluation-
After unwinding the prepared photosensitive transfer material, the lamirol temperature was 120 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 0.5 m / min. It was laminated on a PET substrate with a copper layer under the above-mentioned laminating conditions. After exposure with an ultra-high pressure mercury lamp via a line-and-space pattern mask (duty ratio 1: 1) with a line width of 10 μm without peeling off the temporary support, the temporary support is peeled off after being left at 25 ° C. for 3 hours. Developed. Development was carried out by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25 ° C.
When a line-and-space pattern of 10 μm was formed by the above method, the residue in the space portion was observed and evaluated with a scanning electron microscope (SEM) to determine the exposure amount from which the residue was completely eliminated. The exposure amount is preferably less than 200 mJ / cm ^2.
5: 80mJ / cm ² less than 4: 80mJ / cm ² or more 150 mJ / cm ² less than 3: 150mJ / cm ² or more 200 mJ / cm ² less than ^2: 200mJ / cm 2 or more 300 mJ / cm ² less than 1: 300mJ / cm ² or more

-Evaluation of retention time dependence inhibitory-
After unwinding the prepared photosensitive transfer material, the roll temperature was 120 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 0.5 m / min. It was laminated on a PET substrate with a copper layer under the above-mentioned laminating conditions. After exposure to a line-and-space pattern mask (Duty ratio 1: 1) with a line width of 10 μm without peeling off the temporary support, the exposure amount was free of residue in the above sensitivity evaluation, and then left at 25 ° C. for 12 hours. After that, the temporary support was peeled off and developed. Development was carried out by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25 ° C.
The line width of the obtained line-and-space pattern was observed with a scanning electron microscope (SEM), and the variation of the line width from 10 μm was evaluated. It is preferable that the variation of the line width from 10 μm is less than 1.5 μm.
5: Less than 0.5 μm 4: 0.5 μm or more and less than 1.0 μm 3: 1.0 μm or more and less than 1.5 μm 2: 1.5 μm or more and less than 3 μm 1: 3 μm or more

-Evaluation of resolution-
The prepared photosensitive transfer material was subjected to a roll temperature of 120 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 1.0 m / min. It was laminated on a PET substrate with a copper layer under the above-mentioned laminating conditions.
Without peeling off the temporary support, after exposure with an ultra-high pressure mercury lamp via a line-and-space pattern mask (duty ratio 1: 1) with a line width of 3 μm to 20 μm, the temporary support is peeled off after being left for 3 hours. Developed. Development was carried out by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 25 ° C. Next, the copper layer was etched by a dip method for 60 seconds using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.) at 25 ° C. The remaining photosensitive resin layer was peeled off with a shower using a stripping solution at 50 ° C. (KP-301 manufactured by Kanto Chemical Co., Ltd.) to form a copper wiring having a conductive pattern with a line and space of 10 μm. The LWR (Line Width Roughness, 3σ of the value obtained by measuring the line width of the copper wiring at 250 points) of the copper wiring was obtained, and the linearity was evaluated using the following criteria as an index. 3 or more is a practical level.
5: LWR is 200 nm or less.
4: LWR is a value of 230 nm or less and more than 200 nm.
3: The LWR is a value of 250 nm or less and more than 230 nm.
2: LWR is a value of 300 nm or less and more than 250 nm.
1: LWR is larger than 300 nm, or a conductive pattern could not be formed.

The evaluation results in each Example and each Comparative Example are summarized in Table 2.

From Table 2 above, it can be seen that the photosensitive transfer materials of Examples 1 to 17 are superior in laminating suitability and resolution as compared with the photosensitive transfer materials of Comparative Examples 1 to 5.
Further, from Table 2 above, the photosensitive transfer materials of Examples 1 to 17 are also excellent in sensitivity and retention time dependence inhibitory property.

(Example 101)
On a 100 μm-thick PET substrate, ITO was formed into a film with a thickness of 150 nm by sputtering as a second conductive layer, and copper was formed into a film with a thickness of 200 nm as a conductive layer of the first layer by a vacuum vapor deposition method. This was used as a circuit forming substrate.
The photosensitive transfer material obtained in Example 1 was laminated on a copper layer (laminol temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.). Using a photomask provided with a pattern (hereinafter, also referred to as "pattern A") shown in FIG. 2, which has a structure in which a conductive layer pad is connected in one direction without peeling off the temporary support from the laminated support. Contact pattern exposure.
In the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are light-shielding portions, and the dotted line portion DL is a virtual representation of the alignment alignment frame.
Then, the temporary support was peeled off, developed and washed with water to obtain pattern A. Next, the copper layer is etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched with an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which copper and ITO were both drawn in pattern A was obtained.
Next, the pattern was exposed using a photomask provided with an opening of the pattern shown in FIG. 3 (hereinafter, also referred to as “pattern B”) in a aligned state, and the pattern was developed and washed with water.
In the pattern B shown in FIG. 3, the gray portion G is a light-shielding portion, and the dotted line portion DL is a virtual representation of the alignment alignment frame.
Then, the copper layer was etched with Cu-02, and the remaining photosensitive resin layer was peeled off with a stripping liquid (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and the pattern was clean.

(Example 102)
On a 100 μm-thick PET substrate, ITO was formed into a film with a thickness of 150 nm by sputtering as a second conductive layer, and copper was formed into a film with a thickness of 200 nm as a conductive layer of the first layer by a vacuum vapor deposition method. It was used as a circuit forming board.
The photosensitive transfer material obtained in Example 1 was unwound and laminated on a copper layer (roll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.). The laminated support was exposed to a pattern using a photomask provided with a pattern A having a structure in which the conductive layer pads were connected in one direction without peeling off the temporary support. Then, the temporary support was peeled off, developed and washed with water to obtain pattern A. Next, the copper layer is etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched with an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which copper and ITO were both drawn in pattern A was obtained.
Next, PET (A) was laminated as a protective layer on the remaining resist. In this state, the pattern was exposed using a photomask provided with an opening of the pattern B in an aligned state, and after the PET (A) was peeled off, development and washing with water were performed. Then, the copper wiring was etched with Cu-02, and the remaining photosensitive resin layer was peeled off with a stripping liquid (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and the pattern was clean.

(Example 103)
On a 100 μm thick cycloolefin polymer (COP) substrate, ITO is formed into a film with a thickness of 150 nm as a second layer conductive layer by sputtering, and copper is deposited on the first layer as a conductive layer with a thickness of 200 nm by a vacuum vapor deposition method. Was formed into a substrate for forming a conductive pattern.
The photosensitive transfer material obtained in Example 1 was bonded onto a copper layer on a substrate (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To form a laminated body. The laminated body was exposed to a pattern using a photomask provided with a pattern A having a structure in which the conductive layer pads were connected in one direction without peeling off the temporary support. After that, the temporary support was peeled off, developed, and washed with water to obtain a resin pattern drawn in pattern A. Next, the copper layer is etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched with an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) to remove the solution. By peeling using (KP-301 manufactured by Kanto Chemical Co., Ltd.), a substrate in which copper and ITO were both drawn in pattern A was obtained.
Next, the photosensitive transfer material obtained in Example 1 was bonded onto the remaining resist (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.). In this state, pattern exposure was performed using a photomask provided with an opening of pattern B in an aligned state, and after peeling off the temporary support of the photosensitive transfer material, development and washing with water were performed. Then, the copper wiring was etched with Cu-02, and the remaining photosensitive resin layer was peeled off with a stripping solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board having a conductive pattern. ..
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and the pattern was clean.

The disclosure of Japanese Patent Application No. 2018-098331 filed May 22, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Is incorporated herein by reference.

10: Temporary support, 12: Photosensitive resin layer, 14: Cover film, 100: Photosensitive transfer material, SL: Solid line part, G: Gray part, DL: Dotted line part

Claims (11)

Temporary support and
It has a photosensitive resin layer and
The photosensitive resin layer contains a polymer component satisfying at least one of the following a1 and a2, and a photoacid generator.
A photosensitive transfer material having a glass transition temperature of the polymer component of 90 ° C. or lower.
a1: Polymer component containing a structural unit having an acid group protected by an acid-degradable group and a polymer having a structural unit having a pKaH of 3 or more a2: Acid group protected by an acid-degradable group A polymer component having a structural unit having a pKaH of 3 or more and a polymer having a structural unit having a pKaH of 3 or more. The photosensitive group according to claim 1, wherein the proportion of the groups having a pKaH of 3 or more contained in the polymer component among all the groups having a pKaH of 3 or more contained in the photosensitive resin layer is 30 mol% or more. Sex transfer material. Claim 1 or claim 2 in which the ratio of the groups having a pKaH of 3 or more contained in the polymer component is 50 mol% or more among all the groups having a pKaH of 3 or more contained in the photosensitive resin layer. The photosensitive transfer material according to. Any of claims 1 to 3, wherein the polymer in the polymer component further has a structural unit other than a structural unit having an acid group protected by an acid-degradable group and a structural unit having a pKaH of 3 or more. The photosensitive transfer material according to claim 1. The photosensitive transfer material according to any one of claims 1 to 4, wherein the structural unit having three or more groups of pKaH is a structural unit represented by the following formula I or formula II.

In formulas I and II, R ₁ represents a hydrogen atom or a methyl group, Z is a single bond, a methylene group, an arylene group, -O-, -C (= O) -NH- or -C (= O)-. Representing O-, R ₂ is a carbon which may have at least one group selected from the group consisting of a single bond or an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of number 1-10, where R ₃ and R ₄ are independently hydrogen atoms or ether bonds, thioether bonds, hydroxy groups, formyl groups, acetoxy groups, cyano. A linear, branched group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond and an aromatic group. Representing a cyclic or cyclic alkyl group, R ₂ and R ₃ , R ₂ and R ₄ , or R ₃ and R ₄ may be bonded to each other to form a ring, and Q ₁ has a nitrogen atom. Represents an aromatic group or a nitrogen-containing heteroaromatic group. The photosensitive transfer material according to claim 5, wherein the structural unit having a group having 3 or more pKaH is the structural unit represented by the formula I. The photosensitive transfer material according to any one of claims 1 to 6, wherein the structural unit having an acid group protected by the acid-degradable group is a structural unit represented by the following formula A.

In formula A, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or an aryl group. An aryl group may be represented, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ is a single-bonded or divalent linking group. Represents. The step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate and bonding them together.
The process of pattern exposure of the photosensitive resin layer and
A method for producing a resin pattern, which comprises a step of developing the exposed photosensitive resin layer to form a pattern, and the process of forming a pattern in this order. A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate having a conductive layer and bonding them together.
The process of pattern exposure of the photosensitive resin layer and
The step of developing the exposed photosensitive resin layer to form a pattern, and
A method for manufacturing a circuit wiring including a step of etching a conductive layer in a region where the pattern is not arranged, and a step of etching the conductive layer in this order. The method for manufacturing a circuit wiring according to claim 9, wherein the conductive layer is a layer containing copper. A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate having a conductive layer and bonding them together.
The process of pattern exposure of the photosensitive resin layer and
The step of developing the exposed photosensitive resin layer to form a pattern, and
A method for manufacturing a touch panel, which comprises a step of etching a conductive layer in a region where the pattern is not arranged, and a step of etching the conductive layer in this order.

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