CN116194839A - Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel - Google Patents

Abstract

The present invention provides a photosensitive transfer material, and a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel using the photosensitive transfer material, wherein the photosensitive transfer material comprises a protective film, a photosensitive resin layer, a 1 st resin layer, a 2 nd resin layer, and a temporary support in this order, the 1 st resin layer contains particles, the 1 st resin layer is in contact with the 2 nd resin layer, the 1 st resin layer and the 2 nd resin layer are peelable, and the 2 nd resin layer contains a resin having a polyethylene structure.

Description

Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel

Technical Field

The invention 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.

Background

In a display device (an organic Electroluminescence (EL) display device, a liquid crystal display device, or the like) including a touch panel such as a capacitive input device, a conductive layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition portion, a wiring of a peripheral wiring portion, and a wiring of a lead-out wiring portion is provided inside the touch panel.

In general, in the formation of a patterned layer, the number of steps for obtaining a desired pattern shape is small, and therefore, a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate through a mask having a desired pattern by using a photosensitive transfer material and then developing the exposed layer is widely used.

As a conventional photosensitive transfer material, a photosensitive transfer material described in patent document 1 is known.

Patent document 1 describes a photosensitive transfer material having a photosensitive layer, an intermediate layer, an adhesive layer, and a temporary support in this order on a cover film, wherein the intermediate layer contains particles, the intermediate layer is in contact with the adhesive layer, the intermediate layer and the adhesive layer are peelable, and the surface of the intermediate layer after peeling the intermediate layer and the adhesive layer has irregularities formed of the particles.

Patent document 1: international publication No. 2019/146380

Disclosure of Invention

Technical problem to be solved by the invention

An object of an embodiment of the present invention is to provide a photosensitive transfer material having excellent releasability between a 1 st resin layer and a 2 nd resin layer after a protective film is released and a photosensitive transfer material is attached.

Another object of the present invention is to provide a method for producing a resin pattern, a method for producing a circuit wiring, and a method for producing a touch panel, each of which uses the photosensitive transfer material.

Means for solving the technical problems

The following means are included in the means for solving the above problems.

<1> a photosensitive transfer material comprising, in order, a protective film, a photosensitive resin layer, a 1 st resin layer, a 2 nd resin layer, and a temporary support, wherein the 1 st resin layer contains particles, the 1 st resin layer is in contact with the 2 nd resin layer, the 1 st resin layer is peelable from the 2 nd resin layer, and the 2 nd resin layer contains a resin having a polyethylene structure.

<2> the photosensitive transfer material according to <1>, wherein,

the resin having a polyethylene structure is a resin having an ethylene- (meth) acrylic acid copolymer structure.

<3> the photosensitive transfer material according to <1> or <2>, wherein,

the above-mentioned resin having a polyethylene structure is an ionomer resin having an ethylene- (meth) acrylic acid metal salt copolymerized structure.

<4> the photosensitive transfer material according to any one of <1> to <3>, wherein,

The peel force between the 1 st resin layer and the 2 nd resin layer is 1.0gf/cm or more.

<5> the photosensitive transfer material according to any one of <1> to <4>, wherein,

the peel force between the 1 st resin layer and the 2 nd resin layer is greater than the peel force between the photosensitive resin layer and the protective film.

<6> the photosensitive transfer material according to any one of <1> to <5>, wherein,

the water contact angle on the surface of the 2 nd resin layer on the 1 st resin layer side is 90 degrees or less.

<7> the photosensitive transfer material according to any one of <1> to <6>, wherein,

the surface of the 1 st resin layer after the 1 st resin layer and the 2 nd resin layer are peeled off has irregularities formed of the particles.

<8> a method for producing a resin pattern, comprising, in order:

a step of peeling the protective film from the photosensitive transfer material according to any one of <1> to <7 >; a step of bringing an outermost layer of the photosensitive transfer material from which the protective film has been peeled off, into contact with a base material, and bonding the outermost layer; a step of peeling the temporary support and the 2 nd resin layer from the photosensitive transfer material bonded to the substrate; exposing the photosensitive resin layer with the exposure mask in contact with the 1 st resin layer with the exposure mask interposed therebetween; and developing the photosensitive resin layer to form a resin pattern.

<9> a method for manufacturing a circuit wiring, comprising the steps of:

the method of producing a resin pattern according to <8>, wherein the conductive layer is etched using the resin pattern formed by the method of producing a resin pattern as a mask.

<10> a method for manufacturing a touch panel, comprising the steps of:

the wiring for a touch panel is formed by etching the conductive layer using the resin pattern formed by the method for producing a resin pattern described in <8> as a mask.

Effects of the invention

According to an embodiment of the present invention, there can be provided a photosensitive transfer material excellent in releasability between the 1 st resin layer and the 2 nd resin layer after the photosensitive transfer material is attached by peeling the protective film.

Further, according to another embodiment of the present invention, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel using the photosensitive transfer material can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of a layer structure of a photosensitive transfer material used in the present invention.

Fig. 2 is a schematic plan view showing the pattern a.

Fig. 3 is a schematic plan view showing a pattern B.

Detailed Description

The following describes the content of the present invention. In addition, although the description is made with reference to the drawings, the symbols may be omitted.

In the present specification, the numerical range indicated by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the present specification, "(meth) acrylic acid" means either or both of acrylic acid and methacrylic acid, "(meth) acrylic acid ester" means either or both of acrylic acid ester and methacrylic acid ester, "(meth) acryl" means either or both of acryl and methacryl.

In the present specification, the amount of each component in the composition refers to the total amount of the corresponding plurality of substances present in the composition unless otherwise specified, in the case where a plurality of substances corresponding to each component are present in the composition.

In the present specification, the term "process" refers not only to an independent process but also to a process that is not clearly distinguished from other processes, if the desired purpose of the process is achieved.

In the labeling of groups (atomic groups) in the present specification, the unsubstituted and unsubstituted labels include groups having no substituent and groups having substituents. For example, "alkyl" means to include not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Unless otherwise specified, in the present specification, "exposure" means not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. The light used for exposure generally includes an open spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and activation rays (active energy rays) such as electron beams.

In addition, 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 invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are the following molecular weights unless otherwise specified: the samples were measured by a Gel Permeation Chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by TOSOH CORPORATION), and converted using a solvent THF (tetrahydrofuran) and a differential refractometer, and polystyrene was used as a standard substance.

(photosensitive transfer Material)

The photosensitive transfer material according to the present invention includes, in order, a protective film, a photosensitive resin layer, a 1 st resin layer, a 2 nd resin layer, and a temporary support, wherein the 1 st resin layer contains particles, the 1 st resin layer is in contact with the 2 nd resin layer, the 1 st resin layer and the 2 nd resin layer are peelable, and the 2 nd resin layer contains a resin having a polyethylene structure.

As a result of the detailed study by the present inventors, the present inventors have found that, in a conventional photosensitive transfer material having a protective film, a photosensitive resin layer, a 1 st resin layer, a 2 nd resin layer, and a temporary support in this order, after the photosensitive transfer material is attached by peeling off the cover film, the peelability between the 1 st resin layer and the 2 nd resin layer is insufficient, and the peeling between the above layers is difficult.

In the photosensitive transfer material according to the present invention, it was found that the 1 st resin layer contains particles, and the 2 nd resin layer contains a resin having a polyethylene structure, and the 1 st resin layer and the 2 nd resin layer after the photosensitive transfer material is attached by peeling the protective film are excellent in peelability.

The mechanism of action based on the excellent effects of the above structure is not clear, but is presumed as follows.

In the resin having a polyethylene structure, since the glass transition temperature (Tg) of the homopolymer of ethylene is as low as-125 ℃, the resin is excellent in flexibility and has an appropriate adhesiveness, and further, since the polyethylene structure is

Water and therefore hydrogen bond based interactions are small. The 1 st resin layer has particles that act as anchors to improve the peeling force between the 1 st resin layer and the 2 nd resin layer, and also act as matting agents to obtain proper peelability. It is assumed that the release property between the 1 st resin layer and the 2 nd resin layer after the photosensitive transfer material is attached by peeling the protective film by the synergistic effect thereof is excellent.

The photosensitive transfer material according to the present invention includes, in order, a protective film, a photosensitive resin layer, a 1 st resin layer, a 2 nd resin layer, and a temporary support.

The photosensitive transfer material according to the present invention may have other layers between the photosensitive resin layer and the 1 st resin layer, between the protective film and the photosensitive resin layer, and the like.

In the photosensitive transfer material according to the present invention, from the viewpoint of releasability between the 1 st resin layer and the 2 nd resin layer after the photosensitive transfer material is attached by peeling the protective film (also referred to as "1 st resin layer/2 nd resin layer releasability"), the release force between the 1 st resin layer and the 2 nd resin layer is preferably greater than the release force between the photosensitive resin layer and the protective film.

In the photosensitive transfer material according to the present invention, the value of (the peeling force between the 1 st resin layer and the 2 nd resin layer) - (the peeling force between the photosensitive resin layer and the protective film) is preferably-0.2 gf/cm or more, more preferably-0.1 gf/cm or more, still more preferably 0gf/cm or more, and particularly preferably 0.5gf/cm or more, from the viewpoints of the peelability of the 1 st resin layer/the 2 nd resin layer and the peelability between the photosensitive resin layer and the protective film (also referred to as "peelability of the photosensitive resin layer/the protective film"). The upper limit value is preferably 10gf/cm or less, more preferably 8gf/cm or less, and particularly preferably 5gf/cm or less.

In the photosensitive transfer material according to the present invention, the peeling force between the 1 st resin layer and the 2 nd resin layer is preferably 0.8gf/cm or more, more preferably 1.0gf/cm or more, still more preferably 1.5gf/cm to 10gf/cm, and particularly preferably 1.5gf/cm to 5gf/cm, from the viewpoints of the 1 st resin layer/2 nd resin layer peelability and the photosensitive resin layer/protective film peelability.

In the photosensitive transfer material according to the present invention, the peeling force between the photosensitive resin layer and the protective film is preferably 0.1gf/cm to 2gf/cm, more preferably 0.2gf/cm to 1.5gf/cm, and particularly preferably 0.3gf/cm to 1.0gf/cm, from the viewpoints of the 1 st resin layer/2 nd resin layer peelability and the photosensitive resin layer/protective film peelability.

The peel force between the 1 st resin layer and the 2 nd resin layer was measured by the following method.

A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method, and a PET substrate with a copper layer was produced.

After the protective film was peeled off from the photosensitive transfer material, the protective film was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4 m/min.

The photosensitive transfer material laminated on the obtained copper-clad PET substrate was cut into a width of 4.5cm, and a copper-clad PET substrate side was attached to a 1 mm-thick polycarbonate sheet to which a double-sided tape was attached, to prepare a test sample.

The test sample obtained was stretched by Tensilon in a direction of bending the temporary support of the photosensitive transfer material by 180 degrees, and the peeling force between the 1 st resin layer and the 2 nd resin layer was measured. The peel force was measured at a peel speed of 300 mm/min.

The peel force between the photosensitive resin layer and the protective film was measured by the following method.

A copper layer having a thickness of 200nm was formed on a PET film having a thickness of 100 μm by a sputtering method, and a PET substrate with a copper layer was formed.

The photosensitive transfer material was cut into a width of 4.5cm, and a temporary support was attached to a 1mm thick polycarbonate plate to which a double-sided tape was attached, to prepare a test sample.

The obtained test sample was stretched by Tensilon in a direction of bending the protective film of the photosensitive transfer material by 180 degrees, and the peeling force between the photosensitive resin layer and the protective film was measured. The peel force was measured at a peel speed of 300 mm/min.

[ protective film ]

The photosensitive transfer material has a protective film.

The photosensitive resin layer is preferably in direct contact with the protective film.

As a material constituting the protective film, a resin film and paper are exemplified, and from the viewpoint of strength and flexibility, a resin film is preferable.

Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.

The surface of the protective film in contact with the photosensitive resin layer is preferably subjected to a mold release treatment. Examples of the mold release treatment include films made of silicone resins, fluorine resins, polyolefin resins, and the like. Examples of the release-treated film include Cerapeel WZ, cerapeel MDA, cerapeel MFA, cerapeel TK07, cerapeel BKE, cerapeel BX8A, cerapeel SY, cerapeel PJ271, cerapeel PJ111, cerapeel HP2, and Cerapeel PJ101 manufactured by TORAY INDUSTRIES, INC..

The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.

Further, from the viewpoint of further excellent resolution, the arithmetic average roughness Ra value of the surface of the protective film (hereinafter, also simply referred to as "surface of the protective film") in contact with the photosensitive resin layer is preferably 0.3 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less. This is considered to be because the Ra value of the surface of the protective film is in the above range, and the uniformity of the layer thickness of the photosensitive resin layer and the resin pattern formed is improved.

The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more.

The Ra value of the surface of the protective film was measured by the following method.

The surface profile of the protective film was measured using a three-dimensional optical profiler (New View7300, manufactured by Zygo corporation) under the following conditions, to obtain the surface profile of the optical film.

As the measurement/analysis software, microscope Application of MetroPro ver8.3.2 was used. Then, the Surface Map screen is displayed by the analysis software, and histogram data is obtained in the Surface Map screen. An arithmetic average roughness is calculated from the obtained histogram data, thereby obtaining an Ra value of the surface of the protective film.

When the protective film is attached to the photosensitive transfer material, the protective film may be peeled off from the photosensitive transfer material, and the Ra value of the peeled surface may be measured.

[ photosensitive resin layer ]

The photosensitive transfer material used in the present invention has a photosensitive resin layer.

The photosensitive resin layer may be a negative type photosensitive resin layer or a positive type photosensitive resin layer, but is preferably a negative type photosensitive resin layer in which the solubility of the exposed portion in a developer is reduced by exposure and the non-exposed portion is removed by development.

The photosensitive resin layer preferably contains an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator, and more preferably contains an alkali-soluble resin based on the total mass of the photosensitive resin layer: 10 to 90 mass percent; olefinically unsaturated compounds: 5 to 70 mass percent; photopolymerization initiator: 0.01 to 20 mass%.

The respective components will be described in order below.

< alkali-soluble resin >

The photosensitive resin layer preferably contains an alkali-soluble resin.

In the present specification, "alkali-soluble" means that the solubility in 100g of a 1 mass% aqueous solution of sodium carbonate is 0.1g or more at 22 ℃.

The alkali-soluble resin is not particularly limited, and for example, a known alkali-soluble resin used for an etching resist can be preferably used.

And, the alkali-soluble resin is preferably a binder polymer.

As the alkali-soluble resin, an alkali-soluble resin having an acid group is preferable.

Among them, the alkali-soluble resin is preferably a polymer a described later.

Polymer A-

As the alkali-soluble resin, polymer a is preferably contained.

The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and even more preferably less than 190mgKOH/g, from the viewpoint of further excellent resolution by suppressing swelling of the photosensitive resin layer due to the developer.

The lower limit of the acid value of the polymer A is not particularly limited, but is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, particularly preferably 170mgKOH/g or more, from the viewpoint of further excellent developability.

The acid value was the mass [ mg ] of potassium hydroxide required for neutralization of 1g of the sample,

in the present specification, the unit is referred to as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The acid value of the polymer a may be adjusted according to the type of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.

The weight average molecular weight of polymer a is preferably 5,000 ～ 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge meltability and chipping property when the photosensitive resin laminate is produced, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge meltability means the ease with which the photosensitive resin layer overflows from the end surface of the roller when the photosensitive transfer material is wound into a roll shape. The chipability refers to the degree of difficulty in chipping when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, the chips are transferred to a mask in a subsequent exposure step or the like, and cause defective products. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0. In the present invention, the molecular weight is a value measured by gel permeation chromatography. And the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing the line width from becoming thicker or the resolution from deteriorating when the focus position is shifted during exposure, the photosensitive resin layer preferably contains a monomer component having an aromatic hydrocarbon as the polymer a. Examples of such aromatic hydrocarbons include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content ratio of the monomer component having an aromatic hydrocarbon in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more, based on the total mass of the total monomer components. The upper limit is not particularly limited, but is preferably 95 mass% or less, more preferably 85 mass% or less. The content of the monomer component having aromatic hydrocarbon when the plurality of polymers a are contained was determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, a styrene dimer, a styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is styrene, the content of the styrene monomer component is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of the total monomer components.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.

Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group, for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like; vinyl monomers having a benzyl group, for example, vinylbenzyl chloride, vinylbenzyl alcohol, and the like. Among them, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer a is benzyl (meth) acrylate, the content of the benzyl (meth) acrylate monomer component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of the total monomer components.

The polymer a containing a monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon with at least 1 of the first monomers described later and/or at least 1 of the second monomers described later.

The polymer a containing no monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing at least 1 kind of a first monomer described later, more preferably by copolymerizing at least 1 kind of the first monomer with at least 1 kind of a second monomer described later.

The first monomer is a monomer having a carboxyl group in a molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is preferable.

The content of the first monomer in the polymer a is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of the total monomer components.

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of the total monomer components. The copolymerization ratio is preferably 10 mass% or more, more preferably 15 mass% or more, and even more preferably 20 mass% or more from the viewpoint of exhibiting good developability, controlling edge meltability, and the like. The copolymerization ratio is preferably 50 mass% or less from the viewpoint of high resolution of the resist pattern and the curl shape, and more preferably 35 mass% or less, further preferably 30 mass% or less, particularly preferably 27 mass% or less from the viewpoint of chemical resistance of the resist pattern.

The second monomer is a non-acidic monomer having at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth) acrylonitrile, etc. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is particularly preferable.

The content of the second monomer in the polymer a is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass, based on the total mass of the total monomer components.

From the viewpoint of suppressing the line width thickening or the deterioration of resolution at the time of focus position shift at the time of exposure, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.

In one embodiment, the polymer a preferably contains 25 to 40% by mass of a monomer component having an aromatic hydrocarbon, 20 to 35% by mass of a first monomer component, and 30 to 45% by mass of a second monomer component. In another embodiment, the polymer preferably contains 70 to 90 mass% of the monomer component having an aromatic hydrocarbon and 10 to 25 mass% of the first monomer component.

The polymer a may have a branched structure or an alicyclic structure in a side chain. The polymer a may have a linear structure in a side chain. The branched structure or alicyclic structure can be introduced into the side chain of the polymer a by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. The group having an alicyclic structure may be monocyclic or polycyclic.

Specific examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, sec-isoamyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, tert-octyl (meth) acrylate, and the like. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.

Specific examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, there may be mentioned (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (also referred to as "carbon atom number"). More specific examples thereof include (bicyclo [2.2.1] heptyl-2) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyl adamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) acrylate, 3, 5-triethyl-1-adamantyl (meth) acrylate, 7-octahydro-indene (meth) acrylate, 1-menthyl (meth) acrylate, 1-adamantyl (meth) acrylate, 1-2-adamantyl (meth) acrylate, 2-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methano-indene (meth) acrylate, and (meth) acrylate 3-hydroxy-2, 6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy bicyclo [4.1.0] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Among these (meth) acrylic esters, cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecane (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is particularly preferable.

The polymer a may be used alone or in combination of 2 or more. When 2 or more kinds of polymers are used in combination, it is preferable to use 2 kinds of polymers a containing a monomer component having an aromatic hydrocarbon in combination, or to use a polymer a containing a monomer component having an aromatic hydrocarbon in combination with a polymer a not containing a monomer component having an aromatic hydrocarbon. In the latter case, the ratio of the polymer a containing the monomer component having an aromatic hydrocarbon to be used is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the whole of the polymer a.

Regarding the synthesis of polymer a, it is preferable to proceed as follows: to a solution obtained by diluting one or more of the above-described monomers with a solvent such as acetone, methyl ethyl ketone, isopropyl alcohol, etc., a proper amount of a radical polymerization initiator such as benzoyl peroxide, azoisobutyronitrile, etc., is added, and heating and stirring are performed. In some cases, synthesis may be performed while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, in addition to the solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The glass transition temperature Tg of the polymer A is preferably 30℃or more and 135℃or less. By using the polymer a having a Tg of 135 ℃ or less in the photosensitive resin layer, it is possible to suppress the line width from becoming thicker or the resolution from deteriorating when the focus position is shifted during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130℃or lower, still more preferably 120℃or lower, and particularly preferably 110℃or lower. Further, from the viewpoint of improving the edge melting resistance, it is preferable to use the polymer a having Tg of 30 ℃ or higher. From this viewpoint, the Tg of the polymer A is more preferably 40℃or higher, still more preferably 50℃or higher, particularly preferably 60℃or higher, and most preferably 70℃or higher.

The photosensitive resin layer may contain a resin other than the alkali-soluble resin.

Examples of the resin other than the alkali-soluble resin include acrylic resins, styrene-acrylic copolymers (wherein the styrene content is 40 mass% or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyamide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimine, polyallylamine and polyalkylene glycols.

The alkali-soluble resin may be used alone or in combination of 2 or more.

The proportion of the alkali-soluble resin to the total mass of the photosensitive resin layer is preferably in the range of 10 to 90 mass%, more preferably 30 to 70 mass%, and even more preferably 40 to 60 mass%. From the viewpoint of controlling the development time, the proportion of the alkali-soluble resin to the photosensitive resin layer is preferably 90 mass% or less. On the other hand, from the viewpoint of improving the edge melting resistance, the ratio of the alkali-soluble resin to the photosensitive resin layer is preferably 10 mass% or more.

(ethylenically unsaturated Compound)

The photosensitive resin layer preferably contains an ethylenically unsaturated compound.

In the present specification, the "ethylenically unsaturated compound" means a compound that is polymerized by the action of a photopolymerization initiator described later, and is a compound different from the above-described alkali-soluble resin.

The ethylenically unsaturated compound is a component contributing to photosensitivity (i.e., photocurability) of the negative photosensitive resin layer and strength of the cured film.

The ethylenically unsaturated compound is a compound having 1 or more ethylenically unsaturated groups.

The photosensitive resin layer preferably contains an ethylenically unsaturated compound having 2 or more functions.

The ethylenically unsaturated compound having 2 or more functions herein means a compound having 2 or more ethylenically unsaturated groups in 1 molecule.

As the ethylenically unsaturated group, (meth) acryl is more preferable.

As the ethylenically unsaturated compound, (meth) acrylate compounds are preferred.

The photosensitive resin layer preferably contains an ethylenically unsaturated compound having a polymerizable group.

The polymerizable group of the ethylenically unsaturated compound is not particularly limited as long as it is a group involved in polymerization reaction, and examples thereof include a group having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group; and a group having a cationically polymerizable group such as an epoxy group and an oxetanyl group.

The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group.

The ethylenically unsaturated compound is preferably a compound having 2 or more ethylenically unsaturated groups in 1 molecule (polyfunctional ethylenically unsaturated compound) from the viewpoint of more excellent photosensitivity of the photosensitive resin layer.

Further, from the viewpoint of further excellent resolution and releasability, the number of the ethylenically unsaturated groups in 1 molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, and still more preferably 2 or less.

From the viewpoint of more excellent balance of photosensitivity, resolution and releasability of the photosensitive resin layer, the photosensitive resin layer preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in 1 molecule, more preferably contains a 2-functional ethylenically unsaturated compound having 2 ethylenically unsaturated groups in 1 molecule.

From the viewpoint of excellent releasability, the content of the 2-functional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60 mass% or more, more preferably more than 70 mass%, and still more preferably 90 mass% or more with respect to the content of the ethylenically unsaturated compound. The upper limit is not particularly limited, and may be 100 mass%. That is, all of the ethylenically unsaturated compounds contained in the photosensitive resin layer may be 2-functional ethylenically unsaturated compounds.

Further, as the ethylenically unsaturated compound, (meth) acrylate compounds having a (meth) acryloyl group as a polymerizable group are preferable.

Olefinically unsaturated compounds B1-

The photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and 2 ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in 1 molecule among the above ethylenically unsaturated compounds.

From the viewpoint of more excellent resolution, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 55 mass% or more, and particularly preferably 60 mass% or more. The upper limit is not particularly limited, but is preferably 99 mass% or less, more preferably 95 mass% or less, further preferably 90 mass% or less, and particularly preferably 85 mass% or less from the viewpoint of releasability.

Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferable, and benzene ring is more preferable. The aromatic ring may have a substituent.

The ethylenically unsaturated compound B1 may have only 1 aromatic ring or may have 2 or more aromatic rings.

The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive resin layer due to the developer.

Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and a bisphenol a structure is preferable.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure.

The bisphenol structure may be directly bonded to 2 polymerizable groups at both ends, or may be bonded to each other with 1 or more alkylene oxide groups interposed therebetween. As the alkylene oxide group added to both ends of the bisphenol structure, ethylene oxide group or propylene oxide group is preferable, and ethylene oxide group is more preferable. The number of alkylene oxide groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule.

The olefinically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated into the present specification.

As the ethylenically unsaturated compound B1, a 2-functional ethylenically unsaturated compound having a bisphenol a structure is preferable, and 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.

Examples of 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitachi Chemical Co, ltd.) propane, 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecyloxypropoxy) phenyl) propane (manufactured by FA-3200MY,Hitachi ChemicalCo, ltd.), 2-bis (4- (methacryloxypentadecoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical, manufactured by NK-37co.), and bis (NK-10, manufactured by NK-10, ltd.) phenol.

As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

[ chemical formula 1]

In the formula (Bis), R ₁ R is R ₂ Each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ B is C ₃ H ₆ ，n ₁ N is as follows ₃ Each independently is an integer of 1 to 39 and n ₁ +n ₃ Is an integer of 2 to 40, n ₂ N is as follows ₄ Each independently is an integer of 0 to 29 and n ₂ +n ₄ The repeating units of- (A-O) -and- (B-O) -may be arranged in a random or block form, and are integers of 0 to 30. Also, in the case of the block, either one of- (A-O) -and- (B-O) -may be on the bisphenol structure side.

In one aspect, n ₁ +n ₂ +n ₃ +n ₄ Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. And n is ₂ +n ₄ Preferably an integer of 0 to 10, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2, and particularly preferably 0.

The ethylenically unsaturated compound B1 may be used alone or in combination of 2 or more.

From the viewpoint of further excellent resolution, the content of the ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 70 mass% or less, more preferably 60 mass% or less, from the viewpoints of transferability and edge melting (a phenomenon in which components in the photosensitive resin layer bleed out from the end portion of the photosensitive transfer material).

The photosensitive resin layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1.

The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited, and may be appropriately selected from known compounds. Examples thereof include compounds having 1 ethylenically unsaturated group in 1 molecule (monofunctional ethylenically unsaturated compounds), 2-functional ethylenically unsaturated compounds having no aromatic ring, and ethylenically unsaturated compounds having 3 or more functions.

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of alkylene glycol di (meth) acrylates include tricyclodecane dimethanol diacrylate (A-DCP, shin-Nakamura Chemical Co., ltd.), tricyclodecane dimethanol dimethacrylate (DCP, shin-Nakamura Chemical Co., ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, shin-Nakamura Chemical Co., ltd.), 1, 6-hexanediol diacrylate (A-HD-N, shin-Nakamura Chemical Co., ltd.), ethylene glycol dimethacrylate, 1, 10-decane diol diacrylate and neopentyl glycol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.

Examples of urethane di (meth) acrylates include propylene oxide modified urethane di (meth) acrylates and ethylene oxide and propylene oxide modified urethane di (meth) acrylates. Examples of the commercial products include 8UX-015A (Taisei Fine Chemical Co., ltd.), UA-32P (Shin-Nakamura Chemical Co., ltd.), and UA-1100H (Shin-Nakamura Chemical Co., ltd.).

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof.

Here, "tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate. In one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 3 or more functional ethylenically unsaturated compounds, and more preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 2 or more ethylenically unsaturated compounds 3 or more functional ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the ethylenically unsaturated compound having 3 or more functions is preferably (total mass of the ethylenically unsaturated compounds B1): (total mass of the ethylenically unsaturated compounds having 3 or more functions) =1:1 to 5:1, more preferably 1.2:1 to 4:1, still more preferably 1.5:1 to 3:1.

In one embodiment, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and 2 or more kinds of 3-functional ethylenically unsaturated compounds.

Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical Co., ltd., A-9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compounds (Nippon Kayaku Co., ltd., KAYARAD RP-1040, shin-Nakamura Chemical Co., ltd., ATM-35E and A-9300, DAICEL-ALLNEX LTD, EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (Shin-Nakamura Chemical Co., ltd., A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (AGOSEI CO., LTD. Etc.), ARONIX M-520 (AGOSEI CO., LTD. TOOSEI. 510).

Further, as the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, the ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of japanese unexamined patent publication No. 2004-239942 can be used.

From the viewpoints of resolution and linearity, the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound in the photosensitive resin layer to the content Mb of the alkali-soluble resin is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 to 0.9.

Further, from the viewpoint of curability and resolution, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth) acryloxy compound.

Further, from the viewpoints of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive resin layer more preferably contains a (meth) acryloyloxy compound, and the content of the acryloyloxy compound is 60 mass% or less relative to the total mass of the (meth) acryloyloxy compound contained in the photosensitive resin layer.

The molecular weight (weight average molecular weight (Mw) in the case of having a distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

The ethylenically unsaturated compound may be used alone or in combination of at least 2 kinds.

The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 20 to 50% by mass, based on the total mass of the photosensitive resin layer.

< photopolymerization initiator >

The photosensitive resin layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that starts polymerization of an ethylenically unsaturated compound upon receiving activation light such as ultraviolet light, visible light, or X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

Examples of the photo-radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkyl benzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a bisimidazole compound.

As the photo radical polymerization initiator, for example, those described in paragraphs 0031 to 0042 of JP 2011-95716 and 0064 to 0081 of JP 2015-14783 can be used.

Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p ' -dimethoxybenzyl) anisyl ester, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF corporation), omnifad651 and 369 (trade name: IGM Resins B.V. Co., ltd.), and 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bisimidazole (Tokyo Chemical Industry Co., ltd.).

Examples of the commercially available photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (o-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG,IGM Resins B.V. Manufactured by Omni-phenyl) -2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: omni 907,IGM Resins B.V. Manufactured by Omni 907,IGM Resins B.V), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropoyl) benzyl ] phenyl } -2-methylpropanene (trade name: omni-4-morpholinyl) phenyl ] -1-butanone (trade name: omni 3, manufactured by Omni-4-methylphenyl) methyl ] -1-butanone, IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: omnirad 1173,IGM Resins B.V), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184,IGM Resins B.V, manufactured) 2, 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651,IGM Resins B.V, manufactured), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (trade name: omnirad TPO H, IGM Resins b.v.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819,IGM Resins B.V), oxime ester-based photopolymerization initiator (trade name: lunar 6,DKSH Holding Ltd), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, hampford corporation) and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: BCTB, tokyo Chemical Industry co., ltd.).

The photo cation polymerization initiator (photoacid generator) is a compound that receives activating light to generate an acid. The photo cation polymerization initiator is preferably a compound which generates an acid in response to an activating light having a wavelength of 300nm or more, preferably 300 to 450nm, but the chemical structure thereof is not limited. The photo cation polymerization initiator which does not directly induce the activating light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by inducing the activating light having a wavelength of 300nm or more by being used in combination with the sensitizer.

The photo-cation polymerization initiator is preferably a photo-cation polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, and is preferably-10.0 or more, for example.

Examples of the photo-cationic polymerization initiator include an ionic photo-cationic polymerization initiator and a nonionic photo-cationic polymerization initiator.

Examples of the ionic photo-cation polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

As the ionic photo-cation polymerization initiator, the ionic photo-cation polymerization initiator described in paragraphs 0114 to 0133 of Japanese unexamined patent publication No. 2014-85643 can be used.

Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-s-triazine, diazomethane compound and imide sulfonate compound, those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494 can be used. Further, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be used.

The photosensitive resin layer may contain 1 kind of photopolymerization initiator alone or 2 or more kinds of photopolymerization initiators.

The content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1.0 mass% or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10 mass% or less, more preferably 5 mass% or less, relative to the total mass of the photosensitive resin layer.

< pigment >

The photosensitive resin layer preferably contains a dye, and more preferably contains a dye having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm at the time of color development and a maximum absorption wavelength that changes by an acid, an alkali or a radical (also simply referred to as "dye N") from the viewpoints of visibility of an exposed portion and a non-exposed portion, visibility of a pattern after development, and resolution. When pigment N is contained, although the detailed mechanism is not clear, the adhesion to the adjacent layers (for example, the temporary support and the 1 st resin layer) is improved, and the resolution is further excellent.

In the present specification, the "the dye whose wavelength is greatly changed by an acid, a base or a radical" may refer to any one of a method in which the dye in a color developed state is decolorized by an acid, a base or a radical, a method in which the dye in a decolorized state is developed by an acid, a base or a radical, and a method in which the dye in a color developed state is changed to a color developed state of another hue.

Specifically, the dye N may be a compound that changes color from a decolored state by exposure, or may be a compound that changes color from a decolored state by exposure. In this case, the coloring matter may be a coloring matter which changes the state of color development or decoloration by generating an acid, an alkali or a radical in the photosensitive resin layer by exposure to light and causing a reaction, or a coloring matter which changes the state of color development or decoloration by changing the state (for example, pH) in the photosensitive resin layer by an acid, an alkali or a radical. Further, the coloring matter may be a coloring matter which is not exposed to light but is directly stimulated by an acid, an alkali or a radical to change the state of color development or decoloration.

Among them, from the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical.

From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive resin layer preferably contains a dye whose maximum absorption wavelength is changed by radicals as both the dye N and the photo radical polymerization initiator.

Further, the coloring matter N is preferably a coloring matter that develops color by an acid, an alkali or a radical from the viewpoint of visibility of the exposed portion and the non-exposed portion.

Examples of the coloring mechanism of the coloring matter N in the present invention include the following: a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator) or a photo alkali generator is added to the photosensitive resin layer, and a radical reactive pigment, an acid reactive pigment or a base reactive pigment (for example, a leuco pigment) develops color by radicals, acids or bases generated by the photo radical polymerization initiator, the photo cation polymerization initiator or the photo alkali generator after exposure.

The maximum absorption wavelength at the wavelength range of 400nm to 780nm at the time of color development of the dye N is preferably 550nm or more, more preferably 550nm to 700nm, still more preferably 550nm to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion.

The dye N may have only 1 maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development, or may have 2 or more. When the dye N has a maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development of 2 or more, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of pigment N is obtained by: under atmospheric ambient gas, a spectrophotometer was used: UV3100 (manufactured by Shimadzu Corporation), the transmission spectrum of a solution containing pigment N (liquid temperature: 25 ℃ C.) was measured in a range of 400nm to 780nm, and the wavelength at which the intensity of light became extremely small (maximum absorption wavelength) was detected.

Examples of the coloring matter which is developed or decolored by exposure to light include colorless compounds.

Examples of the coloring matter to be decolorized by exposure to light include colorless compounds, diarylmethane-based coloring matters, oxazine-based coloring matters, xanthene-based coloring matters, iminonaphthoquinone-based coloring matters, azomethine-based coloring matters, and anthraquinone-based coloring matters.

The coloring matter N is preferably a colorless compound from the viewpoint of visibility of the exposed portion and the non-exposed portion.

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a colorless compound having an indolyl phthalide skeleton (indolyl phthalide-based dye), and a colorless compound having a colorless gold amine skeleton (colorless gold amine-based dye).

Among them, triarylmethane-based pigments or fluoran-based pigments are preferable, and colorless compounds having a triphenylmethane skeleton (triphenylmethane-based pigments) or fluoran-based pigments are more preferable.

The colorless compound is preferably a lactone ring, a sultone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator, whereby the colorless compound is changed to a closed-loop state to be decolorized, or the colorless compound is changed to an open-loop state to be developed. As the colorless compound, a compound having a lactone ring, a sultone ring, or a sultone ring and the lactone ring, the sultone ring, or the sultone ring is developed by free radical or acid ring opening is preferable, and a compound having a lactone ring and the lactone ring is developed by free radical or acid ring opening is more preferable.

Examples of the dye N include the following dyes and colorless compounds.

Specific examples of the dye in pigment N include brilliant green (brillon green), ethyl violet, methyl green, crystal violet, basic fuchsine (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metandine yellow (metandil yellow), thymol sulfophthalein (thymol sulfonphthalein), xylenol blue, methyl orange, para-methyl red, congo red, benzored violet (4B, alpha-naphthalene red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), paragood red (parafuchsin), victoria pure blue (victoria pure blue) -naphthalene sulfonate, victoria pure blue (Hodogaya Chemical co., ltd), oil blue #603 (Orient Chemical Industries co., ltd), oil pink #312 (Orient Chemical Industries co., ltd), oil red 5B (Orient Chemical Industries co., ltd), oil scarlet #308 (Orient Chemical Industries co., ltd), oil red OG (Orient ChemicalIndustries co., ltd), oil red RR (Orient Chemical Industries co., ltd), oil green #502 (Orient Chemical Industries co., ltd), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co., ltd), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, gold amine, 4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyl iminonaphthoquinone, gold amine, 2-carboxyoctadecylamino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-beta-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the colorless compound in the dye N include p, p', p "-hexamethyltriphenylamine methane (colorless crystal violet), pergascript Blue SRB (Ciba-Geigy Co.), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidinyl) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylanilino fluoran, 3- (N, N-diethylamino) -6-chloro-7-methylanilino-fluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-anilino-fluoran, and 4-dimethylamino-fluoran 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-dimethylanilinofluoran, 3-hydropyridyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-ethyl-2-methylindol-3-yl) phthalide, 3- (1-ethyl-2-methylindol-3-yl) phthalide, 6 '-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.

The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals, and more preferably a dye whose color is developed by radicals, from the viewpoints of visibility of the exposed portion and the non-exposed portion, visibility of the pattern after development, and resolution.

As pigment N, preference is given to leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate.

The pigment may be used alone or in combination of 1 or more than 2.

The content of the coloring matter is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative to the total mass of the photosensitive resin layer, from the viewpoints of visibility of the exposed portion and the non-exposed portion, visibility of the pattern after development, and resolution.

The content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative to the total mass of the photosensitive resin layer, from the viewpoints of visibility of the exposed portion and the non-exposed portion, visibility of the pattern after development, and resolution.

The content of the dye N is the content of the dye when all the dye N contained in the photosensitive resin layer is in a color development state. Hereinafter, a method for determining the content of the dye N will be described by taking a dye that develops color by a radical as an example.

2 solutions were prepared in which 0.001g or 0.01g of pigment was dissolved in 100mL of methyl ethyl ketone. To each of the obtained solutions, irgacure OXE01 (trade name, BASF Japan ltd.) as a photo radical polymerization initiator was added, and 365nm light was irradiated, thereby generating radicals and bringing all the pigments into a color development state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under atmospheric air using a spectrophotometer (manufactured by UV3100, shimadzu Corporation), and a calibration curve was prepared.

Next, absorbance of the solution in which all the pigments were developed was measured in the same manner as described above, except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive resin layer was calculated based on the calibration curve from the absorbance of the obtained solution containing the photosensitive resin layer.

< other ingredients >

The photosensitive resin layer may contain components other than the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, and the pigment.

Surfactant-containing compositions

From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (Nonion) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.

As a commercial product of the fluorine-based surfactant, for example, examples of the materials include Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, F-565, and EXP.MFS-578R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above DIC Corporation), fluorad (trade name) FC430, FC431, FC171 (above Sumitomo 3M Limited), surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above AGC Inc. system), polyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (above OMNOVA Solutions Inc. system), ftergent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by Neos Company Limited above), U-120E (Uni-chem Co., ltd.), and the like.

The fluorine-based surfactant may preferably be an acrylic compound having a molecular structure including a functional group containing a fluorine atom, and the fluorine atom may be volatilized by cutting a portion of the functional group containing a fluorine atom when heat is applied. Examples of the fluorine-containing surfactant include Megafac (trade name) DS series (chemical industry daily report (2016, 2, 22 days), daily necessities, news (2016, 2, 23 days)) manufactured by DIC Corporation, for example Megafac (trade name) DS-21.

The fluorine-based surfactant is preferably a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound, each of which has a fluorinated alkyl group or a fluorinated alkylene ether group.

The fluorine-based surfactant may be a block polymer. The fluorine-containing surfactant may preferably be a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom, and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).

The fluorine-based surfactant may be a fluoropolymer having an ethylenically unsaturated group in a side chain. Examples of the "Megafac" (trade name) include RS-101, RS-102, RS-718K, RS-72-K (DIC Corporation).

The fluorine-based surfactant is preferably a surfactant derived from a substitute material of a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), from the viewpoint of improving environmental suitability.

Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol octacosanoate, sorbitan fatty acid ester, pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (above, manufactured by BASF corporation), tetronic (trade name) 304, 701, 704, 901, 904, 150R1, hydroplaat WE 3323 (above manufactured by BASF corporation), solsperse (trade name) 20000 (above manufactured by Lubrizol Japan limited), NCW-101, NCW-1001, NCW-1002 (above manufactured by FUJIFILM Wako Pure Chemical Corporation), piomin (trade name) D-1105, D-6112-W, D-6315 (above manufactured by Takemoto Oil & Fat co., ltd), olfine E1010, surfynol 104, 400, 440 (above manufactured by Nissin Chemical co., ltd).

The silicone surfactant includes a linear polymer composed of siloxane bonds, and a modified siloxane polymer having an organic group introduced into a side chain or a terminal thereof.

Specific examples of the silicone surfactant include EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2 (manufactured by DIC Corporation, supra), DOWSIL (trade name) 8032ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicone SH PA, toray Silicone SH8400 (Dow Corning Toray Co, supra), ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354-A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (above, et-su Co.); ltd), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (BYK 300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, manufactured by Momentive Performance Materials inc. Above, BYK378 (BYK Chemie Co., ltd.).

The photosensitive resin layer may contain 1 kind of surfactant alone or 2 or more kinds of surfactants.

The content of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, based on the total mass of the photosensitive resin layer.

Additive-

The photosensitive resin layer may contain a known additive as required in addition to the above components.

Examples of the additive include a polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, benzotriazoles, carboxybenzotriazoles, and a solvent. The photosensitive resin layer may contain 1 kind of each additive alone or 2 or more kinds of additives.

The photosensitive resin layer may contain a polymerization inhibitor. The polymerization inhibitor is preferably a radical polymerization inhibitor.

Examples of the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenyl hydroxylamine aluminum salt, and diphenyl nitrosoamine. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenyl hydroxylamine aluminum salt is preferably used as a polymerization inhibitor.

Examples of the benzotriazoles include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

Examples of carboxybenzotriazoles include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. As the carboxybenzotriazoles, for example, commercially available products such as CBT-1 (JOHOKU CHEMICAL CO., LTD. Product name) can be used.

The total content of the polymerization inhibitor, benzotriazole and carboxybenzotriazole is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, based on the total mass of the photosensitive resin layer. The content is preferably 0.01 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, the content is preferably 3 mass% or less.

The photosensitive resin layer may contain a sensitizer.

The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone (xanthone) compound, a thioxanthone (thioxanthone) compound, an acridone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (e.g., 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.

The photosensitive resin layer may contain 1 sensitizer alone or 2 or more sensitizers.

When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing speed by balancing the polymerization speed and chain transfer, the content is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% with respect to the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least 1 selected from plasticizers and heterocyclic compounds.

Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International publication No. 2018/179640.

The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from the photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

The photosensitive resin layer may contain known additives such as metal oxide particles, antioxidants, dispersants, acid-proliferation agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents.

The additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643, the contents of which are incorporated herein by reference.

< physical Properties etc.)

The layer thickness of the photosensitive resin layer is preferably 0.1 μm to 300. Mu.m, more preferably 0.2 μm to 100. Mu.m, still more preferably 0.5 μm to 50. Mu.m, still more preferably 0.5 μm to 15. Mu.m, particularly preferably 0.5 μm to 10. Mu.m, and most preferably 0.5 μm to 8. Mu.m. This can improve the developability of the photosensitive resin layer and improve the resolution.

In one embodiment, the thickness is preferably 0.5 μm to 5. Mu.m, more preferably 0.5 μm to 4. Mu.m, and still more preferably 0.5 μm to 3. Mu.m.

The layer thicknesses of the layers included in the photosensitive transfer material were measured as follows: a cross section in a direction perpendicular to the main surface of the photosensitive transfer material was observed by a scanning electron microscope (SEM: scanning Electron Microscope), and the thickness of each layer was measured at 10 points or more based on the obtained observation image, and the average value was calculated.

Further, from the viewpoint of further excellent adhesion, the light transmittance of the photosensitive resin layer at 365nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

< method of Forming >

The method for forming the photosensitive resin layer is not particularly limited as long as the layer containing the above components can be formed.

As a method for forming the photosensitive resin layer, for example, the following methods are mentioned: a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, and the like is prepared, and the photosensitive resin composition is applied to a surface of a temporary support or the like, and a coating film of the photosensitive resin composition is dried to form the photosensitive resin composition.

Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, any of the above components, and a solvent.

In order to adjust the viscosity of the photosensitive resin composition and facilitate formation of the photosensitive resin layer, the photosensitive resin composition preferably contains a solvent.

Solvent-

The solvent contained in the photosensitive resin composition is not particularly limited as long as it is a solvent capable of dissolving or dispersing the alkali-soluble resin, the ethylenically unsaturated compound, the photopolymerization initiator, and any of the above components, and a known solvent can be used.

Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing 2 or more of these solvents.

In the case of producing a photosensitive transfer material including a temporary support, a 2 nd resin layer, a 1 st resin layer, a photosensitive resin layer, and a protective film, the photosensitive resin composition preferably contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. More preferably, the solvent mixture contains at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least 1 selected from the group consisting of a ketone solvent and a cyclic ether solvent, and still more preferably contains at least 3 selected from the group consisting of at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.

As the solvent, a solvent described in paragraphs 0092 to 0094 of international publication No. 2018/179640 and a solvent described in paragraph 0014 of japanese patent application laid-open No. 2018-177889, which are incorporated herein by reference, can be used.

The photosensitive resin composition may contain 1 kind of solvent alone or 2 or more kinds of solvents.

The content of the solvent in the application of the photosensitive resin composition is preferably 50 to 1 part by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.

The method for producing the photosensitive resin composition is not particularly limited, and the following methods are exemplified: a solution in which each component is dissolved in the above solvent is prepared in advance, and the obtained solution is mixed in a predetermined ratio to prepare a photosensitive resin composition.

Before forming the photosensitive resin layer, the photosensitive resin composition is preferably filtered using a filter having a pore diameter of 0.2 μm to 30 μm.

The method of applying the photosensitive resin composition is not particularly limited, and the photosensitive resin composition may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

The photosensitive resin layer may be formed by applying a photosensitive resin composition to a protective film described later and drying the same.

[ 1 st resin layer ]

The 1 st resin layer in the photosensitive transfer material according to the present invention contains particles.

In the photosensitive transfer material according to the present invention, it is preferable that the 1 st resin layer is in contact with the 2 nd resin layer, the 1 st resin layer and the 2 nd resin layer are peelable, and the 1 st resin layer after peeling the 1 st resin layer and the 2 nd resin layer has irregularities formed of the particles on the surface thereof.

The 1 st resin layer and the 2 nd resin layer are in contact with each other, and means that the 1 st resin layer is in contact with at least a part of the 2 nd resin layer, or that the 1 st resin layer is in contact with the 2 nd resin layer as a whole, preferably at least in the contact exposure, in the part of the mask in contact with the 1 st resin layer, the 1 st resin layer is in contact with the 2 nd resin layer.

< Concavo-convex >

The term "the surface of the 1 st resin layer after the 1 st resin layer and the 2 nd resin layer are peeled off" means that the surface of the 1 st resin layer after the peeling off has irregularities formed by particles, and the irregularities are formed in the shape of the particles.

In the case where the 1 st resin layer contains a 1 st resin layer binder polymer described later, the irregularities may be formed by exposing the particles from a layer based on the 1 st resin layer binder polymer, or may be formed by coating a part or all of the particles with the 1 st resin layer binder polymer.

In the present invention, the surface of the 1 st resin layer after the peeling has irregularities formed of particles, and the surface of the 1 st resin layer after the peeling can be confirmed by observation with a Scanning Electron Microscope (SEM).

< particle >

The particles contained in the 1 st resin layer are preferably metal oxide particles or organic polymer particles, and more preferably contain at least 1 kind of particles selected from silica particles, alumina particles and organic polymer particles, from the viewpoint of releasability of the 1 st resin layer/2 nd resin layer.

Since the refractive index of the silica particles (refractive index: 1.4 to 1.5), the alumina particles (refractive index: 1.6 to 1.65) and the organic polymer particles (refractive index: 1.4 to 1.7) is close to the refractive index of the organic substance (refractive index: 1.4 to 1.6) such as the resin contained in the 1 st resin layer, scattering of light is suppressed and linearity of the resin pattern is good, which is preferable.

Metal oxide particles

The metal of the metal oxide particles in the present invention further includes a semi-metal such as B, si, ge, as, sb, te.

The metal oxide particles are preferably oxide particles containing an atom such as Be, mg, ca, sr, ba, sc, Y, la, ce, gd, tb, dy, yb, lu, ti, zr, hf, nb, mo, W, zn, B, al, si, ge, sn, pb, sb, bi, te, more preferably silica, alumina, titania, a titanium composite oxide, zinc oxide, zirconia, indium/tin oxide or antimony/tin oxide, further preferably silica, alumina, titania, a titanium composite oxide or zirconia, and particularly preferably silica or alumina.

Organic Polymer particles

Examples of the organic polymer particles include homopolymers and copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester; cellulose polymers such as nitrocellulose, methyl cellulose, ethyl cellulose, and cellulose acetate; vinyl polymers such as polyethylene, polypropylene, polystyrene, vinyl chloride-based copolymer, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinyl butyral, and polyvinyl alcohol, and copolymers of vinyl compounds; a condensation polymer such as polyester, polyurethane, and polyamide, and a rubber thermoplastic polymer such as butadiene-styrene copolymer; a polymer obtained by polymerizing or crosslinking a photopolymerizable or thermally polymerizable compound such as an epoxy compound; melamine compounds, and the like.

Among these, the organic polymer particles may preferably be acrylic resin particles, and more preferably polymethyl methacrylate particles.

Surface treatment-

In order to impart dispersion stability, the particles used in the present invention may also have their surfaces treated with an organic material or an inorganic material. The particles are preferably particles whose surfaces are hydrophilic. For example, the use of a surface with a surface area of

Particles in which the surface of the aqueous particles is hydrophilized.

Particle size-

The average particle diameter of the particles is preferably 10nm to 1,000nm, more preferably 20nm to 300nm, still more preferably 30nm to 100nm, and particularly preferably 50nm to 80nm, from the viewpoint of releasability of the 1 st resin layer/2 nd resin layer.

The average particle diameter of the particles can be obtained by measuring the diameters of 20 particles of the 1 st resin layer slice observed by a transmission electron microscope and taking the diameters as an arithmetic average value.

The 1 st resin layer may contain 1 kind of particles alone, or 2 or more kinds may be used in combination.

From the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, the content of the particles is preferably 1 to 80% by mass, more preferably 2 to 30% by mass, and even more preferably 5 to 10% by mass relative to the total mass of the 1 st resin layer.

< 1 st adhesive Polymer for resin layer >

The 1 st resin layer used in the present invention preferably further contains a binder polymer for the 1 st resin layer.

The binder polymer for the 1 st resin layer is preferably a water-soluble or alkali-soluble polymer.

In the present invention, "water-soluble" means that the solubility of the aqueous alkali solution in water at pH7.0 is 0.1 mass% or more at 25 ℃, and "alkali-soluble" means that the solubility of the aqueous alkali solution in water at pH8.5 or more is 0.1 mass% or more at 25 ℃.

The "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or both water-soluble and alkali-soluble.

Examples of the binder polymer for the 1 st resin layer include novolac resins such as phenol formaldehyde resins, m-cresol formaldehyde resins, p-cresol formaldehyde resins, m-and p-mixed cresol formaldehyde resins, phenol/cresol (either m-, or m-or p-mixed), phenol/cresol mixed formaldehyde resins, etc., pyrogallol acetone resins, polyhydroxystyrene resins, modified cellulose resins, acrylic resins having hydroxyl groups (for example, homo-or copolymers of hydroxyalkyl (meth) acrylates), starches, glycogen, chitin, agarose, carrageenan, pra Lu Landuo saccharide, acacia, sorghum (Sorghum), polyamide resins, epoxy resins, polyacetal resins, acrylic resins, polystyrene resins, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyvinyl pyrrolidone, polyester resins, polyethyleneimine, polyallylamine, polyalkylene glycol, etc.

Among these, from the viewpoints of dispersibility of particles and patterning, at least 1 resin selected from the group consisting of modified cellulose resins and polyvinyl alcohols is preferable as the binder polymer, and when the photosensitive resin layer is a positive photosensitive resin layer, the modified cellulose resin is more preferable. The modified cellulose resin is more preferable because deformation and deterioration of the pattern can be prevented.

The modified cellulose resin is preferably hydroxyalkylated cellulose or carboxyalkyl cellulose from the viewpoints of dispersibility of particles and patterning property.

Examples of the hydroxyalkylated cellulose include preferably hydroxymethyl cellulose, hydroxyethyl cellulose, polyhydroxyethyl cellulose, hydroxypropyl methylcellulose, glyoxalated hydroxypropyl methylcellulose, and hydroxypropyl methylcellulose phthalate.

As the carboxyalkyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and the like are preferable.

Among them, from the viewpoints of dispersibility and pattern formability of particles, at least 1 resin selected from hydroxypropyl cellulose and hydroxypropyl methylcellulose is preferable, and hydroxypropyl methylcellulose is more preferable.

In the case where the photosensitive resin layer is a negative photosensitive resin layer, the binder polymer for the 1 st resin layer preferably contains polyvinyl alcohol from the viewpoints of dispersibility of particles and patterning properties. The inclusion of polyvinyl alcohol is more preferable because of improved sensitivity and improved pattern quality.

In the case where the photosensitive resin layer is a negative photosensitive resin layer, polyvinylpyrrolidone is preferably contained as the binder polymer for the 1 st resin layer from the viewpoint of adhesion between the photosensitive resin layer and the 1 st resin layer.

The weight average molecular weight of the binder polymer for the 1 st resin layer is preferably 1,000 or more, more preferably 2,000 ～ 100,000, and even more preferably 10,000 ～ 50,000, from the viewpoints of dispersibility of particles, pattern formation, solubility in a developer after exposure, and transferability.

The 1 st resin layer may contain 1 kind of binder polymer for the 1 st resin layer alone or 2 or more kinds of binder polymers.

From the viewpoints of adhesion between the 1 st resin layer and the photosensitive resin layer, pattern formation, solubility in a developer after exposure, and transferability, the content of the 1 st resin layer binder polymer in the 1 st resin layer is preferably 10% by mass or more and 98% by mass or less, more preferably 20% by mass or more and 95% by mass or less, still more preferably 40% by mass or more and 90% by mass or less, and particularly preferably 65% by mass or more and 85% by mass or less, relative to the total mass of the 1 st resin layer.

The 1 st resin layer preferably contains polyvinyl alcohol and silica particles, more preferably contains polyvinyl alcohol, polyvinylpyrrolidone and silica particles, from the viewpoints of dispersibility of particles, pattern formation, adhesion of the photosensitive resin layer to the 1 st resin layer, and releasability of the 1 st resin layer/2 nd resin layer.

< other additives >

In the present invention, the 1 st resin layer may contain a known additive as needed in addition to the particles and the binder polymer for the 1 st resin layer.

The other additives used in the photosensitive resin layer may be preferably other additives.

< layer thickness of the 1 st resin layer >

The layer thickness of the 1 st resin layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and even more preferably 0.3 μm to 2 μm from the viewpoint of patterning.

The layer thickness of the 1 st resin layer is preferably smaller than the layer thickness of the photosensitive resin layer.

< method for Forming 1 st resin layer >

The method for forming the 1 st resin layer is not particularly limited, and the 1 st resin layer can be formed by applying the 1 st resin layer forming composition for forming the 1 st resin layer to the photosensitive resin layer, and the 1 st resin layer is prepared by mixing the components and a solvent (preferably, an aqueous solvent) in a predetermined ratio and by an arbitrary method, and stirring and dissolving the mixture. For example, the composition may be prepared by preparing each component into a solution dissolved in a solvent in advance, and then mixing the obtained solutions at a predetermined ratio. The composition prepared as above can also be used after filtration using a filter or the like having a pore size of 5. Mu.m.

Examples of the aqueous solvent include water and water-soluble solvents such as alcohols.

The method of applying the composition for forming the 1 st resin layer is not particularly limited, and the composition can be applied by a known method such as slit coating, spin coating, curtain coating, or inkjet coating.

Further, the 1 st resin layer may be applied after forming another layer described later on the photosensitive resin layer.

[ 2 nd resin layer ]

The 2 nd resin layer contains a resin having a polyethylene structure.

The 2 nd resin layer is peeled together with the temporary support when the temporary support is peeled.

Examples of the resin having a polyethylene structure include polyethylene and an ethylene copolymer.

Among them, from the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, a resin having an ethylene- (meth) acrylic acid compound copolymerized structure is preferable, and a resin having an ethylene- (meth) acrylic acid copolymerized structure is more preferable.

Further, as the resin having a polyethylene structure, from the viewpoint of improving the peeling force between the 1 st resin layer and the 2 nd resin layer, an ionomer resin is preferable, and an ionomer resin having an ethylene- (meth) acrylic acid metal salt copolymerized structure is more preferable.

From the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, the resin having a polyethylene structure preferably has 50 mass% or more of a structural unit (-CH) derived from ethylene relative to the total mass of the resin ₂ CH ₂ (-) is more preferably 65 mass% or more, still more preferably 80 mass% or more, particularly preferably 90 mass% or more and 99 mass% or less.

Further, from the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, the resin having a polyethylene structure is preferably a resin having an acid group or a salt structure thereof, more preferably a resin having a carboxyl group or a salt structure thereof, and particularly preferably a resin having a salt structure of a carboxyl group.

The counter cation in the salt structure is not particularly limited, and examples thereof include alkali metal cations, quaternary ammonium cations, alkaline earth metal cations, zinc cations, iron cations, chromium cations, cobalt cations, nickel cations, copper cations, silver cations, and the like.

Among them, alkali metal cations or zinc cations are preferable, sodium cations or zinc cations are more preferable, and zinc cations are particularly preferable from the viewpoint of releasability of the 1 st resin layer/2 nd resin layer.

Further, from the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, the resin having a polyethylene structure preferably contains a structural unit having an acid group or a salt structure thereof, more preferably a structural unit represented by the following formula (Ac) or formula (Io), and particularly preferably a structural unit represented by the following formula (Io).

[ chemical formula 2]

In the formula (Ac) and the formula (Io), R ^A Each independently represents a hydrogen atom or a methyl group, and the counter cation in the formula (Io) represents an arbitrary monovalent or polyvalent cation.

In the case where the resin having a polyethylene structure contains a structural unit having an acid group or a salt structure thereof, the content of the structural unit having an acid group or a salt structure thereof is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, still more preferably 2 to 10% by mass, and particularly preferably 3 to 8% by mass relative to the total mass of the resin from the viewpoint of releasability of the 1 st resin layer/2 nd resin layer.

The resin having a polyethylene structure may be used alone in an amount of 1 or in an amount of 2 or more.

From the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, the content of the resin having a polyethylene structure in the 2 nd resin layer is preferably 50 mass% or more and 100 mass% or less, more preferably 80 mass% or more and 100 mass% or less, and particularly preferably 90 mass% or more and 100 mass% or less, relative to the total mass of the 2 nd resin layer.

And, the 2 nd resin layer may contain a polymerization inhibitor.

The polymerization inhibitor contained in the 2 nd resin layer is preferably the above-mentioned polymerization inhibitor in the photosensitive resin layer.

The other material of the 2 nd resin layer is not particularly limited, and may be appropriately selected according to the purpose. For example, a known adhesive or an adhesive can be used.

Examples of the binder include an acrylic binder, a urethane binder, a rubber binder, and a silicone binder. Examples of the adhesive include "evaluation of properties of release paper and release film and adhesive tape and control technique thereof", JOHOKIKO co, ltd, acrylic adhesive, ultraviolet (UV) curable adhesive, silicone adhesive, and the like described in 2004 and chapter 2. Further, the acrylic adhesive means an adhesive comprising a polymer of (meth) acrylic monomer (i.e., a (meth) propylene polymer).

In the case of a binder, a tackifier may be further contained.

Examples of the adhesive include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives. From the standpoint of relatively high adhesive strength and easy control of adhesive strength by introducing a thermally crosslinked or photocrosslinked structure, a urethane resin adhesive or an acrylic resin adhesive is preferable.

< method for Forming resin layer 2 >

The method for forming the 2 nd resin layer is not particularly limited, and the following methods may be mentioned: a method in which the temporary support on which the 2 nd resin layer is formed is laminated so that the 2 nd resin layer is in contact with the 1 st resin layer; a method of laminating in such a manner that the 2 nd resin layer alone contacts the 1 st resin layer; and a method of coating a composition comprising a resin having the above polyethylene structure on the 1 st resin layer.

Among them, from the viewpoint of productivity, a method of laminating the temporary support having the 2 nd resin layer formed thereon so that the 2 nd resin layer is in contact with the 1 st resin layer is preferable.

The method for producing the temporary support having the 2 nd resin layer formed thereon is not particularly limited, and the following methods may be mentioned: a method of extrusion-laminating a 2 nd resin layer on a film such as PET; a method of coating a film such as PET with a 2 nd resin layer composition dissolved in a solvent by drying; and a method of coating a film such as PET with a 2 nd resin layer composition dispersed in water or the like by drying. Among them, a method of extrusion-laminating the 2 nd resin layer on a film such as PET is preferable from the viewpoint of productivity.

< Property of the 2 nd resin layer >

The layer thickness of the 2 nd resin layer in the photosensitive transfer material according to the present invention is preferably 5 to 100 μm from the viewpoint of both adhesion and handleability.

From the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, the layer thickness of the 2 nd resin layer is preferably 0.01 μm or more and 50 μm or less, more preferably 0.1 μm or more and 20 μm or less, and particularly preferably 0.2 μm or more and 10 μm or less.

From the viewpoint of releasability of the 1 st resin layer/2 nd resin layer, the water contact angle on the 1 st resin layer side surface of the 2 nd resin layer is preferably 100 degrees or less, more preferably 95 degrees or less, still more preferably 90 degrees or less, and particularly preferably 75 degrees or more and 90 degrees or less. When the water contact angle on the surface of the 1 st resin layer side is 100 degrees or less, the occurrence of peeling of the 1 st resin layer/2 nd resin layer at the time of peeling the protective film can be suppressed.

In the present invention, the method for measuring the water contact angle on the surface of the 2 nd resin layer on the 1 st resin layer side is performed by the following method.

A copper layer having a thickness of 200nm was formed on a PET film having a thickness of 100 μm by a sputtering method, and a PET substrate with a copper layer was formed.

The photosensitive transfer material from which the protective film was peeled was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4 m/min.

The photosensitive transfer material laminated on the obtained PET substrate with copper layer was peeled off between the 1 st resin layer and the 2 nd resin layer, and the water contact angle of the surface of the 2 nd resin layer was measured by the following method.

The contact angle after 7 seconds was measured by a droplet method after dropping 2 μl of purified water onto the measurement surface at 25 ℃ using a contact angle meter (Kyowa Interface Science co., ltd., dropwmaster-501).

[ temporary support ]

The photosensitive transfer material according to the present invention includes a temporary support.

The temporary support is a support that supports the photosensitive resin layer or a laminate including the photosensitive resin layer and is releasable.

The temporary support preferably has light transmittance from the viewpoint that exposure of the photosensitive resin layer via the temporary support can be performed when pattern exposure is performed on the photosensitive resin layer. In the present specification, "light-transmitting" means that the transmittance of light of a wavelength used for pattern exposure is 50% or more.

From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of light of a wavelength (more preferably, 365nm wavelength) used for pattern exposure of the temporary support is preferably 60% or more, more preferably 70% or more.

The transmittance of the layer included in the photosensitive transfer material is a ratio of the intensity of the light emitted from the layer when the light is incident in a direction perpendicular to the main surface of the layer (thickness direction) to the intensity of the incident light, and is measured using MCPD Series manufactured by Otsuka Electronics co.

In addition, when the photosensitive transfer material according to the present invention is used in a method for producing a resin pattern including, in order, a step of exposing a photosensitive resin layer with a temporary support interposed therebetween, a temporary support having a light transmittance of 60% or less or a temporary support having light scattering properties can be used, the step including: a step of peeling the protective film from the photosensitive transfer material; a step of bringing an outermost layer of the photosensitive transfer material from which the protective film has been peeled off, into contact with a base material, and bonding the outermost layer; a step of peeling the temporary support and the 2 nd resin layer from the photosensitive transfer material bonded to the substrate; exposing the photosensitive resin layer with the exposure mask in contact with the 1 st resin layer with the exposure mask interposed therebetween; and developing the photosensitive resin layer to form a resin pattern.

Examples of the material constituting the temporary support include a glass substrate, a resin film, and paper, and the resin film is preferable from the viewpoints of strength, flexibility, and light transmittance.

Examples of the resin film include polyethylene terephthalate (PET: polyethylene terephthalate) film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.

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

The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, and particularly preferably in the range of 10 μm to 16 μm from the viewpoints of ease of handling and versatility.

Further, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, from the viewpoints of resolution and linearity in exposure through the support.

Further, it is preferable that the film used as the temporary support is free from deformation such as wrinkles, scratches, defects, and the like.

From the viewpoints of the patterning property at the time of pattern exposure via the temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matters, defects, precipitates, and the like contained in the temporary support be small. The number of particles, foreign matters, and defects having a diameter of 1 μm or more is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, it is more preferably 3/10 mm ² Hereinafter, it is particularly preferably 0/10 mm ² 。

Preferable modes of the temporary support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of International publication No. 2012/081680, paragraphs 0029 to 0040 of International publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese patent application laid-open No. 2019-101405, the contents of which are incorporated herein by reference.

The photosensitive transfer material may include a layer other than the above layers (hereinafter, also referred to as "other layer"). As the other layer, for example, a contrast enhancement layer can be cited.

The contrast enhancement layer is described in paragraph 0134 of International publication No. 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of Japanese patent application laid-open No. 2014-85643. The contents of these publications are incorporated into the present specification.

From the viewpoint of further exhibiting the effects of the present invention, the total thickness of each layer of the photosensitive transfer material other than the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

Further, from the viewpoint of further exhibiting the effects of the present invention, the total thickness of the photosensitive resin layer and the 1 st resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[ method for producing photosensitive transfer Material ]

The method for producing the photosensitive transfer material according to the present invention is not particularly limited, and a known production method, for example, a known method for forming each layer, can be used.

A method for producing the photosensitive transfer material used in the present invention will be described below with reference to fig. 1. However, the photosensitive transfer material used in the present invention is not limited to the photosensitive transfer material having the structure shown in fig. 1.

Fig. 1 is a schematic cross-sectional view showing an example of the structure of a photosensitive transfer material used in the present invention. The photosensitive transfer material 100 shown in fig. 1 has a structure in which a temporary support 10, a 2 nd resin layer 12, a 1 st resin layer 14, a photosensitive resin layer 16, and a protective film 18 are laminated in this order.

As the method for producing the photosensitive transfer material 100, for example, a method including the steps of: a step of forming the 2 nd resin layer 12 by melting the 2 nd resin layer resin particles on the surface of the temporary support 10 and forming a film by an extrusion lamination method, or a step of forming the 2 nd resin layer 12 by coating the 2 nd resin layer forming composition on the surface of the temporary support 10 and then drying a coating film of the 2 nd resin layer forming composition, thereby producing the temporary support 10 on which the 2 nd resin layer 12 is formed;

on the other hand, a step of forming the photosensitive resin layer 16 by, for example, coating a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator on the protective film 18, and then drying a coating film of the photosensitive resin composition; a step of forming the 1 st resin layer 14 by applying the 1 st resin layer forming composition on the surface of the photosensitive resin layer 16 and then drying a coating film of the 1 st resin layer composition, and a step of producing a laminate of the photosensitive resin layer 16 and the 1 st resin layer 14 formed on the protective film 18; and

And a step of pressing the temporary support 10 on which the 2 nd resin layer 12 is formed against the 1 st resin layer 14 of the laminate produced as described above so that the 2 nd resin layer 12 is in direct contact with the surface of the 1 st resin layer 14.

Further, as another manufacturing method, a method including the following steps is preferable: a step of forming a photosensitive resin layer 16 by, for example, coating a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator on the protective film 18, and then drying a coating film of the photosensitive resin composition; a step of forming the 1 st resin layer 14 by applying the 1 st resin layer forming composition to the surface of the photosensitive resin layer 16 and then drying a coating film of the 1 st resin layer composition; and a step of forming the 2 nd resin layer 12 by applying the 2 nd resin layer forming composition to the surface of the 1 st resin layer 14 and then drying a coating film of the 2 nd resin layer forming composition.

The photosensitive transfer material 100 is manufactured by pressing the temporary support 10 against the 2 nd resin layer 12 of the laminate manufactured by the above-described manufacturing method.

In the above-described production method, the following composition is preferably used: a composition for a 2 nd resin layer containing at least 1 kind selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents; at least 1 st resin layer composition containing an organic solvent selected from water and water-miscible organic solvents; and a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This can suppress the coating of the 2 nd resin layer forming composition on the surface of the 1 st resin layer 14 and/or the mixing of the component contained in the photosensitive resin layer 16 and the component contained in the 1 st resin layer 14 during the storage of the laminate having the coating film of the photosensitive resin composition, and can suppress the coating of the 2 nd resin layer forming composition on the surface of the 1 st resin layer 14 and/or the mixing of the component contained in the 1 st resin layer 14 and the component contained in the 2 nd resin layer 12 during the storage of the laminate having the coating film of the 2 nd resin layer forming composition.

As a method for producing the photosensitive transfer material according to the present invention, it is preferable to produce the photosensitive transfer material 100 including the protective film 18, the photosensitive resin layer 16, the 1 st resin layer 14, the 2 nd resin layer 12, and the temporary support 10 by a step of pressing the temporary support 10 having the 2 nd resin layer 12 formed thereon against the 1 st resin layer 14 of the laminate obtained by sequentially disposing the photosensitive resin layer 16 and the 1 st resin layer 14 on the protective film 18 so that the 2 nd resin layer 12 is in direct contact with the surface of the 1 st resin layer 14.

After the photosensitive transfer material 100 is manufactured by the above manufacturing method, the photosensitive transfer material 100 may be wound up to manufacture and store a photosensitive transfer material in a wound form. The photosensitive transfer material in the roll form can be directly supplied in this form to a bonding step with a substrate in a roll-to-roll system described later.

The photosensitive transfer material according to the present invention can be preferably used in various applications requiring precise micromachining by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be etched as a coating film, or electroforming mainly including electroplating may be performed. The cured film obtained by patterning can be used as a permanent film, for example, an interlayer insulating film, a wiring protective film having an index matching layer, or the like. The photosensitive transfer material according to the present invention can be preferably used for various wiring formation applications of semiconductor packages, printed boards, sensor boards, conductive films such as touch panels, electromagnetic shield materials, and film heaters, liquid crystal sealing materials, and formation of structures in the micro-mechanical or micro-electronic fields.

(method for producing resin Pattern and method for producing Circuit Wiring)

The method for producing a resin pattern according to the present invention is a method for producing a resin pattern by forming a resin pattern on a substrate using the photosensitive transfer material according to the present invention.

As a method for producing a resin pattern, a method comprising the following steps in this order is preferable: a step of peeling the protective film from the photosensitive transfer material according to the present invention (hereinafter also referred to as a "protective film peeling step"); a step of bonding the outermost layer of the photosensitive transfer material from which the protective film has been peeled off, by contacting the outermost layer with a base material (hereinafter also referred to as a "bonding step"); a step of peeling the temporary support and the 2 nd resin layer from the photosensitive transfer material bonded to the substrate; a step of exposing the photosensitive resin layer with the exposure mask interposed therebetween (hereinafter, also referred to as an "exposure step") by bringing the exposure mask into contact with the 1 st resin layer; and a step of developing the photosensitive resin layer to form a resin pattern (hereinafter also referred to as a "developing step").

The method for producing the circuit wiring according to the present invention is not particularly limited as long as the method using the photosensitive transfer material according to the present invention is used.

As a method for manufacturing a circuit wiring according to the present invention, a method including a step of etching a conductive layer using a resin pattern formed by the method for manufacturing a resin pattern according to the present invention as a mask (hereinafter also referred to as an "etching step") is preferable, and a method including the following steps in this order is more preferable: a step of peeling the protective film from the photosensitive transfer material according to the present invention: a step of bringing an outermost layer of the photosensitive transfer material from which the protective film has been peeled off, into contact with a substrate having a conductive layer, and bonding the outermost layer; peeling the temporary support and the 2 nd resin layer from the photosensitive transfer material bonded to the substrate; exposing the photosensitive resin layer to light with the exposure mask in between by bringing the exposure mask into contact with the 1 st resin layer; developing the photosensitive resin layer to form a resin pattern; and etching the conductive layer using the formed resin pattern as a mask.

Hereinafter, each step included in the method for manufacturing a resin pattern and the method for manufacturing a circuit wiring will be described, but unless otherwise mentioned, the description of each step included in the method for manufacturing a resin pattern is also applicable to each step included in the method for manufacturing a circuit wiring.

< protective film peeling Process >

The method for producing a resin pattern preferably includes a step of peeling the protective film from the photosensitive transfer material according to the present invention. The method of peeling the protective film is not limited, and a known method can be applied.

< bonding Process >

The method for producing the resin pattern preferably includes a bonding step.

In the bonding step, it is preferable that the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support is brought into contact with the substrate (the conductive layer in the case where the conductive layer is provided on the surface of the substrate), so that the photosensitive transfer material is pressed against the substrate. In the above-described aspect, since the adhesion between the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the temporary support and the substrate is improved, the patterned photosensitive resin layer after exposure and development can be preferably used as an etching resist for etching the conductive layer.

In the bonding step, when the photosensitive transfer material further includes a layer (e.g., a high refractive index layer and/or a low refractive index layer) other than the protective film on the surface of the photosensitive resin layer on the side not facing the temporary support, the surface of the photosensitive resin layer on the side not facing the temporary support is bonded to the substrate with the layer interposed therebetween.

The method for pressing the substrate against the photosensitive transfer material is not particularly limited, and a known transfer method and lamination method can be used.

The photosensitive transfer material is preferably bonded to the substrate by superposing an outermost layer of the photosensitive transfer material on the side of the temporary support having the photosensitive resin layer on the substrate, and applying pressure and heat by a mechanism such as a roller. For lamination, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator that can further improve productivity can be used.

The method for manufacturing the resin pattern and the method for manufacturing the circuit wiring including the bonding step are preferably performed in a roll-to-roll manner.

The roll-to-roll system will be described below.

The roll-to-roll system is the following system: as the substrate, a substrate that can be wound and unwound is used, and a step of winding out the substrate or a structure including the substrate (also referred to as a "winding-out step") and a step of winding up the substrate or a structure including the substrate (also referred to as a "winding-up step") are included before any step included in the method for manufacturing a resin pattern or the method for manufacturing a circuit wiring, and at least any step (preferably all steps or all steps except for a heating step) is performed while carrying the substrate or the structure including the substrate.

The winding-out method in the winding-out step and the winding-up method in the winding-up step are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.

< substrate >

As the substrate used in the method for producing a resin pattern according to the present invention, a known substrate can be used, but a substrate having a conductive layer is preferable, and a conductive layer is more preferable on the surface of the substrate.

The substrate may have any layer other than the conductive layer as needed.

Examples of the base material constituting the substrate include glass, silicon, and a film.

The base material constituting the substrate is preferably transparent. In the present specification, "transparent" means that the transmittance of light having a wavelength of 400nm to 700nm is 80% or more.

The refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

As the transparent glass substrate, tempered glass typified by gorilla glass of Corning Incorporated can be given. As the transparent glass substrate, materials used in japanese patent application laid-open publication nos. 2010-86684 and 2010-152809 and 2010-257492 can be used.

When a film substrate is used as the substrate, a film substrate having a small optical strain and/or high transparency is preferably used. Examples of such a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymer.

When the substrate is manufactured by a roll-to-roll method, a film substrate is preferable. In the case of manufacturing a circuit wiring for a touch panel by a roll-to-roll method, it is preferable that the substrate is a sheet-like resin composition.

Examples of the conductive layer included in the substrate include a conductive layer used for a normal circuit wiring or a touch panel wiring.

The conductive layer is preferably at least 1 layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer, from the viewpoints of conductivity and fine line formability.

The substrate may have 1 conductive layer alone or 2 or more layers. In the case of having 2 or more conductive layers, conductive layers of different materials are preferable.

As a material of the conductive layer, a metal and a conductive metal oxide can be given.

As the metal, al, zn, cu, fe, ni, cr, mo, ag and Au are exemplified.

Examples of the conductive metal oxide include ITO (indium tin oxide), IZO (indium zinc oxide) and SiO ₂ 。

In the present specification, the term "conductivity" means that the volume resistivity is less than 1×10 ⁶ Omega cm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 ⁴ Ωcm。

In the case of manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

The conductive layer is preferably an electrode pattern of a sensor corresponding to a visual recognition portion used in a capacitive touch panel or a wiring of a peripheral lead portion.

< Exposure procedure >

In the method for producing a resin pattern, it is preferable that the method further includes a step of exposing the photosensitive resin layer to a pattern after the bonding step (exposure step).

The detailed arrangement and specific dimensions of the pattern in the pattern exposure are not particularly limited. In order to improve the display quality of a display device (e.g., a touch panel) including an input device having circuit wiring manufactured by a circuit wiring manufacturing method and to reduce the area occupied by lead-out wiring, at least a part of the pattern (preferably, an electrode pattern of the touch panel and/or a portion of the lead-out wiring) preferably includes a thin line having a width of 20 μm or less, and more preferably includes a thin line having a width of 10 μm or less.

The light source used for exposure may be appropriately selected and used as long as it is a light source that irradiates light (e.g., 365nm or 405 nm) of a wavelength at which the photosensitive resin layer can be exposed. Specifically, an ultra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode: light emitting diode) are mentioned.

As the exposure amount, 5mJ/cm is preferable ² ～200mJ/cm ² More preferably 10mJ/cm ² ～100mJ/cm ² 。

In the exposure step, the temporary support may be removed from the photosensitive resin layer and then subjected to pattern exposure, or the temporary support may be removed after pattern exposure is performed through the temporary support before the temporary support is removed. In the case of peeling the temporary support before exposure, the mask may be exposed in contact with the photosensitive resin layer or may be exposed close to it without contact. In the case of exposing without peeling the temporary support, the mask may be exposed in contact with the temporary support or may be exposed in the vicinity of the temporary support without contact. In order to prevent contamination of the mask due to contact between the photosensitive resin layer and the mask and to avoid influence on exposure by foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling off the temporary support. In addition, in the exposure system, the contact exposure system can be appropriately selected and used in the case of contact exposure, and in the case of non-contact exposure system, the proximity exposure system, the projection exposure system of a lens system or a mirror system, the direct exposure system using exposure laser, or the like can be appropriately selected and used. In the case of projection exposure by a lens system or a mirror system, an exposure machine having an appropriate number of openings (NA) of lenses can be used depending on the required resolution and focal depth. In the case of the direct exposure method, the photosensitive resin layer may be directly drawn, or the photosensitive resin layer may be subjected to reduced projection exposure via a lens. The exposure may be performed not only under the atmosphere but also under reduced pressure or vacuum, and may be performed by separating a liquid such as water between the light source and the photosensitive resin layer.

< developing Process >

In the method for producing a resin pattern, it is preferable that the method further includes a step of developing the exposed photosensitive resin layer to form a resin pattern (developing step) after the exposure step.

In the development step, the 1 st resin layer of the non-image portion is also removed together with the photosensitive resin layer of the non-image portion. In the developing step, the 1 st resin layer of the exposed portion may be removed in a form of being dissolved or dispersed in a developing solution.

The exposed photosensitive resin layer in the developing step can be developed with a developer.

The developer is not particularly limited as long as the non-image portion of the photosensitive resin layer can be removed, and for example, a known developer such as the developer described in japanese unexamined patent publication No. 5-72724 can be used.

The developer is preferably an aqueous alkali developer containing a compound having pka=7 to 13 at a concentration of 0.05mol/L to 5mol/L (liter). The developer may contain a water-soluble organic solvent and/or a surfactant. The developer described in paragraph 0194 of International publication No. 2015/093271 is also preferable.

The development method is not particularly limited, and may be any of spin-coating immersion development, shower and spin development, and immersion development. The development by showering is a development process in which a developing solution is sprayed onto the photosensitive resin layer after exposure by showering to remove the non-exposed portion.

Preferably, after the developing step, the cleaning agent is sprayed and sprayed, and the developing residues are removed while wiping with a brush.

The liquid temperature of the developer is not particularly limited, but is preferably 20 to 40 ℃.

< etching Process >

The method for manufacturing the circuit wiring preferably includes a step of etching the substrate in a region where the resin pattern is not arranged (etching step).

In the etching step, a resin pattern formed of a photosensitive resin layer is used as an etching resist, and an etching treatment of the conductive layer is performed.

As a method of etching treatment, known methods can be applied, and examples thereof include the method described in paragraphs 0209 to 0210 of japanese patent application laid-open publication No. 2017-120435, the method described in paragraphs 0048 to 0054 of japanese patent application laid-open publication No. 2010-152155, a wet etching method in which an etching solution is immersed, and a dry etching method by plasma etching or the like.

The etching liquid used in the wet etching may be appropriately selected from acidic or alkaline etching liquids according to the object to be etched.

Examples of the acidic etching liquid include an aqueous solution of an acidic component alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt selected from ferric chloride, ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components.

Examples of the alkaline etching liquid include an aqueous solution of an alkali component alone selected from sodium hydroxide, potassium hydroxide, ammonia, an organic amine and a salt of an organic amine (such as tetramethylammonium hydroxide), and a mixed aqueous solution of an alkali component and a salt (such as potassium permanganate). The alkali component may be a component obtained by combining a plurality of alkali components.

< removal Process >

In the method for manufacturing the circuit wiring, a step of removing the remaining resin pattern (removal step) is preferably performed.

The removal step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.

The method for removing the residual resin pattern is not particularly limited, and a method for removing the residual resin pattern by chemical treatment is preferable, and a method for removing the residual resin pattern by using a removing liquid is preferable.

The photosensitive resin layer is removed by immersing the substrate having the remaining resin pattern in a removing liquid under stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes.

Examples of the removing liquid include a removing liquid obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

The removal liquid may be removed by a known method such as spraying, showering, spin-coating or immersing.

< other procedure >

The method for producing a resin pattern and the method for producing a circuit wiring may include any process (other process) other than the above process. For example, the following steps may be mentioned, but the present invention is not limited to these steps.

Further, examples of the exposure step, the development step, and other steps which can be applied to the method for producing a circuit wiring include the steps described in paragraphs 0035 to 0051 of JP 2006-23696A.

Procedure for reducing the reflectivity of visible light

The method for manufacturing the circuit wiring may include a step of performing a process of reducing the visible ray reflectance of a part or all of the plurality of conductive layers included in the substrate.

As the treatment for reducing the reflectance of visible light, an oxidation treatment is given. When the substrate has a conductive layer containing copper, the visible ray reflectance of the conductive layer can be reduced by oxidizing copper to produce copper oxide and blackening the conductive layer.

The treatment for reducing the reflectance of visible light is described in paragraphs 0017 to 0025 of Japanese unexamined patent publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese unexamined patent publication No. 2013-206315, and the contents of these publications are incorporated herein by reference.

A step of forming an insulating film, a step of forming a new conductive layer on the surface of the insulating film

The method for manufacturing the circuit wiring preferably includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film.

Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.

The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film may be used. Further, an insulating film having a desired pattern can be formed by photolithography using an insulating photosensitive material.

The step of forming a new conductive layer on the insulating film is not particularly limited, and for example, a new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

In the method for manufacturing the circuit wiring, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and to form circuits successively or simultaneously with respect to the conductive layers formed on both surfaces of the substrate. With this structure, a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a substrate and a second conductive pattern is formed on the other surface can be formed. Further, it is also preferable to form the circuit wiring for the touch panel having such a structure from both sides of the substrate in a roll-to-roll manner.

< use of Circuit Wiring >

The circuit wiring manufactured by the method of manufacturing the circuit wiring can be applied to various devices. As a device including the circuit wiring manufactured by the above-described manufacturing method, for example, an input device is given, and a touch panel is preferable, and a capacitive touch panel is more preferable. The input device can be applied to a display device such as an organic EL display device or a liquid crystal display device.

(method for manufacturing touch Panel)

The method for manufacturing a touch panel according to the present invention is not particularly limited as long as the method using the photosensitive transfer material according to the present invention is used.

As a method for manufacturing a touch panel according to the present invention, a method including a step of forming a wiring for a touch panel by etching a conductive layer using a resin pattern formed by the method for manufacturing a resin pattern according to the present invention as a mask is preferable, and a method including the following steps in this order is more preferable: a step of peeling the protective film from the photosensitive transfer material according to the present invention: a step of bringing an outermost layer of the photosensitive transfer material from which the protective film has been peeled off, into contact with a substrate having a conductive layer, and bonding the outermost layer; peeling the temporary support and the 2 nd resin layer from the photosensitive transfer material bonded to the substrate; exposing the photosensitive resin layer to light with the exposure mask in between by bringing the exposure mask into contact with the 1 st resin layer; developing the photosensitive resin layer to form a resin pattern; and forming a wiring for a touch panel by etching the conductive layer using the formed resin pattern as a mask.

The specific modes of the steps in the method for manufacturing a touch panel, the order in which the steps are performed, and the like are preferably the same as those described in the above-described items of "method for manufacturing a resin pattern" and "method for manufacturing a circuit wiring".

As a method for manufacturing a touch panel, a known method for manufacturing a touch panel may be referred to in addition to forming a wiring for a touch panel by the above-described method.

The method for manufacturing the touch panel may include any step (other step) other than the above.

Fig. 2 and 3 show an example of a pattern of a mask used for manufacturing a touch panel.

In the pattern a shown in fig. 2 and the pattern B shown in fig. 3, GR is a non-image portion (light shielding portion), EX is an image portion (exposure portion), and DL virtually represents an alignment frame. In the method for manufacturing a touch panel, for example, the photosensitive resin layer is exposed to light through a mask having a pattern a shown in fig. 2, whereby a touch panel having a circuit wiring having a pattern a corresponding to EX can be manufactured. Specifically, the method described in FIG. 1 of International publication No. 2016/190405 can be used. In one example of the manufactured touch panel, the central portion (pattern portion formed by connecting four corners) of the exposure portion EX is a portion where a transparent electrode (electrode for touch panel) is formed, and the peripheral portion (thin line portion) of the exposure portion EX is a portion where wiring of the peripheral lead portion is formed.

The touch panel having at least the wiring for the touch panel is manufactured by the above-described method for manufacturing a touch panel. The touch panel preferably has a transparent substrate, an electrode, an insulating layer, or a protective layer.

As a detection method in the touch panel, a known method such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method can be given. Among them, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include a so-called in-line type (for example, those described in fig. 5, 6, 7, and 8 of japanese patent application laid-open publication No. 2012-517051), a so-called out-line type (for example, those described in fig. 19 of japanese patent application laid-open publication No. 2013-168125, and those described in fig. 1 and 5 of japanese patent application laid-open publication No. 2012-89102), an OGS (One Glass Solution: monolithic glass Touch technology), a TOL (Touch-on-Lens: overlay Touch) type (for example, those described in fig. 2 of japanese patent application laid-open publication No. 2013-54727), and various types of plug-ins (for example, those described in fig. 6 of japanese patent application laid-open publication No. 2013-164871, such as GG 1-G2, GFF 2, GF1, and G1F).

Examples of the touch panel include the touch panel described in paragraph 0229 of japanese patent application laid-open No. 2017-120435.

Examples

The following examples are presented to more specifically describe embodiments of the present invention. The materials, amounts used, proportions, processing contents, processing order, and the like shown in the examples below can be appropriately modified without departing from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.

(examples 1 to 14 and comparative examples 1 to 3)

< preparation of photosensitive resin composition 1 >

The respective components used for preparing the photosensitive resin composition 1 are as follows.

[ Polymer A ]

Polymer A was synthesized according to the following method. In the synthesis of polymer a, the following abbreviations represent the following compounds, respectively.

St: styrene (FUJIFILM Wako Pure Chemical Corporation system)

MAA: methacrylic acid (FUJIFILM Wako Pure Chemical Corporation system)

MMA: methyl methacrylate (FUJIFILM Wako Pure Chemical Corporation)

V-601:2,2' -azobis (isobutyric acid) dimethyl (manufactured by FUJIFILM Wako Pure Chemical Corporation, polymerization initiator)

PGMEA: propylene glycol monomethyl ether acetate

PGMEA (116.5 parts) was added to a three-neck flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked flask at 90.+ -. 2 ℃, a mixture of St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts) and PGMEA (116.5 parts) was added dropwise to the three-necked flask over 2 hours. After completion of the dropwise addition, the mixed solution was stirred for 2 hours while maintaining the liquid temperature at 90±2 ℃, whereby a composition containing 30.0 mass% of polymer a was obtained. The acid value of the polymer A was 189mgKOH/g, the weight-average molecular weight was 60,000, and the glass transition temperature was 131 ℃.

[ ethylenically unsaturated Compound B ]

B-1: NK ester BPE-500 (2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane, shin-Nakamura Chemical Co., ltd.

B-2: ARONIX M-270 (polypropylene glycol diacrylate, TOAGOSEI CO., LTD.)

[ photopolymerization initiator ]

B-CIM (photo radical polymerization initiator, 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, manufactured by Hampford Co., ltd.)

[ sensitizer ]

SB-PI 701 (4, 4' -bis (diethylamino) benzophenone, sanyo tracking Co., ltd.)

[ color developer ]

N-1: LCV (colorless crystal violet, tokyo Chemical Industry co., ltd., pigment developed by free radical)

[ chain transfer agent ]

N-phenylglycine (Tokyo Chemical Industry Co., ltd.)

[ antirust agent ]

CBT-1 (carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD.)

[ polymerization inhibitor ]

TDP-G (phenothiazine, kawaguchi Chemical Industry Co., LTD.)

[ antioxidant ]

Phenanthrone (Tokyo Chemical Industry Co., ltd.)

[ surfactant ]

Megafac F-552 (fluorine-based surfactant, DIC Corporation)

The following components were mixed to prepare a photosensitive resin composition 1.

Polymer A (solid content concentration 30.0%): 50.00 parts

B-1:36.20 parts

B-2:5.00 parts

Photopolymerization initiator: 7.00 parts

Sensitizer: 0.50 part

N-1:0.40 part

Chain transfer agent: 0.20 part

Rust inhibitor: 0.10 part

Polymerization inhibitor: 0.30 part

Antioxidant: 0.01 part

Surfactant: 0.29 min

Methyl ethyl ketone (SANKYO chemistry co., ltd.): 396.00 parts

PGMEA (SHOWA DENKO k.k.): 170.00 parts

< preparation of composition 1 for Forming resin layer >

The composition 1 was prepared in the following manner, and was filtered through a polytetrafluoroethylene filter having a pore size of 5.0. Mu.m, to obtain a composition 1 for forming a resin layer.

Water: 915.0 parts by mass

Methanol: 915.0 parts by mass

Kuraray Poval PVA-205 (polyvinyl alcohol, KURARAY co., ltd.): 46.7 parts by mass

Polyvinylpyrrolidone K-30 (NIPPON shokubaci co., ltd.): 23.3 parts by mass

Snowtex ozl (silica particles, particle size 50nm to 80nm,Nissan Chemical Corporation): 150 parts by mass

Megafac F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.05 part by mass

< preparation of photosensitive transfer Material >

The photosensitive resin composition 1 was applied to the protective film described in table 1 using a slit nozzle so that the dry film thickness became 3.0 μm. After the coating, the resultant was dried in a convection oven at 100℃for 2 minutes to form a photosensitive resin layer. After the formation of the photosensitive resin layer, the 1 st resin layer-forming composition 1 was applied to the photosensitive resin layer so that the dry film thickness became 1.0 μm. Thereafter, the film was dried for 2 minutes using a convection oven at 100℃to prepare a film A having the 1 st resin layer on the photosensitive resin layer.

On the temporary support (corona-treated surface side in the case of corona-treated PET) shown in table 1, resin particles for the 2 nd resin layer shown in table 1 were melted so that the resin temperature under the die became 290 ℃, and film B having the 2 nd resin layer formed thereon was produced at a dry film thickness of 5 μm by the extrusion lamination method at a speed of 80 m/min.

The photosensitive transfer material was produced by heat lamination at 60℃and a speed of 10 m/min so that the 1 st resin layer of the film A and the 2 nd resin layer of the film B were in contact.

In comparative example 1, a solution of 20 mass% of the solid content of the resin described in table 1 (methyl ethyl ketone: pgmea=4:1 (mass ratio) was used as the solvent) was applied so that the dry film thickness became 5 μm. Thereafter, the film B having the 2 nd resin layer formed thereon was dried by a convection oven at 100 ℃ for 2 minutes. A photosensitive transfer material was produced in the same manner as in example 1 except for example 1 and comparative example 1.

In comparative examples 2 and 3, PANAPROTECT GS-38 (thickness of the temporary support 38 μm, manufactured by PANAC Corporation) which is a temporary support with a 2 nd resin layer (2 nd resin layer) or Nitto adhesive tape No.31B (thickness of the temporary support 25 μm, manufactured by Nitto DenKO CORPORATION) which is an adhesive with no polyethylene structure was used as the film B.

< production of PET substrate with copper layer >

A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method, and a PET substrate with a copper layer was produced.

< preparation of resin Pattern >

After the protective film was peeled off from the photosensitive transfer material thus produced, the photosensitive transfer material was laminated on the copper-layer-equipped PET substrate under a lamination condition of a line pressure of 0.6MPa and a line speed (lamination speed) of 3.6 m/min.

Then, the temporary support with the 2 nd resin layer was peeled off, and the photosensitive resin layer of the photosensitive transfer material and a mask made of glass and having a pattern of lines and spaces (Duty ratio 1:1) with a line width of 3 μm to 20 μm were brought into contact with each other while adjusting the exposure position (alignment), and after exposure with an ultra-high pressure mercury lamp with the mask interposed therebetween, the resist was left standing for 30 minutes and developed to form a resin pattern. For development, a 1.0 mass% aqueous sodium carbonate solution at 28 ℃ was used, and development by spraying was performed for 40 seconds.

< preparation of Circuit Wiring Pattern >

The patterned test piece was etched with a copper etching solution (Cu-02:KANTO CHEMICAL CO, inc.) at 23 ℃ for 30 seconds, and the resist was peeled off with a 4 mass% sodium hydroxide solution, whereby a circuit wiring pattern was produced.

The circuit wiring boards obtained in examples 1 to 14 were observed under a microscope, and thus, the circuit wiring boards were free from peeling, chipping, and the like, and were excellent in pattern.

[ evaluation ]

< evaluation of planarity of the 2 nd resin layer >

The flatness of the surface of the 2 nd resin layer formed on the temporary support was evaluated by observation with an objective lens and a differential interferometry by reflecting with an optical microscope.

3: no shading due to the irregularities was observed.

2: the irregularities were slightly observed.

1: a strong shadow was observed.

And 2 or more is an allowable range.

< measurement of peel force between 1 st resin layer/2 nd resin layer >

After the protective film was peeled off from the photosensitive transfer material thus produced, the protective film was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4 m/min.

The photosensitive transfer material laminated on the obtained copper-clad PET substrate was cut into a width of 4.5cm, and a copper-clad PET substrate side was attached to a 1 mm-thick polycarbonate sheet to which a double-sided tape was attached, to prepare a test sample.

The test sample obtained was stretched by Tensilon in a direction of bending the temporary support of the photosensitive transfer material by 180 degrees, and the peeling force between the 1 st resin layer and the 2 nd resin layer was measured. The peel force was measured at a peel speed of 300 mm/min.

< measurement of Release force between photosensitive resin layer/protective film >

The photosensitive transfer material thus produced was cut into a width of 4.5cm, and a temporary support was attached to a 1mm thick polycarbonate plate to which a double-sided tape was attached, thereby producing a test sample.

The obtained test sample was stretched by Tensilon in a direction of bending the protective film of the photosensitive transfer material by 180 degrees, and the peeling force between the photosensitive resin layer and the protective film was measured. The measurement was carried out at a peeling speed of 300 mm/min.

< measurement of Water contact Angle of the 2 nd resin layer >

The photosensitive transfer material thus produced was laminated on the copper-layer-equipped PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4 m/min.

The photosensitive transfer material laminated on the obtained PET substrate with copper layer was peeled off between the 1 st resin layer and the 2 nd resin layer, and the water contact angle of the surface of the 2 nd resin layer was measured by the following method.

The contact angle after 7 seconds was measured by a droplet method after dropping 2 μl of purified water onto the measurement surface at 25 ℃ using a contact angle meter (Kyowa Interface Science co., ltd., dropwmaster-501).

< evaluation of laminating Property >

The film B having the 2 nd resin layer formed on the temporary support was bonded to the film a having the 1 st resin layer and the dry photosensitive resin layer coated on the protective film at a speed of 10 m/min, so that the 1 st resin layer was brought into contact with the 2 nd resin layer, and then the adhesion state of the 1 st resin layer and the 2 nd resin layer was confirmed.

3: can be bonded at a lamination temperature of 25 ℃.

2: it is impossible to bond at a lamination temperature of 25 ℃, but it is possible to bond at a lamination temperature of 60 ℃.

1: even if the lamination temperature is set to 60 ℃, lamination cannot be performed.

< evaluation of protective film peelability >

The photosensitive transfer material thus prepared was cut into 4.5cm×9cm pieces 10 times, and the protective film was peeled off to confirm the peeling interface.

3: all of the layers were peeled off at the interface between the protective film and the photosensitive resin layer 10 times.

2: the protective film is peeled off from the photosensitive resin layer at the interface between the protective film and the photosensitive resin layer 1 to 9 times.

1: all of the layers were peeled off at the interface other than the interface between the protective film and the photosensitive resin layer 10 times.

< evaluation of peelability between 1 st resin layer/2 nd resin layer >

The photosensitive transfer material thus produced was cut into 4.5cm×9cm pieces, and after peeling off the protective film, the resultant was laminated on the copper-clad PET substrate under lamination conditions of a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4 m/min.

The temporary support of the photosensitive transfer material laminated on the obtained PET substrate with copper layer was peeled off repeatedly 10 times to confirm the peeling interface.

3: all of 10 times peeled off at the interface of the 1 st resin layer and the 2 nd resin layer.

2: in the number of times of 1 to 9, peeling is performed at the interface between the 1 st resin layer and the 2 nd resin layer.

All 1.10 times were peeled off at the interface other than the interface of the 1 st resin layer and the 2 nd resin layer.

The evaluation results are summarized in table 2.

TABLE 1

TABLE 2

The details of the comments described in table 2 are as follows.

* 1): since the resin layer 2 is peeled off from the temporary support, the peeling force cannot be measured.

* 2): since the photosensitive resin layer is broken by aggregation, the peel force cannot be measured.

* 3): since the resin layer 2 is peeled off from the temporary support, the roughness cannot be measured.

* 4): since the photosensitive resin layer is broken by aggregation, the roughness cannot be measured.

The abbreviations described in Table 1 other than those described above are described in detail below.

< protective film >

PET: polyethylene terephthalate film with thickness of 25 μm

Cerapeel BX8A: release PET film with a thickness of 25 μm (TORAY INDUSTRIES, INC.)

< 2 nd resin layer >

Evolue SP1071C: linear Low Density Polyethylene (LLDPE), prime Polymer co., ltd

EVA EV550: ethylene-vinyl acetate copolymer (E/VA), content of structural units derived from vinyl acetate 14% by mass, melt mass flow rate (190 ℃ C./2.16 kg load) 15g/10 min, DOW-MITSUI POLYCHEMICALS CO., LTD. EVAFLEX EV550

EVA P1007: ethylene-vinyl acetate copolymer (E/VA), content of structural units derived from vinyl acetate 10% by mass, melt mass flow rate (190 ℃ C./2.16 kg load) 9g/10 min, DOW-MITSUI POLYCHEMICALS CO., LTD. EVAFLEX P1007

NUCREL AN4214C: ethylene-methacrylic acid copolymer (E/MA), content of structural unit derived from methacrylic acid 4 mass%, melt mass flow rate (190 ℃ C./2.16 kg load) 7g/10 min, DOW-MITSUI POLYCHEMICALS CO., LTD. Preparation

NUCREL AN4228C: ethylene-methacrylic acid copolymer (E/MA), content of structural unit derived from methacrylic acid 4 mass%, melt mass flow rate (190 ℃ C./2.16 kg load) 14g/10 min, DOW-MITSUIPOLYCHEMICALS CO., LTD. Co., ltd

HIMILAN AM7326: a portion of Zn salt (E/MA Zn), melt mass flow rate (190 ℃ C./2.16 kg load) of 1.1g/10 min, DOW-MITSUI POLYCHEMICALS CO., LTD. Preparation of ethylene-methacrylic acid copolymer

HIMILAN 1652: a portion of Zn salt (E/MA Zn), melt mass flow rate (190 ℃ C./2.16 kg load) 5.5g/10 min, DOW-MITSUI POLYCHEMICALS CO., LTD. Preparation of ethylene-methacrylic acid copolymer

Synthetic mw=18,000: resin obtained by copolymerizing Ethyl Acrylate (EA)/Methyl Methacrylate (MMA) =40/60 (mass ratio)

< temporary support >

Corona treatment of PET: a Lumirror #25E-S105 μm thick, which is a single-sided corona-treated PET temporary support made of TORAY INDUSTRIES, INC., was used to form a 2 nd resin layer or the like on the corona-treated side.

As shown in tables 1 and 2, the photosensitive transfer materials of examples 1 to 14 showed less variation in line width of the resin pattern with the lapse of the exposure time than the photosensitive transfer materials of comparative examples 1 to 3.

The photosensitive transfer materials of examples 1 to 14 also had excellent planarity, lamination properties and protective film peelability of the 2 nd resin layer.

The disclosure of japanese patent application No. 2020-156733, filed on even 17, 9/2020, is incorporated herein by reference in its entirety.

All documents, patent applications and technical standards described in this specification are incorporated by reference into this specification to the same extent as if each document, patent application and technical standard was specifically and individually described to be incorporated by reference.

Symbol description

10-temporary support, 12-2 nd resin layer, 14-1 st resin layer, 16-photosensitive resin layer, 18-protective film, 100-photosensitive transfer material, GR-light shielding portion (non-image portion), EX-exposure portion (image portion), DL-alignment frame.

Claims (10)

1. A photosensitive transfer material comprising, in order, a protective film, a photosensitive resin layer, a 1 st resin layer, a 2 nd resin layer, and a temporary support,

the 1 st resin layer contains particles,

the 1 st resin layer is in contact with the 2 nd resin layer,

the 1 st resin layer and the 2 nd resin layer can be peeled off,

the 2 nd resin layer contains a resin having a polyethylene structure.

2. The photosensitive transfer material according to claim 1, wherein,

the resin having a polyethylene structure is a resin having an ethylene- (meth) acrylic acid copolymerized structure.

3. The photosensitive transfer material according to claim 1 or 2, wherein,

the resin having a polyethylene structure is an ionomer resin having an ethylene- (meth) acrylic acid metal salt copolymerization structure.

4. The photosensitive transfer material according to any one of claims 1 to 3, wherein,

the peel force between the 1 st resin layer and the 2 nd resin layer is 1.0gf/cm or more.

5. The photosensitive transfer material according to any one of claims 1 to 4, wherein,

the peel force between the 1 st resin layer and the 2 nd resin layer is a value greater than the peel force between the photosensitive resin layer and the protective film.

6. The photosensitive transfer material according to any one of claims 1 to 5, wherein,

the water contact angle on the 1 st resin layer side surface of the 2 nd resin layer is 90 degrees or less.

7. The photosensitive transfer material according to any one of claims 1 to 6, wherein,

the surface of the 1 st resin layer after the 1 st resin layer and the 2 nd resin layer are peeled off has irregularities formed of the particles.

8. A method for manufacturing a resin pattern, comprising, in order:

a step of peeling the protective film from the photosensitive transfer material according to any one of claims 1 to 7;

a step of bringing an outermost layer of the photosensitive transfer material from which the protective film has been peeled off, into contact with a base material, and bonding the outermost layer;

a step of peeling the temporary support and the 2 nd resin layer from the photosensitive transfer material bonded to the base material;

a step of exposing the photosensitive resin layer with the exposure mask in between by bringing the exposure mask into contact with the 1 st resin layer; a kind of electronic device with high-pressure air-conditioning system

And developing the photosensitive resin layer to form a resin pattern.

9. A method for manufacturing a circuit wiring includes the steps of:

The conductive layer is etched using the resin pattern formed by the method for manufacturing a resin pattern according to claim 8 as a mask.

10. A method for manufacturing a touch panel includes the steps of:

the wiring for a touch panel is formed by etching the conductive layer using the resin pattern formed by the method for manufacturing a resin pattern according to claim 8 as a mask.

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