CN117465091A

CN117465091A - Laminate and electronic device

Info

Publication number: CN117465091A
Application number: CN202310938743.2A
Authority: CN
Inventors: 片山晃男; 有富隆志
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2022-07-28
Filing date: 2023-07-28
Publication date: 2024-01-30

Abstract

The invention aims to provide a laminate which has excellent shape stability and excellent transparency of a conductive pattern even after heating. A laminate having a substrate and a conductive pattern comprising a metal nanoparticle and a resin, wherein the substrate has a total light transmittance of 75% or more and a glass transition temperature of 120 ℃ or more, and an electronic device comprising the laminate. The glass transition temperature of the substrate is preferably 200 ℃ or higher, and the thermal expansion coefficient of the substrate at 100 ℃ to 200 ℃ is preferably 10×10 ^‑6 Above (/ K) and 50X 10 ^‑6 (/ K) or below.

Description

Laminate and electronic device

Technical Field

The present invention relates to a laminate and an electronic device.

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, conductive patterns such as electrode patterns of sensors corresponding to a visual recognition portion, wirings of peripheral wiring portions, and lead-out wiring portions are provided inside the touch panel.

Generally, 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 using a photosensitive transfer material through a mask having a desired pattern and then developing the exposed layer is widely used.

In addition, conventionally, printed conductive patterns have been widely used in various fields as various sensors such as pressure sensors and biosensors, printed boards, solar cells, capacitors, electromagnetic wave shields, touch panels, antennas, and the like.

As a conventional dry film resist, a dry film resist described in patent document 1 is known.

Patent document 1 describes a dry film resist having a multilayer structure, wherein a photosensitive layer is provided on a support layer, and a non-photoreactive overcoat layer is provided between the support layer and the photosensitive layer made of a photoreactive composition.

Patent document 1: japanese patent laid-open No. 11-15150

Disclosure of Invention

An object of an embodiment of the present invention is to provide a laminate which has excellent shape stability of a conductive pattern even after heating and excellent flexibility.

Another object of another embodiment of the present invention is to provide an electronic device including the above laminate.

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

<1> a laminate, which has: a substrate; and a conductive pattern comprising a metal nanoparticle and a resin, wherein the total light transmittance of the substrate is 75% or more and the glass transition temperature of the substrate is 120 ℃ or more.

<2> the laminate according to <1>, wherein the glass transition temperature of the substrate is 200 ℃ or higher.

<3>According to<1>Or (b)<2>The laminate has a thermal expansion coefficient of 10X 10 per Kelvin at 100-200deg.C ^-6 Above 50×10 ^-6 The following is given.

<4> the laminate according to any one of <1> to <3>, wherein the substrate has a dimensional change rate of more than-1% and less than +1% at 100 ℃ to 200 ℃.

<5> the laminate according to any one of <1> to <4>, wherein the substrate is a polyimide substrate.

<6> the laminate according to any one of <1> to <5>, wherein the metal nano-body is a metal nano-wire.

<7> the laminate according to any one of <1> to <6>, wherein the metal nanoparticle is a nanoparticle having an aspect ratio of 1:1 to 1:10 and a sphere equivalent diameter of 1nm to 200 nm.

<8> the laminate according to any one of <1> to <7>, further comprising a protective layer on the side of the conductive pattern opposite to the side having the substrate.

<9> the laminate according to <8>, wherein the protective layer contains sulfur atoms, and the mass ratio of the amount of sulfur atoms contained in the protective layer to the amount of metal atoms contained in the conductive pattern is more than 0.10% and 20% or less.

<10> the laminate according to <9>, wherein the sulfur atom contained in the protective layer contains a sulfur atom derived from a thiol compound or a thioether compound.

<11> the laminate according to <10>, wherein the thiol compound or the thioether compound is a compound having an aromatic ring or a heteroaromatic ring.

<12> the laminate according to any one of <8> to <11>, wherein the elastic modulus of the protective layer is 4000MPa to 7000MPa.

<13>According to<8>To the point of<12>The laminate according to any one of the preceding claims, wherein 1000mJ/cm of the laminate is obtained by a high-pressure mercury lamp ² The elastic modulus of the protective layer before and after exposure of the protective layer varies by less than 10%.

<14> the laminate according to any one of <8> to <13>, wherein the elastic modulus of the protective layer changes by less than 10% after heating at 100 ℃ for 120 minutes.

<15> the laminate according to any one of <1> to <14>, further comprising a base layer between the base material and the conductive pattern.

<16> the laminate according to <15>, wherein the base layer contains any one of an acrylic resin and a styrene-acrylic resin.

<17> the laminate according to any one of <1> to <16>, further comprising a nonconductive pattern on at least a part of the substrate between the conductive patterns.

<18> the laminate according to <17>, wherein the conductive pattern and the nonconductive pattern comprise resins having the same structural unit.

<19> an electronic device comprising the laminate of any one of <1> to <18 >.

Effects of the invention

According to an embodiment of the present invention, a laminate having excellent shape stability and excellent bendability of a conductive pattern even after heating can be provided.

According to another embodiment of the present invention, an electronic device including the above-described laminate can be provided.

Drawings

Fig. 1 is a schematic diagram showing an example of the structure of a photosensitive transfer material.

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. Note that, although the description is given with reference to the drawings, the reference numerals 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 both or either acrylic acid and methacrylic acid, "(meth) acrylic acid ester" means both or either acrylic acid ester and methacrylic acid ester, "(meth) acryl" means both or either acryl or methacryl.

In addition, in the present specification, with respect to the amounts of each component in the composition, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, it means the total amount of the corresponding plurality of substances present in the composition.

In the present specification, the term "process" includes not only an independent process but also the term if the intended purpose of the process can be achieved even if it cannot be clearly distinguished from other processes.

In the labeling of groups (atomic groups) in the present specification, the label not labeled with a substituted or unsubstituted includes not only a group having no substituent but also a group having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, unless otherwise specifically indicated, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam, an ion beam, or the like. 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), active rays (active energy rays) such as X-rays and 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 2 or more preferred embodiments is a more preferred embodiment.

In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400nm to 700nm is 80% or more, preferably 90% or more.

In the present invention, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, ltd.

In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights obtained by performing detection using solvent THF (tetrahydrofuran) and a differential refractometer and converting them into standard substances using polystyrene, using a column Gel Permeation Chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both are commercial names manufactured by Tosoh Corporation).

In the present specification, "total solid component" means the total mass of components after removal of solvent from all the constituents of the composition. As described above, the term "solid component" refers to a component from which the solvent has been removed, and may be solid or liquid at 25 ℃.

(laminate)

The laminate of the present invention comprises a substrate and a conductive pattern comprising a metal nanoparticle and a resin, wherein the substrate has a total light transmittance of 75% or more and a glass transition temperature of 120 ℃ or more.

The present inventors have found that a laminate having a conductive pattern including a metal nanoparticle and a resin has problems that the conductive pattern has insufficient shape stability and insufficient bendability after heating.

As a result of intensive studies, the present inventors have found that the above-described method is excellent in shape stability of the conductive pattern and in flexibility of the laminate even after heating.

It is assumed that the above embodiment has excellent heat resistance of the substrate, can suppress shape change due to heat, suppresses the substrate from being dull and turbid due to heat, and further has excellent flexibility of the conductive pattern itself, and has excellent shape stability of the conductive pattern and excellent flexibility of the laminate even after heating, because the conductive pattern includes the metal nano-body and the resin, and has small strain and excellent follow-up property when bending together with the substrate having a high glass transition temperature.

The laminate according to the present invention will be described in detail below.

< substrate >

The laminate of the present invention comprises a substrate, wherein the total light transmittance of the substrate is 75% or more, and the glass transition temperature of the substrate is 120 ℃ or more.

The total light transmittance of the base material is 75% or more, preferably 80% or more, more preferably 85% or more and 100% or less, from the viewpoints of transparency and shape stability of the conductive pattern before and after heating.

The total light transmittance of the substrate in the present invention is a value measured by a haze meter under the condition of a D65 light source (wavelength 380nm to 780 nm), and as the haze meter, NDH-4000 (NIPPONDENSHOKU INDUSTRIES co., LTD) can be used, for example.

The glass transition temperature of the substrate is 120 ℃ or higher, preferably 150 ℃ or higher, more preferably 200 ℃ or higher, and particularly preferably 250 ℃ or higher and 400 ℃ or lower, from the viewpoints of shape stability of the conductive pattern before and after heating and flexibility of the laminate.

In addition, the glass transition temperature (Tg) of the substrate in the present invention was measured using a solid viscoelasticity measuring machine RSA-G2 (manufactured by TA Instruments Japan Inc.).

The thermal expansion coefficient of the substrate at 100 to 200 ℃ is preferably 1×10 from the viewpoint of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate ^-6 (/ K) above and 200X 10 ^-6 (/ K) or less, more preferably 5X 10 ^-6 (/ K) above and 100X 10 ^-6 (/ K) or less, particularly preferably 10X 10 ^-6 Above (/ K) and 50X 10 ^-6 (/ K) or below.

The dimensional change rate of the substrate at 100 to 200 ℃ is preferably greater than-2% and less than +2%, more preferably greater than-1% and less than +1%, and particularly preferably greater than-1% and less than 0%, from the viewpoints of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate.

In addition, regarding the Coefficient of Thermal Expansion (CTE) and the dimensional change rate of the substrate in the present invention, measurement was performed at a temperature ranging from 100 ℃ to 200 ℃ using a thermal analyzer TMA7100 (manufactured by Hitachi High-Tech Corporation), unless otherwise specifically described.

As the substrate used in the present invention, a resin substrate is preferable.

Examples of the substrate include polyethylene terephthalate (PET) substrate, cellulose acylate substrate, polyethylene naphthalate (PEN) substrate, polycarbonate substrate, polyimide substrate, and cycloolefin polymer substrate.

Among them, from the viewpoints of shape stability of the conductive pattern before and after heating and flexibility of the laminate, a polyethylene naphthalate substrate, a polycarbonate substrate, a polyimide substrate, or a cycloolefin polymer substrate is preferable, a polyethylene naphthalate substrate, a polycarbonate substrate, or a polyimide substrate is more preferable, and a polyimide substrate is particularly preferable.

When the substrate is manufactured in a roll-to-roll manner, a film substrate is preferable. When the circuit wiring for the touch panel is manufactured by a roll-to-roll method, the substrate is preferably a sheet-like resin composition.

The substrate may have 1 layer of the conductive pattern alone or 2 or more layers of the conductive pattern. When the conductive pattern has 2 or more layers, conductive patterns of different materials are preferable.

The substrate may have the conductive pattern on only one surface, or may have the conductive pattern on both surfaces.

The substrate may also have a wiring which is routed. The substrate as described above can be suitably used as a substrate for a touch panel.

As a material of the routing wiring, metal is preferable.

Examples of the metal used for the wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and an alloy of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium is preferable as a material of the wiring, and copper is particularly preferable.

The average thickness of the substrate is not particularly limited, but is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm.

The average thickness of each layer and the substrate in the present invention is an average value of 10 portions measured by observing a cross section in a direction perpendicular to the in-plane direction using a Scanning Electron Microscope (SEM).

< conductive Pattern >

The laminate according to the present invention has a conductive pattern including a metal nano-body and a resin.

The conductive pattern is preferably formed, for example, in a wiring pattern, if necessary.

In addition, from the viewpoints of shape stability of the conductive patterns before and after heating and flexibility of the laminate, the laminate according to the present invention preferably further has a nonconductive pattern on at least a part of the substrate between the conductive patterns, and more preferably has a layer formed of the conductive pattern and the nonconductive pattern on at least a part of the substrate.

From the viewpoint of more effectively exhibiting the effects of the present invention, the conductive pattern preferably includes a conductive pattern having a line width of 200 μm or less, more preferably includes a conductive pattern having a line width of 150 μm or less, and particularly preferably includes a conductive pattern having a line width of 100 μm or less.

In the present invention, "conductive" means that the volume resistivity is less than 1X 10 ⁶ The property of Ω cm, "non-conductive" means a volume resistivity of 1×10 ⁶ And omega cm or more.

The volume resistivity of the conductive pattern is preferably less than 1×10 ⁴ Ωcm。

The volume resistivity was measured by a commercially available resistivity measuring instrument (for example, loresta GX MCP-T700 manufactured by Mitsubishi Chemical Analytech).

Metal nano-body-

The conductive pattern includes a metal nano-body.

As a material of the metal nano-body included in the conductive pattern, copper, silver, zinc, iron, chromium, molybdenum, nickel, aluminum, gold, platinum, palladium, an alloy composed of two or more of these, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide: indium zinc Oxide), conductive silica, and the like can be used, but copper, silver, nickel, aluminum, gold, platinum, palladium, or an alloy thereof is preferable from the viewpoints of resistance value, cost, sintering temperature, and the like, silver, copper, or an alloy thereof is more preferable, and particularly, silver or an alloy of silver is more preferable from the viewpoints of sintering temperature and oxidation inhibition. That is, the metal nano-body is particularly preferably a nano-body of silver or a silver compound.

The shape of the metal nanoparticle is not particularly limited as long as it is a known shape, but the metal nanoparticle is preferably a metal nanoparticle or a metal nanowire, and more preferably a metal nanowire.

Examples of the shape of the metal nanowire include a columnar shape, a rectangular parallelepiped shape, a columnar shape having a polygonal cross section, and the like. In applications requiring high transparency, it is preferable that the metal nanowire has at least one of a cylindrical shape and a cylindrical shape having a polygonal cross section.

The cross-sectional shape of the metal nanowire can be observed using, for example, a Transmission Electron Microscope (TEM).

The diameter (so-called short axis length) of the metal nanowire is not particularly limited, and is preferably 50nm or less, more preferably 35nm or less, and further preferably 20nm or less from the viewpoint of transparency, for example.

For example, the lower limit of the diameter of the metal nanowire is preferably 5nm or more from the viewpoints of oxidation resistance and durability.

The length of the metal nanowire (so-called long axis length) is not particularly limited, and is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 30 μm or more from the viewpoint of conductivity, for example.

For example, from the viewpoint of suppressing the formation of aggregates during the production process, the upper limit of the length of the metal nanowire is preferably 1mm or less.

As for the diameter and length of the metal nanowire, for example, measurement can be performed using a Transmission Electron Microscope (TEM) or an optical microscope.

Specifically, the diameters and lengths of 300 metal nanowires randomly selected from among metal nanowires observed using a Transmission Electron Microscope (TEM) or an optical microscope in magnification were measured. The measured values are arithmetically averaged and the obtained values are taken as the diameter and length of the metal nanowires.

The metal nanoparticles may be spherical particles, flat particles, or irregularly shaped particles.

The average primary particle diameter of the metal nanoparticles is preferably 0.1nm to 500nm, more preferably 1nm to 200nm, particularly preferably 1nm to 100nm, from the viewpoints of stability and Fusion (Fusion) temperature.

The average primary particle diameter of the metal nanoparticles in the present invention is obtained by taking a scanning electron microscope photograph (SEM image) of 100 particles by a scanning electron microscope (for example, S-3700N, manufactured by Hitachi High-Technologies Corporation), measuring the particle diameter by using an image processing measuring device (LUZEXAP; manufactured by NIRECO CORPORATION), and obtaining an arithmetic average value. That is, the particle diameter referred to in the present invention is expressed by the diameter of the particles when the projected shape of the particles is a circle, and by the diameter of the particles when the projected shape of the particles is an irregular shape other than a sphere, and the projected area of the particles is the same as the area of the circle.

From the viewpoint of conductivity, the metal nanoparticles preferably contain a metal more noble than silver, and in this case, flat particles at least a part of which is coated with gold are more preferably contained. Wherein, "a metal more noble than silver" means "a metal having a standard electrode potential higher than that of silver".

The ratio of the metal more noble than silver to silver in the metal nanoparticles is preferably 0.01 to 5 atomic%, more preferably 0.1 to 2 atomic%, and even more preferably 0.2 to 0.5 atomic%.

The content of the metal more noble than silver can be measured by, for example, high-frequency inductively coupled plasma (Inductively Coupled Plasma:icp) emission spectrometry after dissolving the sample with an acid or the like.

The metal nanoparticle is preferably a nanoparticle having an aspect ratio of 1:1 to 1:10 and a sphere equivalent diameter of 1nm to 200nm from the viewpoints of dispersibility and conductivity.

In addition, the aspect ratio of the metal nano-body is the length of the long axis of the metal nano-body/the length of the short axis of the metal nano-body.

The metal nano-body in the conductive pattern may be used alone or in combination of two or more.

From the viewpoints of conductivity and dispersion stability, the content of the metal nano-body is preferably 1 to 99 mass%, more preferably 1 to 95 mass%, and even more preferably 1 to 90 mass% relative to the total mass of the conductive pattern.

Resin

The conductive pattern includes a resin.

The non-conductive pattern preferably includes a resin.

From the viewpoints of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate, the resin contained in the conductive pattern and the resin contained in the nonconductive pattern preferably have the same structural unit, more preferably have 50 mass% or more of the same structural unit with respect to the total mass of the resin, still more preferably have 80 mass% or more of the same structural unit with respect to the total mass of the resin, and particularly preferably have 90 mass% or more of the same structural unit with respect to the total mass of the resin.

In addition, from the viewpoints of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate, the resin contained in the conductive pattern and the resin contained in the nonconductive pattern preferably have the same resin.

From the viewpoint of durability, the above resins are preferably each independently a binder polymer.

Examples of the resin include an acrylic resin [ e.g., poly (methyl methacrylate) ], a polyester resin [ e.g., polyethylene terephthalate (PET) ], a polycarbonate resin, a polyimide resin, a polyamide resin, a polyolefin (e.g., polypropylene), polynorbornene, a cellulose resin, polyvinyl alcohol (PVA), and polyvinylpyrrolidone.

Examples of the cellulose resin include hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), methylcellulose (MC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), cellulose, and the like.

The resins may be conductive polymer materials, respectively.

Examples of the conductive polymer material include polyaniline and polythiophene.

Among them, from the viewpoints of dispersibility of the metal nanoparticle and dimensional stability of the conductive pattern after the energization, the resin preferably contains at least one resin selected from the group consisting of cellulose resin, polyvinyl alcohol and polyvinylpyrrolidone, and more preferably contains cellulose resin.

Further, from the viewpoints of dispersibility of the metal nanoparticle and dimensional stability of the conductive pattern before and after heating, the resin preferably contains an acrylic-urethane copolymer resin, and more preferably contains a cellulose resin and an acrylic-urethane copolymer resin.

From the viewpoint of dimensional stability of the conductive pattern after the energization, the glass transition temperature (Tg) of the resin is independently preferably 180 ℃ or less, more preferably 40 to 160 ℃, and particularly preferably 60 to 150 ℃.

In the present invention, the glass transition temperature of the resin can be measured using Differential Scanning Calorimetry (DSC).

Specific measurement methods are carried out according to the methods described in JIS K7121 (1987) or JIS K6240 (2011). The glass transition temperature in the present specification uses an extrapolated glass transition onset temperature (hereinafter, sometimes referred to as Tig).

The method for measuring the glass transition temperature is described in more detail below.

When the glass transition temperature is determined, the device is held at a temperature about 50 ℃ below the Tg of the expected resin until stable, followed by a heating rate: heating at 20deg.C/min to a temperature about 30deg.C higher than the temperature at which the glass transition ends, and making a Differential Thermal Analysis (DTA) curve or DSC curve.

The extrapolated glass transition onset temperature (Tig), i.e., the glass transition temperature Tg in the present specification, is determined as the following temperature: the temperature at which the intersection point of a straight line obtained by extending the low-temperature side base line of the DTA curve or DSC curve toward the high-temperature side and a tangent line drawn at the point where the gradient of the curve of the stepwise change portion of the glass transition is maximum.

The weight average molecular weight (Mw) of the resin is not particularly limited, but is preferably 1,000 ～ 2,000,000, more preferably 10,000 ～ 1,200,000, independently from the viewpoint of dimensional stability of the conductive pattern after the energization.

The resin may be used alone, or two or more kinds may be used in combination.

From the viewpoints of metal film formability and conductivity at the time of sintering, the content of the resin in the conductive pattern is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass%, relative to the total mass of the conductive pattern.

Further, from the viewpoint of shape stability of the conductive pattern before and after heating, the content of the non-conductive pattern resin is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and particularly preferably 80 to 100% by mass, relative to the total mass of the non-conductive pattern.

The conductive pattern and the nonconductive pattern may each independently further include other additives.

The other additives include known additives such as surfactants.

Examples of the surfactant include RADISOL A-90 (manufactured by NOF CORPORATION, solid content concentration: 1%), NAROACTY CL-95 (manufactured by Sanyo Chemical Industries, ltd. Times., solid content concentration: 1%), and the like.

The conductive pattern and the nonconductive pattern may each independently include inorganic particles.

Examples of the inorganic particles include silica, mullite, and alumina.

The conductive pattern and the nonconductive pattern are each independently preferably high in transparency, and the transmittance for light having a wavelength of 380nm to 780nm is preferably 60% or more, more preferably 70% or more.

The thickness of the conductive pattern and the nonconductive pattern is not particularly limited. The average thickness of the conductive pattern and the nonconductive pattern is preferably 1nm to 1,000 μm, more preferably 5nm to 15 μm, still more preferably 10nm to 10 μm, and particularly preferably 10nm to 100nm, independently from each other from the viewpoints of conductivity and film formability.

The method for forming the conductive pattern and the nonconductive pattern is not particularly limited, and a method for forming the conductive pattern and the nonconductive pattern by applying conductive ink, which is a material obtained by dispersing a conductive material containing the metal nano-body in a liquid, and removing at least a part of the metal nano-body forming the nonconductive pattern by wet etching is preferable.

The conductive pattern may be formed by dry etching.

The method of applying the conductive ink is not particularly limited, and examples thereof include an inkjet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, and a die coating method (i.e., a slit coating method).

The conductive ink used in the present invention may be a curable ink, for example, a thermosetting ink, a photo-curable ink, or a thermal and photo-curable ink.

The conductive ink may contain a metal nanomaterial and a resin, and may contain at least any one of a solvent and the other additives.

As the solvent contained in the conductive ink, water and an organic solvent can be used.

As the organic solvent, preferred are hydrocarbons such as toluene, dodecane, tetradecane, cyclododecene, n-heptane, n-undecane, and alcohols such as ethanol and isopropanol.

The removal of the metal nano-body by wet etching will be described in detail in a method for producing a laminate to be described later.

As a method for forming the conductive pattern, a step of drying, calcining, or the like may be included as necessary after coating.

< substrate layer >

From the viewpoints of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate, the laminate according to the present invention preferably further includes a base layer between the base material and the conductive pattern.

The base layer preferably contains a resin.

Examples of the resin contained in the base layer include an acrylic resin, a styrene-acrylic resin, a polyester resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, a phenolic resin, and the like.

Among them, from the viewpoints of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate, the resin in the base layer preferably contains any one of an acrylic resin and a styrene-acrylic resin, and more preferably contains an acrylic resin.

The resin in the base layer may be used alone or in combination of two or more.

From the viewpoints of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate, the content of the resin is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, and particularly preferably 55 to 90% by mass, relative to the total mass of the base layer.

The base layer may contain a polymerizable compound.

When the underlayer contains a polymerizable compound, the underlayer preferably contains a polymerizable compound and a polymerization initiator.

From the viewpoint of curability, the polymerizable compound is preferably an ethylenically unsaturated compound, and more preferably a (meth) acrylate compound.

From the viewpoints of curability and strength of the underlayer, the polymerizable compound is preferably a polymerizable compound having 2 or more functions, more preferably a polymerizable compound having 3 to 10 functions, and particularly preferably a polymerizable compound having 4 to 8 functions.

From the viewpoints of curability and strength of the underlayer, the polymerizable compound preferably contains an ethylenically unsaturated compound having 2 or more functions, and more preferably contains a (meth) acrylate compound having 2 or more functions.

As the polymerizable compound, a polymerizable compound used for a photosensitive resin layer described below can be suitably used.

The polymerizable compound in the base layer may be used alone or in combination of two or more.

From the viewpoints of the shape stability of the conductive pattern before and after heating and the flexibility of the laminate, the content of the polymerizable compound is preferably 5 to 55 mass%, more preferably 10 to 50 mass%, and particularly preferably 20 to 45 mass% with respect to the total mass of the base layer.

The polymerization initiator is preferably a photopolymerization initiator.

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkyl benzophenone structure (hereinafter, also referred to as an "α -aminoalkyl benzophenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkyl benzophenone structure (hereinafter, also referred to as an "α -hydroxyalkyl benzophenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").

Among them, from the viewpoint of curability, the base layer preferably contains at least one polymerization initiator selected from the group consisting of an oxime ester-based photopolymerization initiator, a bisimidazole-based photopolymerization initiator, an alkylbenzene-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator, and more preferably contains an oxime ester-based photopolymerization initiator.

The polymerization initiator in the base layer may be used alone or in combination of two or more.

From the viewpoint of the strength of the underlayer, the content of the polymerization initiator is preferably 0.1 to 20 mass%, more preferably 0.2 to 10 mass%, and particularly preferably 0.5 to 5 mass% relative to the total mass of the underlayer.

The base layer may contain other known additives.

The average thickness of the underlayer is not particularly limited, but is preferably 1nm to 200nm, more preferably 5nm to 100nm, and particularly preferably 15nm to 50nm, from the viewpoint of dimensional stability of the conductive pattern before and after heating.

< resin layer (protective layer) >)

The laminate according to the present invention preferably has a resin layer (also referred to as a "protective layer") containing a resin on the side of the conductive pattern opposite to the side having the base material (i.e., on the conductive pattern on the base material).

The resin contained in the resin layer may preferably be: acrylic resins (for example, dianal series manufactured by Mitsubishi Chemical Corporation, NIPPON SHOKUBIAI CO., LTD. Acryset series manufactured by Acryset al, etc.), POLYESTER resins (for example, elitel series manufactured by UNITKA LTD. Manufactured by Nichigo-PolyESTER series manufactured by Mitsubishi Chemical Corporation, etc.), polyvinyl alcohol resins (for example, KURARAY CO., LTD. Manufactured by POVAL series, etc.), polyvinyl acetal resins (for example, SEKISUI CHEMICAL CO., LTD. Manufactured by S-LEC series, etc.), phenolic resins (for example, PHENOLITE series manufactured by DIC Corporation, etc.).

Among them, from the viewpoint of dimensional stability of the conductive pattern before and after heating, the resin preferably contains at least one resin selected from the group consisting of an acrylic resin, a polyester resin, a polyvinyl acetal resin, and a phenolic resin, and more preferably contains at least one resin selected from the group consisting of a polymer having a structural unit derived from benzyl (meth) acrylate, and a polyester resin.

The glass transition temperature (Tg) of the resin is preferably 150 ℃ or less, more preferably 30 to 140 ℃, still more preferably 40 to 130 ℃, particularly preferably 40 to 120 ℃ from the viewpoint of dimensional stability of the conductive pattern before and after heating.

The acid value of the resin is preferably 0 to 60mgKOH/g, more preferably 0 to 50mgKOH/g, particularly preferably 0 to 40mgKOH/g, from the viewpoints of etching resistance and dimensional stability of the conductive pattern after being electrified.

The acid value of the resin can be measured by a measurement method described later.

The resin in the resin layer may be used alone or in combination of two or more.

From the viewpoints of metal film formability and electrical conductivity during sintering, the content of the resin is preferably 40 to 100 mass%, more preferably 50 to 95 mass%, and particularly preferably 55 to 90 mass% relative to the total mass of the resin layer.

The resin layer may contain a polymerizable compound.

When the resin layer contains a polymerizable compound, the resin layer preferably contains a polymerizable compound and a polymerization initiator.

The polymerizable compound used in the resin layer is preferably a polymerizable compound described in the above underlayer.

The polymerizable compound in the resin layer may be used alone or in combination of two or more.

From the viewpoint of the strength of the resin layer, the content of the polymerizable compound is preferably 5 to 55% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 45% by mass, relative to the total mass of the resin layer.

The polymerization initiator is preferably a photopolymerization initiator.

The polymerization initiator used in the resin layer is preferably a polymerization initiator described in the above base layer.

The polymerization initiator in the resin layer may be used alone or in combination of two or more.

From the viewpoint of the strength of the resin layer, the content of the polymerization initiator is preferably 0.1 to 20 mass%, more preferably 0.2 to 10 mass%, and particularly preferably 0.5 to 5 mass% relative to the total mass of the resin layer.

The resin layer (protective layer) is preferably formed on the conductive pattern and then cured. By performing the curing treatment, for example, in a subsequent process of laminating a laminate including a conductive pattern with other components or the like, the properties of the protective layer are not easily changed even when subjected to heat or the like, and the performance of the circuit can be well maintained.

As a method for curing the protective layer, the above-mentioned polymerization initiator and polymerizable compound are added to the protective layer, and irradiation with radiation and/or heating are performed. When the resin has a polymerizable functional group, the polymerizable functional group is preferably cured by a polymerization reaction.

The cured state of the protective layer can be estimated by evaluating the elastic modulus of the resin portion of the protective layer. The elastic modulus of the cured protective layer is preferably 4000MPa to 7000MPa. When the elastic modulus after curing is within this range, the performance of the conductive pattern circuit can be well maintained.

The elastic modulus is a value measured using an Atomic Force Microscope (AFM), and can be measured, for example, using a Dimension ICON manufactured by Bruker Japan k.k. in PeakForce QNM (Quantitative Nanoscale Mechanical: quantitative nanomechanical) mode, probe: RTESPA-300 (300 kHz, 40N/m) was used.

Furthermore, the cured protective layer is preferably in a state where no further curing reaction occurs, so as to avoid unexpected changes in properties caused by subsequent processes. Specifically, it is preferable that the laminate after curing the protective layer is irradiated with a high-pressure mercury lamp at 1000mJ/cm ² The change in the elastic modulus of the protective layer before and after exposure is less than 10% and/or the change in the elastic modulus of the protective layer after heating the laminate at 100 ℃ for 120 minutes is less than 10%.

The change in the elastic modulus of the protective layer before and after exposure can be obtained by measuring the elastic modulus of the protective layer before and after exposure by the above method and determining the difference between the measured values. The change in the elastic modulus of the protective layer before and after heating can be obtained by measuring the elastic modulus of the protective layer before and after heating by the above-described method and determining the difference between the measured values.

From the viewpoints of adhesion to the conductive pattern and dimensional stability of the conductive pattern after being energized, the resin layer preferably has a compound e capable of bonding or coordinating with a metal contained in the metal nano-body.

The compound e is preferably a compound having an unshared electron pair, more preferably at least one compound selected from the group consisting of a nitrogen-containing compound having an unshared electron pair and a sulfur-containing compound having an unshared electron pair, and particularly preferably a nitrogen-containing compound having an unshared electron pair, from the viewpoints of complexation and dimensional stability of the conductive pattern after being energized.

Further, the compound e is preferably a heterocyclic compound, more preferably a nitrogen-containing heterocyclic compound, a sulfur-containing heterocyclic compound or a nitrogen-and sulfur-containing heterocyclic compound, and particularly preferably a nitrogen-containing heterocyclic compound, from the viewpoints of complexation and dimensional stability of the conductive pattern after energization.

In addition, from the viewpoints of the complexation and the dimensional stability of the conductive pattern after the energization, the nitrogen-containing heterocyclic compound preferably has a heterocyclic ring containing 2 or more nitrogen atoms, more preferably has a heterocyclic ring containing 3 or more nitrogen atoms, and particularly preferably has a heterocyclic ring containing 3 or 4 nitrogen atoms.

The heterocycle of the heterocyclic compound may be any of monocyclic and polycyclic heterocycles.

Examples of the hetero atom of the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably has a nitrogen atom.

Examples of the heterocyclic compound include preferably a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound. Among the above, from the viewpoint of adhesion to the conductive pattern a, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds, and still more preferably at least one compound selected from the group consisting of triazole compounds and tetrazole compounds, and particularly preferably triazole compounds.

Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[ chemical formula 1]

[ chemical formula 2]

As the tetrazolium compound, the following compounds can be exemplified.

[ chemical formula 3]

[ chemical formula 4]

The thiadiazole compounds can be exemplified by the following compounds.

[ chemical formula 5]

As the triazine compound, the following compounds can be exemplified.

[ chemical formula 6]

As the rhodanine compound, the following compounds can be exemplified.

[ chemical formula 7]

As the thiazole compounds, the following compounds can be exemplified.

[ chemical formula 8]

As benzothiazole compounds, the following compounds can be exemplified.

[ chemical formula 9]

As benzimidazole compounds, the following compounds can be exemplified.

[ chemical formula 10]

[ chemical formula 11]

As the benzoxazole compound, the following compounds can be exemplified.

[ chemical formula 12]

The sulfur-containing compound may preferably be a thiol compound, a thioether compound or a disulfide compound.

The thiol compound may preferably be an aliphatic thiol compound or an aromatic thiol compound.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) can be suitably used.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutanoyloxy) butane, pentaerythritol tetrakis (3-mercaptobutanoate), 1,3, 5-tris (3-mercaptobutanoyloxy) ethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolethane tris (3-mercaptobutanoate), tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol dithiopropionate, 1, 4-bis (3-mercaptobutanoyloxy) butane, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexamethylenedithiol, 2' - (ethylenedithiol), and mesoethyl-2-dithiol.

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β -mercaptopropionic acid, methyl-3-mercaptopropionic acid ester, 2-ethylhexyl-3-mercaptopropionic acid ester, n-octyl-3-mercaptopropionic acid ester, methoxybutyl-3-mercaptopropionic acid ester, and stearyl-3-mercaptopropionic acid ester.

Examples of the aromatic thiol compound include thiophenol, 1, 2-benzenedithiol, 3-methoxythiophenol, 4- (methylthio) thiophenol, 1-naphthalenethiol, 2-naphthalenethiol, 1, 5-dimercaptonaphthyl, 4-biphenyldithiol, triphenylmethyl mercaptan, 2-mercaptobenzothiazole, 2, 5-dimercapto-1, 3, 4-thiadiazole, and 2-mercaptobenzimidazole.

Examples of the thioether compound include 2-amino-5- (benzylthio) -1,3, 4-thiadiazole, 5- (benzylthio) -1H-tetrazole, 2- (phenylthio) aniline, 2- (methylthio) benzothiazole, bis (2-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, pentylsulfide, benzylsulfide, benzylphenylsulfide, 4' -thiobis (o-cresol), N- (cyclohexylthio) phthalimide, and bis (benzoylmethyl) sulfide.

The thiol compound or thioether compound is preferably a compound having an aromatic ring or a heteroaromatic ring from the viewpoint of interaction with a metal surface and/or solvent solubility. Examples of the aromatic ring and the heteroaromatic ring include a benzene ring, a naphthalene ring, a thiophene ring, a thiazole ring, a thiadiazole ring, a benzothiophene ring, a benzothiazole ring, a benzimidazole ring, a triazole ring, a benzotriazole ring, and a tetrazole ring.

When both the thiol compound and the thioether compound are contained, it is preferable that at least one of the thiol compound and the thioether compound has an aromatic ring or a heteroaromatic ring from the same viewpoints as described above.

Examples of the disulfide compound include 2- (4 '-morpholinodithio) benzothiazole, 2' -benzothiazole disulfide, bis (2-benzoylaminophenyl) disulfide, 1-thiobis (2-naphthol), bis (2, 4, 5-trichlorophenyl) disulfide, 4 '-dithiomorpholine, tetraethylthiuram disulfide, dibenzyldisulfide, bis (2, 4-dinitrophenyl) disulfide, 4' -diaminodiphenyl disulfide, diallyl disulfide, di-t-butyl disulfide, bis (6-hydroxy-2-naphthyl) disulfide, dicyclohexyldisulfide, isobutyrylthioamine disulfide, 2, 5-bis (octyldisulfide) -1,3, 4-thiadiazole, sulbutiamine (sulbutiamine), and diphenyl disulfide.

The molecular weight of the compound e is preferably less than 1,000, more preferably 50 to 500, further preferably 50 to 200, particularly preferably 50 to 150, from the viewpoint of adhesion to the conductive pattern.

The compound e in the resin layer may be used alone or in combination of two or more.

From the viewpoint of adhesion to the conductive pattern, the content of the compound e is preferably 0.01 to 40% by mass, more preferably 0.1 to 40% by mass, even more preferably 0.3 to 30% by mass, and particularly preferably 0.5 to 30% by mass, relative to the total mass of the resin layer.

From the viewpoint of reliability of the conductive pattern, for example, corrosion resistance under a high humidity environment, the resin layer (protective layer) preferably contains a sulfur atom, more preferably contains a sulfur atom derived from a thiol compound or a thioether compound. When the resin layer (protective layer) is provided on the conductive pattern, the ratio of the amount of sulfur atoms contained in the protective layer to the amount of metal atoms contained in the conductive layer (sulfur atom amount/metal atom amount; mass ratio) is preferably 0.10 mass% or more, more preferably 0.12 mass% or more, and still more preferably 0.15 mass% or more from the viewpoint of corrosion resistance of the conductive pattern. Further, from the viewpoint of conductivity of the conductive pattern, the ratio of the sulfur atom weight to the metal atom weight is preferably 20 mass% or less, more preferably 18 mass% or less, and further preferably 10 mass% or less. The ratio of sulfur atom weight to metal atom weight is preferably more than 0.10 mass% and 20 mass% or less. In the above range, in particular, it is effective when a resin layer (protective layer) containing the compound e is provided on the conductive pattern.

The sulfur atom weight and the metal atom weight were obtained under conditions of an acceleration voltage of 200kV and a probe current of 0.7nA using a scanning transmission electron microscope (for example, talosF200X manufactured by Thermo Fisher Scientific K.K.).

The resin layer may contain other known additives.

The average thickness of the resin layer is not particularly limited, but is preferably 1nm to 200nm, more preferably 5nm to 100nm, and particularly preferably 15nm to 50nm, from the viewpoint of dimensional stability of the conductive pattern after the energization.

The total thickness of the layer formed by combining the conductive pattern and the resin layer after forming the resin layer on the conductive pattern is preferably 15nm to 100nm, more preferably 15nm to 90nm, and particularly preferably 15nm to 60nm. In this case, the total thickness of the layers obtained by combining the conductive pattern and the resin layer may be equal to or different from the total thickness of the layers when the layers are formed individually. For example, when the compatibility between the conductive pattern and the resin contained in the resin layer is high, a layer is formed in which a part of the materials of the conductive pattern and the resin layer are mixed, and therefore, at this time, the total thickness of the layer in which the conductive pattern and the resin layer are combined is not equal to the sum of the layer thicknesses in the case where each layer is formed alone.

The laminate according to the present invention may have a known layer other than the above.

< use >

The laminate according to the present invention can be applied to various devices. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to a display device such as an organic electroluminescence display device or a liquid crystal display device.

The laminate according to the present invention can be suitably applied to a flexible display device, particularly a flexible touch panel.

< method for producing laminate >

The method for producing a laminate according to the present invention is not particularly limited, and preferably includes the following steps in order: step 1, preparing a laminate having a substrate and a conductive pattern a containing a metal nano-body and a resin; step 2, forming a photosensitive resin layer c on the conductive pattern a; step 3, performing pattern exposure and development on the photosensitive resin layer c to obtain a resin pattern c'; and a step 4 of removing the metal nano-bodies in the conductive pattern a by wet etching using the resin pattern c' as a mask, thereby forming the non-conductive pattern.

< procedure 1>

The method for producing a laminate according to the present invention preferably includes step 1: a laminate having a substrate and a conductive pattern a containing a metal nanoparticle and a resin is prepared.

As the base material, the above-described base material can be suitably used.

The metal nano-body and the resin in the conductive pattern a are preferably the metal nano-body and the resin described above.

The resin in the conductive pattern a may be used alone or in combination of two or more.

From the viewpoints of metal film formability and conductivity during sintering, the content of the resin is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass% with respect to the total mass of the conductive pattern a.

The conductive pattern a may further contain other additives.

As the other additive in the conductive pattern a, the above-mentioned other additive can be cited.

The conductive pattern a preferably has high transparency, and the transmittance for light having a wavelength of 380nm to 780nm is preferably 60% or more, more preferably 70% or more.

The thickness of the conductive pattern a is not limited. The average thickness of the conductive pattern a is preferably 0.001 μm to 1,000 μm, more preferably 0.005 μm to 15 μm, and particularly preferably 0.01 μm to 10 μm from the viewpoints of conductivity and film formability.

The method for forming the conductive pattern a is not particularly limited, and is preferably formed by applying conductive ink, which is a material obtained by dispersing a conductive material containing the metal nano-bodies in a liquid.

As a method for forming the conductive pattern a, a step of drying, calcining, or the like may be included as necessary after coating.

The conductive pattern a is preferably formed in a shape larger than the shape of the desired conductive pattern.

Process 1 b-

The method for producing a laminate according to the present invention may further include a step 1b of: on the conductive pattern a, a resin layer b (also referred to as a "protective layer") containing a resin is formed.

The preferred mode of the resin layer b is the same as the preferred mode of the resin layer described above.

The method for forming the resin layer b is not particularly limited, and can be formed by a known coating method.

When step 1b is included, the surface to which the photosensitive transfer material is transferred becomes the resin layer b, as will be described later.

< procedure 2>

The method for producing a laminate according to the present invention preferably includes step 2: a photosensitive resin layer c is formed on the conductive pattern a.

The method for forming the photosensitive resin layer c on the conductive pattern a is not particularly limited, and a known resist forming method can be used. Among them, the step 2 is preferably a step of forming the photosensitive resin layer c by bringing a photosensitive transfer material into contact with the conductive pattern a and transferring the photosensitive transfer material, and more preferably a step of forming the photosensitive resin layer c by bringing a photosensitive transfer material previously formed on a temporary support into contact with the conductive pattern a and transferring the photosensitive transfer material.

The step 2 is preferably a step of sequentially forming a photosensitive resin layer c and an intermediate layer on the conductive pattern a, and more preferably the intermediate layer is a water-soluble resin layer and a thermoplastic resin layer.

As a method of transferring the photosensitive resin layer c onto the conductive pattern a using the photosensitive transfer material, it is preferable that the conductive pattern a is brought into contact with the photosensitive resin layer c in the photosensitive transfer material, and the photosensitive transfer material is brought into pressure contact with the conductive pattern a. In the above-described embodiment, since the adhesion between the photosensitive resin layer c in the photosensitive transfer material and the conductive pattern a is improved, the photosensitive resin layer c having the pattern formed after exposure and development can be suitably used as a resist for etching the conductive pattern.

A preferred embodiment of the photosensitive transfer material used in the method for producing a substrate having a conductive pattern according to the present invention will be described below.

The photosensitive resin layer c may be a positive photosensitive resin layer or a negative photosensitive resin layer.

The photosensitive resin layer c may be preferably any of the following.

The photosensitive resin layer c contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator

The photosensitive resin layer c contains a resin having polarity changed by the action of an acid (preferably an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group), and a photoacid generator

The photosensitive resin layer c contains a resin containing a structural unit having a phenolic hydroxyl group and a quinone diazide compound

Among them, the photosensitive resin layer c preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

The method of pressing the conductive pattern a and 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 conductive pattern a by the following method: for the temporary support in the photosensitive transfer material, the outermost layer on the side having the photosensitive resin layer c is overlapped with the conductive pattern a, and pressurization and heating are performed by a mechanism such as a roller. In the 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 lamination temperature is not particularly limited, but is preferably, for example, 70℃to 130 ℃.

The method for manufacturing a substrate having a conductive pattern according to the present invention is preferably performed in a roll-to-roll manner.

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

The roll-to-roll method is the following: a substrate capable of winding and unwinding is used as the substrate, and includes: a step of unreeling the substrate or the base material having the conductive pattern or the like (also referred to as an "unreeling step") before any of the steps included in the method for producing a laminate according to the present invention; and a step of winding the base material having the conductive pattern or the like (also referred to as a "winding step") after any one of the steps, at least any one of the steps (preferably all the steps or all the steps other than the heating step) is performed while conveying the base material or the base material having the conductive pattern or the like.

The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method can be used in the manufacturing method using the roll-to-roll method.

When the photosensitive transfer material has a protective film, the method for producing a laminate according to the present invention preferably includes a protective film peeling step of peeling the protective film before step 2.

The method of peeling the protective film is not limited, and a known method can be applied.

In the case where the photosensitive transfer material is used, the method for producing a laminate according to the present invention preferably includes a temporary support peeling step of peeling off the temporary support between the step 2 and the step 3 or between the exposure and the development treatment in the step 3.

The method of peeling the temporary support is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP 2010-072589 can be used.

< procedure 3>

The method for producing a laminate according to the present invention preferably includes step 3 of performing pattern exposure and development on the photosensitive resin layer c to obtain a resin pattern c'.

The pattern exposure in step 3 is a pattern-like exposure process, i.e., an exposure process in which an exposed portion and a non-exposed portion are present.

The positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited, and may be appropriately adjusted.

The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited. For example, in order to improve the display quality of a display device (for example, a touch panel) including an input device (having a circuit wiring manufactured by an etching method) and to reduce the area occupied by a lead-out wiring, at least a part of a pattern (preferably an electrode pattern and/or a lead-out wiring portion of the touch panel) 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.

Further, from the viewpoint of more effectively exhibiting the effects of the present invention, the obtained resin pattern preferably has a resin pattern having a line width of 20 μm or less, more preferably has a resin pattern having a line width of 10 μm or less, still more preferably has a resin pattern having a line width of 8 μm or less, and particularly preferably has a resin pattern having a line width of 5 μm or less.

The light source used for exposure can be appropriately selected and used as long as it is a light source that irradiates light (for example, 365nm, 405nm, or 436 nm) of a wavelength capable of exposing the photosensitive resin layer c. 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 。

Examples of preferred embodiments of the light source, the exposure amount, and the exposure method for exposure include those described in paragraphs 0146 to 0147 of International publication No. 2018/155193, which are incorporated herein by reference.

In the case of using the photosensitive transfer material, in step 3, the temporary support may be peeled off from the transfer layer (photosensitive resin layer c and intermediate layer) and then subjected to pattern exposure, or the temporary support may be peeled off after pattern exposure through the temporary support before peeling off the temporary support. When the temporary support is peeled off before exposure, the mask may be exposed in contact with the transfer layer or may be exposed in proximity without contact. When exposing without peeling the temporary support, the mask may be exposed in contact with the temporary support or may be exposed in proximity without contact. In order to prevent contamination of the mask due to contact of the transfer layer with 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, when the exposure method is a contact exposure method, a contact exposure method can be appropriately selected, and when the exposure method is a non-contact exposure method, a proximity exposure method, a lens system or mirror system projection exposure (projection exposure) method, a direct exposure (direct write exposure) method using an exposure laser or the like can be appropriately selected. When the exposure apparatus is a lens system or a mirror system projection exposure apparatus, an exposure apparatus having an appropriate aperture Number (NA) of a lens can be used according to a required resolution and a focal depth. In the case of the direct exposure method, the photosensitive resin layer c may be directly drawn, or the photosensitive resin layer c 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 the exposure may be performed by interposing a liquid such as water between the light source and the transfer layer.

From the viewpoint of resolution, the exposure in step 3 is preferably performed by contact exposure by bringing the transfer layer into contact with a mask.

In addition, the exposure in step 3 is preferably performed by direct-writing exposure or projection exposure, from the viewpoint of reducing the influence on the mask and the photosensitive resin layer.

The development treatment in step 3 is preferably performed using a developer.

The developer is not particularly limited as long as the non-image portion (unnecessary portion) of the photosensitive resin layer c 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.

As the developer, an aqueous alkali developer containing a compound having pka=7 to 13 at a concentration of 0.05mol/L to 5mol/L (liter) is preferable. The developer may contain a water-soluble organic solvent and/or a surfactant.

Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyl trimethylammonium hydroxide).

The developer described in paragraph 0194 of International publication No. 2015/093271 is also preferably used. Examples of the development method that can be suitably used include the development method described in paragraph 0195 of international publication No. 2015/093271.

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

After the developing step, it is preferable to spray a cleaning agent by spraying and remove the developing residues.

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

< procedure 4>

The method for producing a laminate according to the present invention preferably includes step 4: the metal nano-bodies in the conductive pattern a are removed by wet etching using the resin pattern c' as a mask, thereby forming the non-conductive pattern.

In step 4, wet etching of the conductive pattern a is performed using the resin pattern c' formed from the photosensitive resin layer c as a mask (resist).

As a method of etching treatment, a known method 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 an etching solution, and a dry etching method by plasma etching or the like.

The etching liquid used for wet etching may be any etching liquid that is appropriately selected from acidic or basic according to the object to be etched.

Examples of the acidic etching liquid include an aqueous solution of an acidic component 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 iron (II) chloride, iron (III) chloride, iron (II) nitrate, iron (III) nitrate, iron (II) sulfate, iron (III) sulfate, 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.

The etching solution preferably contains at least one selected from the group consisting of ferric nitrate and ferric sulfate.

In order to control the etching rate and the shape of the material to be etched, it is preferable to use other acids, organic solvents, surfactants, amines, inorganic salts, and the like in combination.

< procedure 5>

The method for producing a laminate according to the present invention preferably includes step 5: softening or swelling the resin of the above non-conductive pattern.

Since the method for producing a laminate according to the present invention includes step 5, it is presumed that the resin of the non-conductive pattern is softened or swelled to fill up or reduce the void generated by removing the metal nano-body in step 4, thereby suppressing the metal migration phenomenon and the like, and that the dimensional stability of the conductive pattern after the energization is excellent.

From the viewpoint of dimensional stability of the conductive pattern after the energization, the step 5 is preferably a step of softening the resin of the nonconductive pattern, more preferably a step of softening the resin of the nonconductive pattern by a heat treatment, and particularly preferably a step of softening the resin of the nonconductive pattern by a heat treatment and filling voids generated by removing the metal nano-bodies by the etching.

When step 5 is a step of softening the resin, step 5 may be performed after step 4 or may be performed simultaneously with step 4, that is, in step 4, but is preferably performed after step 4.

When the heat treatment is performed in step 5, the heating temperature may be a temperature at which the resin of the nonconductive pattern is softened, but is preferably 40 to 200 ℃, more preferably 60 to 180 ℃, and particularly preferably 100 to 160 ℃.

The heating time is not particularly limited, but is preferably 1 minute to 24 hours, more preferably 5 minutes to 6 hours, and particularly preferably 10 minutes to 60 minutes.

In the case of having the resin layer, the heating temperature is preferably higher than a temperature lower than the glass transition temperature of the resin of the nonconductive pattern and the glass transition temperature of the resin layer, from the viewpoint of dimensional stability of the conductive pattern after the energization.

In addition, from the viewpoint of dimensional stability of the conductive pattern after the energization, it is particularly preferable that the heat treatment in step 5 is performed at a heating temperature satisfying Tgp < Th < Tgb.

Th represents the highest temperature (. Degree. C.) during the heat treatment in step 5, tgp represents the glass transition temperature (. Degree. C.) of the resin of the above-mentioned nonconductive pattern, and Tgb represents the glass transition temperature (. Degree. C.) of the base material.

The heating means used in the heating process in step 5 is not particularly limited, and known heating means may be used, and examples thereof include a heater, a hot plate, a convection oven (heated air circulation dryer), and a high-frequency heater.

The step 5 is preferably a step of swelling the resin of the nonconductive pattern in the step 4 or after the step 4, and more preferably a step of swelling the resin of the nonconductive pattern in the step 4 or after the step 4 and filling the voids generated by removing the metal nano-bodies by the etching.

The swelling can be suitably performed by bringing a known solvent such as water or an organic solvent into contact with the resin.

Among them, the swelling is preferably performed by using an etching solution in step 4.

The temperature at the time of swelling and the contact time with the solvent are not particularly limited, and can be appropriately selected.

< resin Pattern removal Process >

The method for producing a laminate according to the present invention is preferably performed in a step of removing the remaining resin pattern c' (resin pattern removing step). The resin pattern removal may be performed before step 5 or after step 5, but is preferably performed before step 5.

The method for removing the remaining resin pattern c' is not particularly limited, but a method of removing by chemical treatment is exemplified, and a method of removing using a removing liquid is preferable.

The method for removing the resin pattern c 'includes a method of immersing the substrate having the remaining resin pattern c' in a removing liquid under stirring at a liquid temperature of preferably 30 to 80 ℃, more preferably 40 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 liquid may be removed by a known method such as spraying, sprinkling, or spin-coating immersion.

< other procedure >

The method for producing a laminate according to the present invention may include any step (other step) other than the above steps. 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 that can be applied to the method for producing a laminate according to the present invention include the steps described in paragraphs 0035 to 0051 of JP 2006-23696A.

Examples of the other steps include, but are not limited to, a step of reducing the reflectance of visible light described in paragraph 0172 of international publication No. 2019/022089, a step of forming a new conductive pattern on an insulating film described in paragraph 0172 of international publication No. 2019/022089, and the like.

Procedure for reducing the reflectivity of visible light

The method for producing a laminate according to the present invention may include a step of performing a treatment for reducing the visible light reflectance of a part or all of the conductive pattern such as the conductive pattern.

As the treatment for reducing the reflectance of visible light, an oxidation treatment is given. When the conductive pattern containing copper is provided, copper oxide is formed by oxidizing copper and the conductive pattern is blackened, whereby the visible ray reflectivity of the conductive pattern can be reduced.

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

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

The method for producing a laminate according to the present invention preferably further comprises: forming an insulating film on the surface of the conductive pattern; and forming a new conductive pattern 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 may be formed by photolithography using an insulating photosensitive material.

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

In the method for producing a laminate according to the present invention, it is preferable that a substrate having a plurality of conductive patterns on both surfaces of the substrate is used, and nonconductive patterns are formed successively or simultaneously on the conductive patterns 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 base material 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 support body in a roll-to-roll manner.

That is, in the method for producing a laminate according to the present invention, it is preferable that the conductive pattern d' is further formed on a surface of the base material opposite to the surface on which the conductive pattern a is provided.

< photosensitive transfer Material >

The photosensitive transfer material used in the method for producing a laminate according to the present invention preferably includes a temporary support, a transfer layer including a photosensitive resin layer (forming the photosensitive resin layer c), and more preferably includes a temporary support, a transfer layer including a photosensitive resin layer, and a protective film in this order.

The photosensitive transfer material used in the present invention may have other layers between the temporary support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, and the like.

The photosensitive transfer material used in the present invention preferably further comprises a thermoplastic resin layer and a water-soluble resin layer between the temporary support and the photosensitive resin layer.

The transfer layer preferably further includes a thermoplastic resin layer and a water-soluble resin layer.

The photosensitive transfer material used in the present invention is preferably a roller-shaped photosensitive transfer material from the viewpoint of more effectively exhibiting the effects of the present invention.

An example of the photosensitive transfer material used in the present invention is shown below, but the present invention is not limited thereto.

(1) "temporary support/photosensitive resin layer/refractive index adjustment layer/protective film"

(2) "temporary support/photosensitive resin layer/protective film"

(3) "temporary support/Water-soluble resin layer/photosensitive resin layer/protective film"

(4) "temporary support/thermoplastic resin layer/Water-soluble resin layer/photosensitive resin layer/protective film"

In each of the above structures, the photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, and is preferably a negative photosensitive resin layer. The photosensitive resin layer is also preferably a colored resin layer.

Among them, the photosensitive transfer material is preferably configured as described in (2) to (4) above, for example.

In the case of the photosensitive transfer material having a structure in which the photosensitive resin layer further includes another layer on the side opposite to the temporary support side, the total thickness of the other layer disposed on the side opposite to the temporary support side of the photosensitive resin layer is preferably 0.1% to 30%, more preferably 0.1% to 20%, with respect to the layer thickness of the photosensitive resin layer.

Hereinafter, a photosensitive transfer material used in the present invention will be described by taking a specific example of an embodiment.

Hereinafter, a photosensitive transfer material will be described as an example.

The photosensitive transfer material 20 shown in fig. 1 sequentially includes: a temporary support 11; a transfer layer 12 including a thermoplastic resin layer 13, a water-soluble resin layer 15, and a photosensitive resin layer 17; and a protective film 19.

The photosensitive transfer material 20 shown in fig. 1 is in the form in which the thermoplastic resin layer 13 and the water-soluble resin layer 15 are disposed, but the thermoplastic resin layer 13 and the water-soluble resin layer 15 may not be disposed.

Hereinafter, each element constituting the photosensitive transfer material will be described.

[ temporary support ]

The photosensitive transfer material used in the present invention preferably has 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 the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure. 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, 365 nm) 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 outgoing light emitted through the layer when the light enters in a direction perpendicular to the main surface of the layer (thickness direction) to the intensity of the incoming light, and is measured using MCPD Series manufactured by Otsuka Electronics co., ltd.

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, the flexibility required for adhesion to a substrate, and the light transmittance required in step 3.

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, from the viewpoints of defect suppression, resolution, and linearity of the resin pattern, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, further preferably 20 μm or less, and particularly preferably 16 μm or less.

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 。

From the viewpoints of defect suppression of the resin pattern, resolution, and transparency of the temporary support, it is preferable that the temporary support has a small haze. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, further preferably less than 1.0%, and particularly preferably 0.5% or less.

For the haze value of the present invention, a haze meter (for example, NDH-2000,NIPPON DENSHOKU INDUSTRIES CO, manufactured by ltd.) was used by following JIS K7105: measurements were made by the method of 1981.

From the viewpoint of imparting handleability, a layer (lubricant layer) containing fine particles may be provided on the surface of the temporary support. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be, for example, 0.05 μm to 0.8 μm. The thickness of the lubricant layer can be, for example, 0.05 μm to 1.0 μm.

From the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the surface of the temporary support opposite to the photosensitive resin layer side preferably has an arithmetic average roughness Ra of not less than the arithmetic average roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side.

The surface of the temporary support opposite to the photosensitive resin layer side has an arithmetic average roughness Ra of preferably 100nm or less, more preferably 50nm or less, still more preferably 20nm or less, and particularly preferably 10nm or less, from the viewpoints of conveyability, defect suppression of the resin pattern, and resolution.

The surface of the temporary support on the photosensitive resin layer side has an arithmetic average roughness Ra of preferably 100nm or less, more preferably 50nm or less, still more preferably 20nm or less, and particularly preferably 10nm or less, from the viewpoints of releasability of the temporary support, defect suppression of the resin pattern, and resolution.

Further, from the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the value of the arithmetic average roughness Ra of the surface of the temporary support on the side opposite to the photosensitive resin layer side, i.e., the arithmetic average roughness Ra of the surface of the temporary support on the photosensitive resin layer side, is preferably 0nm to 10nm, more preferably 0nm to 5nm.

The arithmetic average roughness Ra of the surface of the temporary support or protective film of the present invention is measured by the following method.

The surface profile of the film was obtained by measuring the surface of the temporary support or protective film using a three-dimensional optical profiler (for example, new View7300, manufactured by Zygo Corporation) under the following conditions.

As 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. The arithmetic average roughness is calculated from the obtained histogram data, and the Ra value of the surface of the temporary support or protective film is obtained.

When the temporary support or protective film is bonded to the photosensitive resin layer or the like, the temporary support or protective film is peeled from the photosensitive resin layer, and the Ra value of the surface on the peeled side is measured.

The peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive resin layer or the thermoplastic resin layer, is preferably 0.5mN/mm or more, more preferably 0.5mN/mm to 2.0mN/mm, from the viewpoint of peeling inhibition of the temporary support due to adhesion between the stacked layers.

The peel force of the temporary support of the present invention was measured as follows.

A PET substrate with a copper layer was prepared by sputtering a copper layer having a thickness of 200nm on a polyethylene terephthalate (PET) film having a thickness of 100. Mu.m.

The protective film was peeled off from the photosensitive transfer material thus produced, and laminated on the above-mentioned PET substrate with copper layer under lamination conditions of a lamination roller temperature of 100℃and a line pressure of 0.6MPa and a line speed (lamination speed) of 1.0 m/min. Next, after a tape (PRINTACK manufactured by Nitto Denko corporation) was attached to the surface of the temporary support, a laminate having at least the temporary support and the photosensitive resin layer on the PET substrate with the copper layer was cut into 70mm×10mm, and a sample was produced. The PET substrate side of the sample was fixed to a sample stage.

The tape was stretched in the 180-degree direction using a tensile compression tester (manufactured by IMADA-SS corporation, SV-55, for example) at a speed of 5.5 mm/sec to peel between the photosensitive resin layer or thermoplastic resin layer and the temporary support, and the force required for peeling (peeling force) adhesion force was measured.

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.

[ photosensitive resin layer ]

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

The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, and is preferably a negative photosensitive resin layer.

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

The positive photosensitive resin layer is not limited, and a known positive photosensitive resin layer can be used. The positive photosensitive resin layer preferably contains: acid-decomposable resins (i.e., polymers containing structural units having acid groups protected by acid-decomposable groups); photo-acid generator. The positive photosensitive resin layer preferably contains: a resin comprising structural units having phenolic hydroxyl groups; quinone diazide compounds.

Further, the positive photosensitive resin layer is more preferably a chemically amplified positive photosensitive resin layer containing a polymer (containing a structural unit having an acid group protected by an acid-decomposable group) and a photoacid generator.

The components are described in order below. When simply referred to as a "photosensitive resin layer", it means both a positive photosensitive resin layer and a negative photosensitive resin layer.

Polymerizable Compound

The negative photosensitive resin layer preferably contains a polymerizable compound. In the present specification, the term "polymerizable compound" refers to a compound that is polymerized by the action of a photopolymerization initiator described later and is different from an alkali-soluble resin described later.

The polymerizable group of the polymerizable 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 polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth) acrylate compound.

From the viewpoints of resolution and pattern formation, the negative photosensitive resin layer preferably contains a polymerizable compound having 2 or more functions (polyfunctional polymerizable compound), and more preferably contains a polymerizable compound having 3 or more functions.

The 2-functional or more polymerizable compound means a compound having 2 or more polymerizable groups in one molecule.

Further, from the viewpoint of excellent resolution and releasability, the number of polymerizable groups in one molecule of the polymerizable compound is preferably 6 or less.

The negative photosensitive resin layer preferably contains a 2-functional or 3-functional ethylenically unsaturated compound, more preferably contains a 2-functional ethylenically unsaturated compound, from the viewpoint of more excellent balance between photosensitivity and resolution and releasability of the photosensitive resin layer.

From the viewpoint of excellent releasability, the content of the 2-functional or 3-functional ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 60 mass% or more, more preferably more than 70 mass%, and still more preferably 90 mass% or more, relative to the total content of the ethylenically unsaturated compounds. The upper limit is not particularly limited and may be 100 mass%. That is, all of the ethylenically unsaturated compounds contained in the negative photosensitive resin layer may be 2-functional ethylenically unsaturated compounds.

From the viewpoints of resolution and pattern formability, the negative photosensitive resin layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure.

The polymerizable compound having a polyalkylene oxide structure is preferably a polyalkylene glycol di (meth) acrylate or the like described later.

Olefinically unsaturated compounds B1-

The negative 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 one molecule among the ethylenically unsaturated compounds.

In the negative photosensitive resin layer, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound 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, from the viewpoint of further excellent resolution. The upper limit is not particularly limited, but from the viewpoint of releasability, it is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.

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 negative photosensitive resin layer by the developer.

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

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

The bisphenol structure may be directly bonded to 2 ethylenically unsaturated groups at both ends, or may be bonded via 1 or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably ethyleneoxy group or propyleneoxy group, and more preferably ethyleneoxy group. 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 herein by reference.

As the ethylenically unsaturated compound Bl, 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 the 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecaethoxy tetrapropoxy) phenyl) propane (manufactured by FA-3200MY,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical co), and manufactured by ltd.10-b.10, and also, the use of the same.

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

[ chemical formula 13]

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 Are each independently 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 randomly or in blocks, and are integers of 0 to 30. Also, when it is a block, any 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 still 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 singly or in combination of two or more.

From the viewpoint of more excellent resolution, the content of the ethylenically unsaturated compound B1 in the negative photosensitive resin layer is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the negative 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 negative photosensitive resin layer bleed out from the end portion of the photosensitive transfer material).

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

The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited, and can be appropriately selected from known compounds. Examples thereof include compounds having 1 ethylenically unsaturated group in one 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., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 6-hexanediol diacrylate (A-HD-N, shin-Nakamura Chemical Co., manufactured by 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) acrylate include propylene oxide modified urethane di (meth) acrylate and ethylene oxide and propylene oxide modified urethane di (meth) acrylate. 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 negative photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compounds B1 and 3 functional or more, more preferably contains the above-mentioned ethylenically unsaturated compounds B1 and two or more ethylenically unsaturated compounds 3 functional or more. 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 negative photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more 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 (such as KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical co, a-9300-1CL (registered trademark) by ltd), alkylene oxide-modified (meth) acrylate compounds (such as KAYARAD RP-1040, shin-Nakamura Chemical co, ATM-35E and a-9300 (registered trademark) by ltd), and EBECRYL-alinlex ltd (such as EBECRYL (registered trademark) 135 (such as Shin-Nakamura Chemical co, a-GLY-9E (registered trademark) by ltd), aroix (such as TO 2349 (TO co, ltd), aroix M-520 (TO co), and other such as TO co (registered trademark) by ltd), and aroix M-520 (TO co, manufactured by ltd), and other such as TO co (registered trademark) by ltd).

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 negative 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 or more and 0.9 or less.

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

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

The molecular weight (weight average molecular weight (Mw) when 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 further preferably 300 to 2,200.

The ethylenically unsaturated compound may be used singly or in combination of two or more.

The content of the ethylenically unsaturated compound in the negative 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 negative photosensitive resin layer.

Photopolymerization initiator-

The negative photosensitive resin layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound by exposure to active light such as ultraviolet rays, visible rays, and X rays. 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.

Among them, the negative photosensitive resin layer preferably contains a photo radical polymerization initiator from the viewpoints of resolution and pattern formability.

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 -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a bisimidazole compound.

Examples of the photo radical polymerization initiator include those described in paragraphs 0031 to 0042 of JP 2011-95716 and 0064 to 0081 of JP 2015-14783.

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), omnirad651 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) OXE01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetoxime) (trade name: IRGACURE OXE02, manufactured by BASF corporation), IRGACUREOXE 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), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: omni 907,IGM Resins B.V. Manufactured), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropanene (trade name: omni-4-morpholino-1-butanone (trade name: omni 379EG,IGM Resins B.V. Manufactured by Omni) and 2-methylpropanene (trade name: omni 1-4-morpholino-1-butanone), IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropane-1-one (trade name: manufactured by Omnifad 1173,IGM Resins B.V), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184,IGM Resins B.V, manufactured), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad651,IGM Resins B.V), 2,4, 6-trimethyl { bi > benzoyl < bi } -diphenyl phosphine oxide (trade name: omnirad TPO H, IGM Resins b.v.), bis (2, 4, 6-trimethyl { bi > benzoyl < bi }) phenylphosphine oxide (trade name: omnirad 819,IGM Resins B.V, manufactured), photopolymerization initiator of oxime esters (trade name: lunar 6, dksh Japan k.k. manufactured), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by 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 active light to generate an acid. The photo-cation polymerization initiator is preferably a compound which is sensitive to active light having a wavelength of 300nm or more (preferably, a wavelength of 300nm to 450 nm) to generate an acid, but the chemical structure thereof is not limited. The photo-cation polymerization initiator which is not directly sensitive to the active 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 is used in combination with the sensitizer and is sensitive to the active light having a wavelength of 300nm or more to generate an acid.

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, for example, preferably-10.0 or more.

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, imidosulfonate 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 negative photosensitive resin layer may contain one kind of photopolymerization initiator alone or two or more kinds of photopolymerization initiators.

The content of the photopolymerization initiator in the negative-type photosensitive resin layer is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and further preferably 1.0 mass% or more, relative to 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 negative photosensitive resin layer.

Alkali-soluble resin-

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

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

The alkali-soluble resin is not particularly limited, and for example, a known alkali-soluble resin used for resists can be suitably 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-

The alkali-soluble resin preferably contains a polymer a.

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 by the developer.

The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of more excellent developability, it 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.

The acid value is the mass [ mg ] of potassium hydroxide required to neutralize 1g of the sample, and in this 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 by the kind of the structural unit constituting the polymer a and the content of the structural unit having 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, 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 easiness of the photosensitive resin layer overflowing from the end surface of the roller when the photosensitive transfer material is wound into a roll shape. The chipability refers to the ease with which the chips fly off when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin layer or the like, the chips are transferred to a mask in a subsequent exposure step or the like, which causes 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, still more preferably 1.0 to 3.0. In the present invention, the molecular weight is a value measured using 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).

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

Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, monomers having an aralkyl group or styrene are preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group 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 all the monomer components.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) 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 phenethyl (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 and chlorobenzyl (meth) acrylate; vinyl monomers having a benzyl group such as 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 group 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 all the monomer components.

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

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

The first monomer is a monomer having a carboxyl group in the 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 all the monomer components.

The copolymerization ratio of the first monomer is preferably 10 to 50 mass% based on the total mass of all monomer components. The above-mentioned copolymerization ratio is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more from the viewpoint of expressing good developability, controlling edge meltability, and the like. The content 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 non-acidic and is a 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 all the monomer components.

From the viewpoint of suppressing deterioration of line width thickness or 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 group, 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% by mass of the monomer component having an aromatic hydrocarbon group and 10 to 25% by mass of the first monomer component.

The polymer a may have any of a linear structure, a branched structure, and an alicyclic 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, 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.

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, and examples of the monomer include (meth) acrylic acid esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (number of carbon atoms). 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-methyl-5-ethyl-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, octahydro-4, 7-methanoindene (meth) acrylate, 1-menthyl 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 (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is particularly preferable.

The polymer a can be used singly or two or more kinds may be used in combination. When two or more kinds of polymers a containing a monomer component having an aromatic hydrocarbon group are used in combination, it is preferable to use two kinds of polymers a containing a monomer component having an aromatic hydrocarbon group in combination or to use a polymer a containing a monomer component having an aromatic hydrocarbon group and a polymer a containing no monomer component having an aromatic hydrocarbon group in combination. In the latter case, the ratio of the polymer a containing the monomer component having an aromatic hydrocarbon group 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 still more preferably 90% by mass or more, relative to the total amount of the polymer a.

The polymer a is preferably synthesized by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more monomers described in the above with a solvent such as acetone, methyl ethyl ketone or isopropyl alcohol, and heating and stirring the mixture. 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, deterioration of line width thickness and resolution at the time of focus position shift at the time of exposure can be suppressed. From this viewpoint, the Tg of the polymer A is more preferably 130℃or lower, still more preferably 120℃or lower, particularly preferably 110℃or lower. From the viewpoint of improving the edge melting resistance, it is preferable to use the polymer a having a 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 negative photosensitive resin layer may contain a resin other than the alkali-soluble resin.

Examples of the resin other than the alkali-soluble resin include an acrylic resin, a styrene-acrylic copolymer (a copolymer having a styrene content of 40 mass% or less), a polyurethane resin, a polyvinyl alcohol, a polyvinyl formal, a polyamide resin, a polyester resin, an epoxy resin, a polyacetal resin, a polyhydroxystyrene resin, a polyimide resin, a polybenzoxazole resin, a polysiloxane resin, a polyethylenimine, a polyallylamine, and a polyalkylene glycol.

The alkali-soluble resin can be used singly or two or more kinds may be used in combination.

The proportion of the alkali-soluble resin to the total mass of the negative 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 total mass of the negative 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 total mass of the negative photosensitive resin layer is preferably 10 mass% or more.

Compound with unshared electron pair

The photosensitive resin layer preferably contains a compound having an unshared electron pair from the viewpoint of adhesion to the conductive pattern.

From the viewpoint of adhesion to the conductive pattern, the compound having an unshared electron pair is preferably a compound having at least a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a heterocyclic compound, a thiol compound, or a disulfide compound, still more preferably a heterocyclic compound, and particularly preferably a nitrogen-containing heterocyclic compound.

As the compound having an unshared electron pair, the compounds exemplified as the above-mentioned compound e are preferably exemplified.

Pigment is described as

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, pattern visibility after development, and resolution. If pigment N is contained, although the detailed mechanism is not clear, the adhesion to the adjacent layers (for example, the temporary support and the substrate) is improved, and the resolution is further excellent.

In the present invention, the "change in maximum absorption wavelength of the dye by an acid, an alkali or a radical" may refer to any one of a method in which the dye in a developed state is decolorized by an acid, an alkali or a radical, a method in which the dye in a decolorized state is developed by an acid, an alkali or a radical, and a method in which the dye in a developed state is changed to a 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 color removal by generating and acting an acid, an alkali or a radical in the photosensitive resin layer by exposure, or a coloring matter which changes the state of color development or color removal by changing the state (for example, pH) in the photosensitive resin layer by an acid, an alkali or a radical. The coloring matter may be a coloring matter which is not exposed to light but is directly subjected to an acid, an alkali or a radical as a stimulus 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 both a dye whose maximum absorption wavelength of the dye N is changed by a radical, and a photo radical polymerization initiator.

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

Examples of the coloring mechanism of the pigment N of 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 after exposure, a radical reactive dye, an acid reactive dye or a base reactive dye (for example, a leuco dye) is developed by radicals, acids or bases generated by the photo radical polymerization initiator, the photo cation polymerization initiator or the photo alkali generator.

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

The maximum absorption wavelength of pigment N can be measured by using a spectrophotometer in the atmospheric environment: UV3100 (SHIMADZU corporation) is obtained by measuring the transmission spectrum of a dye N-containing solution (liquid temperature 25 ℃) in the range of 400nm to 780nm and detecting the wavelength (maximum absorption wavelength) at which the intensity of light in the above wavelength range becomes minimum.

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.

From the viewpoint of visibility of the exposed portion and the non-exposed portion, a colorless compound is preferable as the coloring matter N.

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 indole phthalide skeleton (indole 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.

From the viewpoint of visibility of the exposed portion and the non-exposed portion, the colorless compound preferably has a lactone ring, a sultone ring (sultone ring), or a sultone ring. 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 to change the colorless compound to a closed state to decolorize the colorless compound, or to change the colorless compound to an open state to develop the colorless compound. As the colorless compound, a compound having a lactone ring, a sultone ring, or a sultone ring, which develops color by free radical or acid ring opening, is preferable, and a compound having a lactone ring, which develops color 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 dyes among the dyes include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsine), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), metamine yellow (metanilow), thymol blue (thymol sulfonphthalein), xylenol blue, methyl orange, para-methyl red, congo red, benzorhodopsin (benzopurline) 4B, alpha-naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), paragrade red (parafuchsin), victorian pure blue (victoria pure blue) -naphthalene sulfonate, victorian pure blue (Hodogaya Chemical, co., ltd, manufactured), oil blue #603 (OrientChemical Industries co., ltd, manufactured), oil pink #312 (Orient Chemical Indu stries co., ltd, manufactured), oil red 5B (Orient Chemical Industries co., ltd, manufactured), oil scarlet #308 (Orient Chemical Industries co., ltd, manufactured), oil red OG (Orient Chemical Industries co., ltd, manufactured), oil red RR (Orient Chemical Industries co., ltd, manufactured), oil green #502 (Orient Chemical Industries co., ltd, manufactured), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co., ltd, manufactured), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, gold amine, 4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearyl amino-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 among the dye N include p, p', p "-hexamethyltriphenylmethane (colorless crystal violet), pergascript Blue SRB (Ciba-Geigy corporation), 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-dimethoxy 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-chloro-N, 3- (N, N-dibenzylamino) -6-methyl-7-anilino-fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-anilino fluoran, 4-amino-ethyl-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-piperidinyl-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-dimethylaminolactone, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-aza-phenylphthalide, 3- (3-ethyl-2-methylindol-3-yl) phthalide, 6 '-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.

From the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution, the dye N is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye which develops color by a radical.

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 singly or in combination of two or more.

From the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution, the content of the dye is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, still 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.

Further, from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility 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%, further 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.

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.

Two solutions were prepared by dissolving 0.001g or 0.01g of pigment 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 to bring all the pigments into a color development state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured using a spectrophotometer (manufactured by UV3100, shimadzu Corporation) under atmospheric conditions, 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.

Thermal crosslinkable Compound

The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound but is treated as a thermally crosslinkable compound.

Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound. Among them, blocked isocyanate compounds are preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

Since the blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group, for example, when the resin and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the formed film decreases, and the function tends to be enhanced when the film obtained by curing the negative photosensitive resin layer is used as a protective film.

The blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃, more preferably 130 to 150 ℃.

The dissociation temperature of the blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry: differential scanning calorimetry) analysis".

As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments inc (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited thereto.

Examples of the blocking agent having a dissociation temperature of 100℃to 160℃include active methylene compounds [ malonic acid diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc) ], oxime compounds (formaldehyde oxime, aldoxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, etc.), and compounds having a structure represented by-C (=N-OH) -, in the molecule.

Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably an oxime compound from the viewpoint of storage stability, for example.

For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving brittleness of the film, improving adhesion to a transfer object, and the like.

The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by subjecting hexamethylene diisocyanate to isocyanurate protection.

Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferable from the viewpoint that the dissociation temperature is more easily set in a preferable range than a compound having no oxime structure and development residues are easily reduced.

The blocked isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferable.

Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, (meth) acrylamide group and styryl group, and a group having an epoxy group such as a glycidyl group.

Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and further preferably an acryloyloxy group.

As the blocked isocyanate compound, commercially available ones can be used.

Examples of the commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, etc. (manufactured by SHOWA DENKO K.K. above), and blocked Duranate series (manufactured by Duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, etc., asahi Kasei Chemicals Corporation).

As the blocked isocyanate compound, a compound having the following structure can be used.

[ chemical formula 14]

The thermally crosslinkable compound may be used singly or in combination of two or more.

When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the photosensitive resin layer.

Polymer having structural unit having acid group protected by acid-decomposable group

The positive photosensitive resin layer preferably contains a polymer (hereinafter, also referred to as "polymer X") containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter, also referred to as "structural unit a"). The positive photosensitive resin layer may contain one kind of polymer X alone or two or more kinds of polymers X.

In the polymer X, the acid group protected by the acid-decomposable group is converted into an acid group by a deprotection reaction by the action of a catalytic amount of an acidic substance (for example, an acid) generated by exposure. By generating an acid group in the polymer X, the solubility of the positive photosensitive resin layer in the developer increases.

The polymer X is preferably a polyaddition type polymer, more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof.

Structural units having acid groups protected by acid-decomposable groups

The polymer X preferably contains a structural unit (structural unit a) having an acid group protected by an acid-decomposable group. The polymer X has the structural unit a, so that the sensitivity of the positive photosensitive resin layer can be improved.

The acid group is not limited, and a known acid group can be used. The acid group is preferably a carboxyl group or a phenolic hydroxyl group.

Examples of the acid-decomposable group include a group which is relatively easily decomposed by an acid and a group which is relatively hardly decomposed by an acid. Examples of the group that is relatively easily decomposed by an acid include acetal group-type protecting groups (e.g., 1-alkoxyalkyl group, tetrahydropyranyl group, and tetrahydrofuranyl group). Examples of the group which is relatively difficult to decompose by an acid include a tertiary alkyl group (for example, a tertiary butyl group) and a tertiary alkoxycarbonyl group (for example, a tertiary butoxycarbonyl group). Among the above, the acid-decomposable group is preferably an acetal-based protecting group.

From the viewpoint of suppressing variation in line width of the resin pattern, the molecular weight of the acid-decomposable group is preferably 300 or less.

From the viewpoints of sensitivity and resolution, the structural unit a is preferably a structural unit represented by the following formula A1, a structural unit represented by the formula A2, or a structural unit represented by the formula A3, and more preferably a structural unit represented by the formula A3. The structural unit represented by formula A3 is a structural unit having a carboxyl group protected by an acetal group-type acid-decomposable group.

[ chemical formula 15]

In the formula A1, R ¹¹ R is R ¹² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ¹¹ R is R ¹² At least one of which is alkyl or aryl, R ¹³ Represents alkyl or aryl, R ¹¹ Or R is ¹² Can be combined with R ¹³ Are linked to form a cyclic ether, R ¹⁴ Represents a hydrogen atom or a methyl group, X ¹ Represents a single bond or a divalent linking group, R ¹⁵ Represents a substituent, and n represents an integer of 0 to 4.

In the formula A2, R ²¹ R is R ²² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ²¹ R is R ²² At least one of (2) is alkyl or aryl, R ²³ Represents alkyl or aryl, R ²¹ Or R is ²² Can be combined with R ²³ Are linked to form a cyclic ether, R ²⁴ Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.

In the formula A3, R ³¹ R is R ³² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ³¹ R is R ³² At least one of (2) is alkyl or aryl, R ³³ Represents alkyl or aryl, R ³¹ Or R is ³² Can be combined with R ³³ Are linked to form a cyclic ether, R ³⁴ Represents a hydrogen atom or a methyl group, X ⁰ Represents a single bond or arylene.

In the formula A3, when R ³¹ Or R is ³² When the alkyl group is an alkyl group, the alkyl group having 1 to 10 carbon atoms is preferable.

In the formula A3, when R ³¹ Or R is ³² When aryl is preferred, phenyl is preferred.

In the formula A3, R ³¹ R is R ³² Preferably, each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3, R ³³ The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

In the formula A3, R is ³¹ ～R ³³ The alkyl group and the aryl group may have a substituent.

In formula A3, R is preferably ³¹ Or R is ³² And R is R ³³ And linked to form a cyclic ether. The number of ring members of the cyclic ether is preferably 5 or 6, more preferably 5.

In the formula A3, X ⁰ Preferably a single bond. Arylene groups can beHas a substituent.

In formula A3, R is from the viewpoint of being able to further lower the glass transition temperature (Tg) of polymer X ³⁴ Preferably a hydrogen atom.

R in formula A3 relative to the total mass of the structural units A contained in the polymer X ³⁴ The content of the structural unit which is a hydrogen atom is preferably 20 mass% or more. R in the structural unit A, in the formula A3 ³⁴ The content of the structural unit which is a hydrogen atom can be determined by ¹³ C-Nuclear magnetic resonance Spectrometry (NMR) was measured and confirmed by the intensity ratio of the peak intensities calculated by a conventional method.

As a preferable embodiment of the formulas A1 to A3, reference can be made to paragraphs 0044 to 0058 of International publication No. 2018/179640.

In the formulae A1 to A3, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, further preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group, from the viewpoint of sensitivity.

The polymer X may have a single structural unit a or may have two or more structural units a.

The content of the structural unit a is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass, relative to the total mass of the polymer X. By making the content of the structural unit a within the above range, the resolution is further improved. When the polymer X contains two or more structural units A, the content of the structural units A represents the total content of the two or more structural units A. The content of structural unit A can be determined by ¹³ The intensity ratio of the peak intensities measured by C-NMR and calculated by a conventional method was confirmed.

Structural units having acid groups

The polymer X may contain a structural unit having an acid group (hereinafter, sometimes referred to as "structural unit B").

The structural unit B is an acid group not protected by an acid-decomposable group, that is, a structural unit containing an acid group having no protecting group. By having the structural unit B in the polymer X, sensitivity at the time of pattern formation becomes good. Further, since the developer is easily dissolved in the alkaline developer in the development step after exposure, the development time can be shortened.

The acid group in the structural unit B means a proton dissociable group having a pKa of 12 or less. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Further, the pKa of the acid group is preferably-5 or more.

Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. The acid group is preferably a carboxyl group or a phenolic hydroxyl group, more preferably a carboxyl group.

The polymer X may have a single structural unit B or may have two or more structural units B.

The content of the structural unit B is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, relative to the total mass of the polymer X. By making the content of the structural unit B within the above range, resolution becomes good. When the polymer X has two or more structural units B, the content of the structural units B described above represents the total content of the two or more structural units B. The content of structural unit B can be determined by ¹³ The intensity ratio of the peak intensities measured by C-NMR and calculated by a conventional method was confirmed.

Other structural units

The polymer X preferably has other structural units (hereinafter, sometimes referred to as "structural unit C") than the structural units a and B described above. By adjusting at least one of the kind and the content of the structural unit C, various characteristics of the polymer X can be adjusted. By having the structural unit C in the polymer X, the glass transition temperature, acid value and hydrophilicity/hydrophobicity of the polymer X can be adjusted.

Examples of the monomer forming the structural unit C include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic anhydrides.

From the viewpoint of adhesion to a substrate, the monomer forming the structural unit C is preferably an alkyl (meth) acrylate, more preferably an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

Examples of the structural unit C include structural units derived from styrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, and ethylene glycol monoacetoacetic acid mono (meth) acrylate. The structural unit C may be a structural unit derived from the compounds described in paragraphs 0021 to 0024 of Japanese patent application laid-open No. 2004-264623.

From the viewpoint of resolution, the structural unit C preferably contains a structural unit having a basic group. Examples of the basic group include a group having a nitrogen atom. Examples of the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic group. The basic group is preferably an aliphatic amino group.

The aliphatic amino group may be any of a primary amino group, a secondary amino group and a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a tertiary amino group is preferable.

As the monomer forming the structural unit having a basic group, for example, examples thereof include 1,2, 6-pentamethyl-4-piperidinemethacrylate, 2- (dimethylamino) ethyl methacrylate, 2, 6-tetramethyl-4-piperidinemethacrylate, 2- (diethylamino) ethyl methacrylate, ethyl 2- (dimethylamino) acrylate, ethyl 2- (diethylamino) acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl ] acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1, 2, 4-triazole. Among the above, 1,2, 6-pentamethyl-4-piperidinemethacrylate is preferable.

From the viewpoint of improving electrical characteristics, the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton. Examples of the monomer forming these structural units include styrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Among the above, cyclohexyl (meth) acrylate is preferable.

The polymer X may have one structural unit C alone or two or more structural units C.

The content of the structural unit C is preferably 90 mass% or less, more preferably 85 mass% or less, and particularly preferably 80 mass% or less, relative to the total mass of the polymer X. The content of the structural unit C is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the polymer X. By setting the content of the structural unit C within the above range, resolution and adhesion to the substrate are further improved. When the polymer X has two or more structural units C, the content of the structural units C described above represents the total content of the two or more structural units C. The content of structural unit C can be determined by ¹³ The intensity ratio of the peak intensities measured by C-NMR and calculated by a conventional method was confirmed.

The preferable examples of the polymer X are shown below. However, the polymer X is not limited to the following examples. The ratio of each structural unit and the weight average molecular weight in the polymer X shown below are appropriately selected to obtain preferable physical properties.

[ chemical formula 16]

Glass transition temperature-

The glass transition temperature (Tg) of the polymer X is preferably 90℃or lower, more preferably 20℃to 60℃and particularly preferably 30℃to 50 ℃. When the positive photosensitive resin layer is formed using a transfer material described later, the transferability of the positive photosensitive resin layer can be improved by setting the glass transition temperature of the polymer X within the above-described range.

As a method for adjusting Tg of the polymer X within the above range, for example, a method using a FOX formula can be mentioned. According to the FOX formula, for example, the Tg of the target polymer X can be adjusted based on the Tg of the individual polymer of each structural unit in the target polymer X and the mass fraction of each structural unit.

Hereinafter, an example in which a copolymer having a first structural unit and a second structural unit is used in the FOX formula will be described.

When the glass transition temperature of the individual polymer of the first structural unit is set to Tg1, the mass fraction of the first structural unit in the copolymer is set to W1, the glass transition temperature of the individual polymer of the second structural unit is set to Tg2, and the mass fraction of the second structural unit in the copolymer is set to W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first structural unit and the second structural unit can be estimated according to the following formula.

FOX formula: 1/Tg 0= (W1/Tg 1) + (W2/Tg 2)

Further, the Tg of the polymer can also be adjusted by adjusting the weight average molecular weight of the polymer.

Acid number-

From the viewpoint of resolution, the acid value of the polymer X is preferably 0mgKOH/g to 50mgKOH/g, more preferably 0mgKOH/g to 20mgKOH/g, particularly preferably 0mgKOH/g to 10mgKOH/g.

The acid number of the polymer represents the mass of potassium hydroxide required to neutralize the acidic component per 1g of polymer. The specific measurement method is described below. First, a measurement sample was dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water=9/1). The obtained solution was subjected to neutralization titration with a 0.1mol/L aqueous sodium hydroxide solution AT 25℃using a potentiometric titrator (for example, trade name: AT-510,Kyoto Electronics Manufacturing Co, manufactured by Ltd.). The acid value was calculated by the following formula with the inflection point of the titration pH curve as the titration end point.

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: the amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for the dropping

f: titration amount of 0.1mol/L sodium hydroxide aqueous solution

w: the mass (g) of the sample was measured (solid content conversion)

Weight average molecular weight-

The weight average molecular weight (Mw) of the polymer X is preferably 60,000 or less in terms of polystyrene. When the positive photosensitive resin layer is formed using a transfer material described later, the positive photosensitive resin layer can be transferred at a low temperature (for example, 130 ℃ or lower) by setting the weight average molecular weight of the polymer X to 60,000 or lower.

The weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

The weight average molecular weight of the polymer X was measured by GPC (gel permeation chromatography). As the measuring device, various commercially available devices can be used. Hereinafter, a method for measuring the weight average molecular weight of the polymer X by GPC will be specifically described.

As a measurement device, HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used.

As the column, a column in which TSKgel (registered trademark) Super HZM-M (manufactured by 4.6 mmID. Times.15 cm, tosoh Corporation), super HZ4000 (manufactured by 4.6 mmID. Times.15 cm, tosoh Corpo ration), super HZ3000 (manufactured by 4.6 mmID. Times.15 cm, tosoh Corporation) and Super HZ2000 (manufactured by 4.6 mmID. Times.15 cm, tosoh Corporatjon) were connected in series, respectively, was used.

THF (tetrahydrofuran) was used as eluent.

The measurement conditions were set as follows: the sample concentration was 0.2 mass%, the flow rate was 0.35 mL/min, the sample injection amount was 10. Mu.L, and the measurement temperature was 40 ℃.

As the detector, a differential Refractive Index (RI) detector is used.

The calibration curve can be made using a "standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: any of the 7 samples "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" were prepared.

Content-

From the viewpoint of high resolution, the content of the polymer X is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total mass of the positive photosensitive resin layer.

Manufacturing method-

The method for producing the polymer X is not limited, and a known method can be used. For example, the polymer X can be produced by polymerizing a monomer for forming the structural unit a using a polymerization initiator in an organic solvent, and further polymerizing a monomer for forming the structural unit B and a monomer for forming the structural unit C as needed. The polymer X can also be produced by a so-called polymer reaction.

< other Polymer >

When the positive photosensitive resin layer contains a polymer (containing a structural unit having an acid group protected by an acid-decomposable group), the positive photosensitive resin layer may contain a polymer (hereinafter, also referred to as "other polymer") that does not contain a structural unit having an acid group protected by an acid-decomposable group, in addition to a polymer having a structural unit having an acid group protected by an acid-decomposable group.

Examples of the other polymer include polyhydroxystyrene. Examples of commercial products of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA P and SMA 3840F, TOAGOSEI CO manufactured by Sartomer Company, inc., ARUFON UC-3000 manufactured by LT D. ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080, and Joncryl 690, joncryl 678, joncryl 67 and Joncryl 586 manufactured by BASF corporation.

The positive photosensitive resin layer may contain one kind of other polymer alone or two or more kinds of other polymers.

When the positive photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50 mass% or less, more preferably 30 mass% or less, and particularly preferably 20 mass% or less, relative to the total mass of the polymer components.

In the present invention, the "polymer component" is a generic term for all polymers contained in the positive photosensitive resin layer. For example, when the positive photosensitive resin layer contains the polymer X and other polymers, the polymer X and other polymers are collectively referred to as "polymer components". The compound corresponding to the crosslinking agent, dispersant and surfactant described later is not contained in the polymer component even if it is a polymer compound.

The content of the polymer component is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total mass of the positive photosensitive resin layer.

Alkali-soluble resin (Positive type)

The positive photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinone diazide compound, and particularly preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinone diazide compound.

Examples of the alkali-soluble resin include resins having a hydroxyl group, a carboxyl group, or a sulfo group in the main chain or a side chain. Examples of the alkali-soluble resin include polyamide resins, polyhydroxystyrenes, polyhydroxystyrene derivatives, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoates, carboxyl group-containing (meth) acrylic resins, and novolak resins. Preferable alkali-soluble resins include, for example, polycondensates of m/p-mixed cresols and formaldehyde and polycondensates of phenol, cresols and formaldehyde.

The alkali-soluble resin may have a phenolic hydroxyl group (-Ar-OH) and a carboxyl group (-CO) ₂ H) Sulfo (-SO) ₃ H) Phosphate group (-OPO) ₃ H) Sulfonamide (-SO) ₂ NH-R) or substituted sulfonamide group (e.g., reactive imide group, -SO ₂ NHCOR、-SO ₂ NHSO ₂ R and-CONHSO ₂ R). Here, ar represents a divalent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

The novolak resin is obtained, for example, by condensing a phenol compound and an aldehyde compound in the presence of an acid catalyst. Examples of the phenol compound include o-cresol, m-cresol or p-cresol, 2, 5-xylenol, 3, 5-xylenol or 3, 4-xylenol, 2,3, 5-trimethylphenol, 2-t-butyl-5-methylphenol, and t-butylhydroquinone. Examples of the aldehyde compound include aliphatic aldehydes (for example, formaldehyde, acetaldehyde, and glyoxal) and aromatic aldehydes (for example, benzaldehyde, and salicylaldehyde). Examples of the acid catalyst include inorganic acids (e.g., hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (e.g., oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (e.g., zinc acetate). The condensation reaction can be carried out according to conventional methods. The condensation reaction is carried out, for example, at a temperature in the range of 60℃to 120℃for 2 hours to 30 hours. The condensation reaction may be carried out in a suitable solvent.

Among them, the alkali-soluble resin is preferably a resin containing a structural unit having a phenolic hydroxyl group such as a novolak resin.

From the viewpoint of pattern formability, weight average of alkali-soluble resinThe molecular weight is preferably 5.0X10 ² ～2.0×10 ⁵ . The number average molecular weight of the alkali-soluble resin is preferably 2.0X10 from the viewpoint of pattern formability ² ～1.0×10 ⁵ 。

For example, a polycondensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent may be used in combination with a polycondensate of tert-butylphenol and formaldehyde, a polycondensate of octylphenol and formaldehyde, or the like as described in U.S. Pat. No. 4123279. A mixture of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent may be used together with a t-butylphenol formaldehyde resin, an octylphenol formaldehyde resin, or the like as described in U.S. Pat. No. 4123279.

The positive photosensitive resin layer may contain one alkali-soluble resin alone or two or more alkali-soluble resins.

The content of the alkali-soluble resin is preferably 30 to 99.9 mass%, more preferably 40 to 99.5 mass%, and particularly preferably 70 to 99 mass%, relative to the total mass of the positive photosensitive resin layer.

< photoacid generator >

The positive photosensitive resin layer preferably contains a photoacid generator as a photosensitive compound. Photoacid generators are compounds capable of generating acids upon irradiation with active light rays (e.g., ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams).

The photoacid generator is preferably a compound that generates an acid by being sensitive to an active light having a wavelength of 300nm or more (preferably, a wavelength of 300nm to 450 nm). The photoacid generator that is not directly sensitive to the active light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound that is sensitive to the active light having a wavelength of 300nm or more by being used in combination with the sensitizer to generate an acid.

The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of the pKa of the acid derived from the photoacid generator is not limited. The pKa of the acid derived from the photoacid generator is, for example, preferably-10.0 or more.

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

Examples of the ionic photoacid generator include onium salt compounds. Examples of the onium salt compound include a diaryliodonium salt compound, a triarylsulfonium salt compound, and a quaternary ammonium salt compound. The ionic photoacid generator is preferably an onium salt compound, and particularly preferably at least one of a triarylsulfonium salt compound and a diaryliodonium salt compound.

As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A2014-85643 can also be preferably used.

Examples of the nonionic photoacid generator include a trichloromethyl s-triazine compound, a diazomethane compound, an imide sulfonate compound, and an oxime sulfonate compound. The nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion to a substrate.

Specific examples of the trichloromethyl s-triazine compound, the diazomethane compound and the imide sulfonate compound include those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be preferably used.

From the viewpoints of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably an oxime sulfonate compound.

Preferable examples of the photoacid generator include photoacid generators having the following structures.

[ chemical formula 17]

Examples of the photoacid generator having absorption at a wavelength of 405nm include ADEKA ARKLS (registered trademark) SP-601 (manufactured by ADEKA Corporation).

From the viewpoints of heat resistance and dimensional stability, the positive photosensitive resin layer preferably contains a quinone diazide compound as an acid generator (preferably a photoacid generator).

The quinone diazide compound can be synthesized, for example, by subjecting a compound having a phenolic hydroxyl group and a quinone diazide sulfonyl halide to a condensation reaction in the presence of a dehydrohalogenating agent.

Examples of the quinone diazide compound include 1, 2-benzoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, 1, 2-naphthoquinone diazide-6-sulfonate, 2, 1-naphthoquinone diazide-4-sulfonate, 2, 1-naphthoquinone diazide-5-sulfonate, 2, 1-naphthoquinone diazide-6-sulfonate, sulfonates of other quinone diazide derivatives, 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 1, 2-naphthoquinone diazide-6-sulfonyl chloride, 2, 1-naphthoquinone diazide-4-sulfonyl chloride, 2, 1-naphthoquinone diazide-5-sulfonyl chloride, and 2, 1-naphthoquinone diazide-6-sulfonyl chloride.

The positive photosensitive resin layer may contain one photoacid generator alone or two or more photoacid generators.

From the viewpoint of sensitivity and resolution, the content of the photoacid generator is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, relative to the total mass of the positive photosensitive resin layer.

< other ingredients >

The photosensitive resin layer may contain components other than the above.

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 surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.

Examples of the surfactant include surfactants described in paragraphs 0060 to 0071 of JP-A-4502784, paragraph 0017 and JP-A-2009-237362.

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

As the commercial product of the fluorine-based surfactant, for example, examples of the materials include MEGAFACE (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, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, and so on RS-72-K, DS-21 (manufactured by DIC Corporation, supra), fluorad (trade name) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, supra), surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc., supra), polyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc, supra), ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, ftergent, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured above as NEOS COMPANY LIMITED), and the like.

The fluorine-based surfactant may preferably be an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and the functional group containing a fluorine atom is partially cleaved to volatilize the fluorine atom when heat is applied. Examples of such a fluorine-based surfactant include the MEGAFACE (trade name) DS series (chemical industry daily report (2016, 2, 22 days), daily industrial news (2016, 2, 23 days)) manufactured by DIC corporation, and for example, MEGAFACE (trade name) DS-21.

In addition, as the fluorine-based surfactant, a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group is also preferably used.

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

Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (trade name) manufactured by Chemical F company, tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (trade name) manufactured by BASF company, solsperse (trade name) 20000 (manufactured by Lubrizol Japan Limid. Above), NCW-101, NCW-1001, NCW-1002 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-6112, D-5712-W, D (trade name) manufactured by Chemical F company, tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (trade name) manufactured by BASF corporation, and so on, manufactured by Talcet al, ltde.400, ltde.g., ltde.400.

In recent years, since compounds having a linear perfluoroalkyl group having 7 or more carbon atoms are considered to have environmental suitability, surfactants using perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) as substitutes are preferably used.

The silicone surfactant includes a linear polymer composed of siloxane bonds, and a modified siloxane polymer obtained by introducing an organic group into a side chain or a terminal.

Specific examples of silicone surfactants include DOWSIL (trade name) 8032ADDIT IVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by Ltd. Above Dow Corning Toray Co.), and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., ltd. Above), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials c. Above), KF-430K, BYK, BYK.sub.323, BYD.330, and the like.

The photosensitive resin layer may contain one kind of surfactant alone or two 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, an alkoxysilane compound, and a solvent. The photosensitive resin layer may contain one kind of each additive alone or two or more kinds of each additive.

Examples of the additives include metal oxide particles, antioxidants, dispersants, acid-proliferating agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents. The preferable modes of these additives are described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643, respectively, which are incorporated herein by reference.

The photosensitive resin layer may contain a polymerization inhibitor. As the polymerization inhibitor, a radical polymerization inhibitor is preferable.

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, an N-nitrosophenyl hydroxylamine aluminum salt is preferably used as a polymerization inhibitor.

The content of the polymerization inhibitor is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, relative to the total mass of the photosensitive resin layer. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.01 mass% or more. On the other hand, from the viewpoint of maintaining sensitivity, 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 (for example, 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 one kind of sensitizer alone or two or more kinds of sensitizers.

When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, and from the viewpoints 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 one selected from the group consisting of 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 (preferably, a positive photosensitive resin layer) may contain an alkoxysilane compound.

Examples of alkoxysilane compounds include gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trialkoxysilane, gamma-glycidoxypropyl alkyl dialkoxysilane, gamma-methacryloxypropyl trialkoxysilane, gamma-methacryloxypropyl alkyl dialkoxysilane, gamma-chloropropyl trialkoxysilane, gamma-mercaptopropyl trialkoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trialkoxysilane and vinyl trialkoxysilane.

Among the above, the alkoxysilane compound is preferably a trialkoxysilane compound, more preferably γ -glycidoxypropyl trialkoxysilane or γ -methacryloxypropyl trialkoxysilane, further preferably γ -glycidoxypropyl trialkoxysilane, and particularly preferably 3-glycidoxypropyl trimethoxysilane.

The photosensitive resin layer may contain one kind of alkoxysilane compound alone or two or more kinds of alkoxysilane compounds.

From the viewpoints of adhesion to a substrate and etching resistance, the content of the alkoxysilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1.0 to 30% by mass, relative to the total mass of the photosensitive resin layer.

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.

< impurity, etc. >

The photosensitive resin layer may contain a predetermined amount of impurities.

Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, the halide ion, sodium ion and potassium ion are easily mixed in the form of impurities, and therefore, the following contents are preferable.

The content of impurities in the photosensitive resin layer is preferably 80ppm or less, more preferably 10ppm or less, and further preferably 2ppm or less on a mass basis. The content of the impurities may be 1ppb or more or 0.1ppm or more on a mass basis.

As a method of setting the impurity in the above range, the following methods are given: selecting a raw material with a small impurity content as a raw material of the composition; preventing impurities from mixing in when manufacturing the photosensitive resin layer; and cleaning and removing. By these methods, the impurity amount can be set within the above-described range.

The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma: inductively coupled plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

The photosensitive resin layer preferably contains a small amount of a compound such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane. The content of these compounds relative to the total mass of the photosensitive resin layer is preferably 100ppm or less, more preferably 20ppm or less, and still more preferably 4ppm or less on a mass basis.

The lower limit may be 10ppb or more or 100ppb or more relative to the total mass of the photosensitive resin layer on a mass basis. These compounds can be suppressed in content by the same method as the impurities of the above metals. Further, the amount can be determined by a known measurement method.

The water content in the photosensitive resin layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, from the viewpoint of improving reliability and lamination.

< residual monomer >

The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the alkali-soluble resin.

From the viewpoints of patterning properties and reliability, the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.

From the viewpoints of patterning properties and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

The residual monomer amount of the monomer in synthesizing the alkali-soluble resin by the polymer reaction is also preferably set within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set within the above range.

The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

Physical Property and the like ]

The 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 improves the developability of the photosensitive resin layer, and can improve resolution.

Further, the layer thickness (thickness) of the photosensitive resin layer is preferably 10 μm or less, more preferably 5.0 μm or less, further preferably 0.5 μm to 4.0 μm, particularly preferably 0.5 μm to 3.0 μm, from the viewpoint of further exhibiting the resolution and the effects of the present invention.

The layer thickness of each layer included in the photosensitive transfer material was measured by observing a cross section in a direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM: scanning Electron Microscope), and measuring the thickness of each layer at 10 points or more based on the obtained observation image and calculating an average value thereof.

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 still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

< Forming method >

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, when it is a negative photosensitive resin layer, there is a method of forming by: a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, and the like is prepared, 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.

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

In order to adjust the viscosity of the photosensitive resin composition and to 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 can dissolve or disperse the alkali-soluble resin, the polymerizable 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 two or more of them.

When a photosensitive transfer material including a temporary support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive resin layer, and a protective film is produced, the photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among them, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least three 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 is further preferable.

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 one solvent alone or two or more solvents.

The content of the solvent at the time of coating the photosensitive resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, per 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 examples thereof include a method in which a solution obtained by dissolving each component in the above solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to produce the photosensitive resin composition.

From the viewpoint of particle removability, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive resin layer, more preferably using a filter having a pore size of 0.2 μm to 10 μm, even more preferably using a filter having a pore size of 0.2 μm to 7 μm, and particularly preferably using a filter having a pore size of 0.2 μm to 5 μm.

The material and shape of the filter are not particularly limited, and known filters can be used.

The filtration is preferably performed 1 or more times, and more preferably performed several times.

The method of applying the photosensitive resin composition is not particularly limited, and 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.

In the photosensitive transfer material of the present invention, it is preferable that another layer is provided between the temporary support and the photosensitive resin layer from the viewpoints of resolution and releasability of the temporary support.

The other layer may preferably be a water-soluble resin layer, a thermoplastic resin layer, a protective film, or the like.

Among them, the transfer layer is preferably a water-soluble resin layer, and more preferably a thermoplastic resin layer and a water-soluble resin layer.

[ Water-soluble resin layer ]

When the photosensitive transfer material has a thermoplastic resin layer described later between the temporary support and the photosensitive resin layer, it is preferable to have a water-soluble resin layer between the thermoplastic resin layer and the photosensitive resin layer. According to the water-soluble resin layer, mixing of components can be suppressed when forming a plurality of layers and when storing.

The water-soluble resin layer is preferably a water-soluble layer from the viewpoints of developability and suppression of mixing of components during application of the multilayer and storage after application. In the present invention, "water-soluble" means that the solubility in 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more.

Examples of the water-soluble resin layer include an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. By using the water-soluble resin layer as the oxygen barrier layer, the sensitivity at the time of exposure is improved, and the time load of the exposure machine is reduced, as a result, the productivity is improved. The oxygen barrier layer used as the water-soluble resin layer may be appropriately selected from known layers. The oxygen barrier layer used as the water-soluble resin layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22 ℃).

Further, the water-soluble resin layer preferably contains an inorganic lamellar compound from the viewpoints of oxygen barrier property, resolution and patterning property.

Examples of the inorganic layered compound include particles having a thin plate-like shape, such as mica compounds including natural mica and synthetic mica, and particles represented by the formula: 3MgO.4SiOH ₂ Talc, perovskite, montmorillonite, saponite, hectorite, zirconium phosphate, etc. represented by O.

Examples of the mica compound include compounds represented by the formula: a (B, C) _2-5 D ₄ O ₁₀ (OH，F，O) ₂ [ wherein A is any one of K, na and Ca, or B and C are any one of Fe (II), fe (III) and Mn, al, mg, V, and D is Si or Al.]The mica group represented by natural mica and synthetic mica.

Among the mica groups, muscovite, sodium mica, phlogopite, biotite and lepidolite are exemplified as natural mica. As synthetic mica, fluorophlogopite KMg may be mentioned ₃ (AlSi ₃ O ₁₀ )F ₂ Potassium tetrasilicon mica KMg _2.5 (Si ₄ O ₁₀ )F ₂ Equal non-swelling mica and sodium tetra-silicon mica NaMg _2.5 (Si ₄ O ₁₀ )F ₂ Na or Li olivine (Na, li) Mg ₂ Li(Si ₄ O ₁₀ )F ₂ Montmorillonite Na or Li magnesium lithium silicate (Na, li) _1/8 Mg _2/5 Li _1/8 (Si ₄ O ₁₀ )F ₂ And swellable mica. In addition, synthetic smectites are also useful.

From the viewpoint of controlling diffusion, the thinner the thickness is, the better the shape of the inorganic layered compound, and the larger the planar size is, as long as the smoothness of the coated surface or the transmittance of the active light is not impaired. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is a ratio of the major axis to the thickness of the particles, and can be measured from a projection view of a particle-based photomicrograph, for example. The larger the aspect ratio, the greater the effect obtained.

The average long diameter of the particle diameter of the inorganic layered compound is preferably 0.3 μm to 20. Mu.m, more preferably 0.5 μm to 10. Mu.m, particularly preferably 1 μm to 5. Mu.m. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, particularly preferably 0.01 μm or less. Specifically, for example, in the case of swellable synthetic mica as a representative compound, it is preferable that the thickness is about 1nm to 50nm and the surface size (long diameter) is about 1 μm to 20 μm.

From the viewpoints of oxygen barrier property, resolution and pattern formation property, the content of the inorganic lamellar compound is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass, relative to the total mass of the water-soluble resin layer.

The water-soluble resin layer preferably contains a resin. Examples of the resin contained in the water-soluble resin layer include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. The resin contained in the water-soluble resin layer is preferably a water-soluble resin.

From the viewpoint of suppressing the mixing of components between the layers, the resin contained in the water-soluble resin layer is preferably a resin different from both the polymer a contained in the negative photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer.

Further, the water-soluble resin layer preferably contains a water-soluble compound, more preferably contains a water-soluble resin, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation property.

The water-soluble compound is not particularly limited, but is preferably one or more compounds selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives and amide compounds, and more preferably at least one water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl methylcellulose, from the viewpoints of oxygen barrier property, developability, resolution and patterning property.

Examples of the water-soluble resin include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylic amide resins, (meth) acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

Among them, the water-soluble compound preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation.

The degree of hydrolysis of the polyvinyl alcohol is not particularly limited, but is preferably 73mol% to 99mol% from the viewpoints of oxygen barrier property, developability, resolution and pattern formation.

Further, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation property, the polyvinyl alcohol preferably contains ethylene as a monomer unit.

The water-soluble resin layer preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen barrier property and the ability to suppress mixing of components at the time of coating a plurality of layers and at the time of storage after coating.

The water-soluble resin layer may contain one resin alone or two or more resins.

The content of the water-soluble compound in the water-soluble resin layer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to the total mass of the water-soluble resin layer, from the viewpoint of oxygen barrier property and the capability of suppressing mixing of components at the time of coating the multilayer and at the time of storage after coating.

The water-soluble resin layer may contain an additive as required. Examples of the additive include surfactants.

The thickness of the water-soluble resin layer is not limited. The average thickness of the water-soluble resin layer is preferably 0.1 μm to 5. Mu.m, more preferably 0.5 μm to 3. Mu.m. When the thickness of the water-soluble resin layer is within the above range, mixing of components at the time of forming a plurality of layers and at the time of storage can be suppressed without lowering the oxygen barrier property, and an increase in the time for removing the water-soluble resin layer at the time of development can be suppressed.

The method for forming the water-soluble resin layer is not limited as long as the layer containing the above components can be formed. As a method for forming the water-soluble resin layer, for example, a method of applying the water-soluble resin layer composition to the surface of the thermoplastic resin layer or the photosensitive resin layer and then drying the coating film of the water-soluble resin layer composition can be cited.

Examples of the water-soluble resin layer composition include a composition containing a resin and any additives. In order to adjust the viscosity of the water-soluble resin layer composition and to easily form the water-soluble resin layer, the water-soluble resin layer composition preferably contains a solvent. The solvent is not limited as long as it is a solvent capable of dissolving or dispersing the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, more preferably water or a mixed solvent of water and water-miscible organic solvents.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

[ thermoplastic resin layer ]

The photosensitive transfer material used in the present invention may have a thermoplastic resin layer. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. This is because, since the photosensitive transfer material has the thermoplastic resin layer between the temporary support and the photosensitive resin layer, the following property to the adherend is improved, and the mixing of bubbles between the adherend and the photosensitive transfer material is suppressed, and as a result, the adhesion between layers is improved.

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin is preferably an acrylic resin from the viewpoints of developability and adhesion of layers adjacent to the thermoplastic resin layer. Here, the "acrylic resin" refers to a resin having at least one selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide.

In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, relative to the total mass of the acrylic resin.

Also, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonate group, and a carboxyl group is preferable.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, more preferably a carboxyl-containing acrylic resin having an acid value of 60mgKOH/g or more. The upper limit of the acid value is not limited. The acid value of the alkali-soluble resin is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is not limited, and can be appropriately selected from known resins. Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more from among the polymers described in paragraph 0025 of JP-A2011-95716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more from among the polymers described in paragraphs 0033 to 0052 of JP-A2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more from among the binder polymers described in paragraphs 0053 to 0068 of JP-A2016-224162.

The content of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass, relative to the total mass of the carboxyl group-containing acrylic resin.

The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoints of developability and adhesion of layers adjacent to the thermoplastic resin layer.

The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxyl group and a carboxyl group), and a polyaddition reactive group (e.g., an epoxy group and a (block) isocyanate group).

The alkali-soluble resin preferably has a weight average molecular weight (Mw) of 1,000 or more, more preferably 1 to 10 tens of thousands, particularly preferably 2 to 5 tens of thousands.

The thermoplastic resin layer may contain one or more alkali-soluble resins alone.

The content ratio of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoints of developability and adhesion of the layers adjacent to the thermoplastic resin layer.

The thermoplastic resin layer preferably contains a dye (hereinafter, also referred to as "dye B") having a maximum absorption wavelength of 450nm or more and a maximum absorption wavelength that changes by an acid, an alkali or a radical in the wavelength range of 400nm to 780nm, which is the wavelength range at the time of color development. The preferred embodiment of the dye B is the same as that of the dye N described above, except for the point described below.

From the viewpoints of visibility of an exposed portion, visibility of a non-exposed portion, and resolution, the dye B 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 an acid.

From the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, and resolution, the thermoplastic resin layer preferably contains a dye whose maximum absorption wavelength is changed by an acid as the dye B, and a compound C described later.

The thermoplastic resin layer may contain one or two or more pigments B alone.

From the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion, the content of the dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, even more preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass% relative to the total mass of the thermoplastic resin layer.

The content of the pigment B is a content of the pigment when all the pigment B contained in the thermoplastic resin layer is in a color-developed state. Hereinafter, a method for quantifying the content of the dye B will be described by taking a dye that develops color by a radical as an example. Two solutions were prepared by dissolving pigment (0.001 g) and pigment (0.01 g) in methyl ethyl ketone (100 mL). After IRGACURE OXE01 (manufactured by BASF corporation) was added as a photo radical polymerization initiator to each of the obtained solutions, 365nm light was irradiated to generate radicals, thereby bringing all the pigments into a colored state. Next, the absorbance of each solution having a liquid temperature of 25 ℃ was measured using a spectrophotometer (manufactured by UV3100, shimadzu Corporation) under atmospheric conditions, and a calibration curve was prepared. Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that the thermoplastic resin layer (0.1 g) was dissolved in methyl ethyl ketone instead of the pigments. The amount of the pigment contained in the thermoplastic resin layer was calculated from the absorbance of the obtained solution containing the thermoplastic resin layer based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, sometimes referred to as "compound C"). The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving active light rays (e.g., ultraviolet rays and visible rays). Examples of the compound C include a known photoacid generator, a photoacid generator, and a photoradical polymerization initiator (photoradical generator). Compound C is preferably a photoacid generator.

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. The photo-cation polymerization initiator that may be contained in the photosensitive resin layer is preferably the same as the photo-cation polymerization initiator except for the point described below.

The photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.

The photoacid generator is also preferably one having the following structure.

[ chemical formula 18]

The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, O-carbamoyl hydroxyamide, O-carbamoyl oxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl } cyclohexylamine, bis [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane-1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexamine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine, 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine.

The thermoplastic resin layer may contain a photo radical polymerization initiator. The photo radical polymerization initiator may be contained in the photosensitive resin layer, for example, and the same preferable embodiment is also applicable.

The thermoplastic resin layer may contain one or two or more compounds C alone.

The content ratio of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass% with respect to the total mass of the thermoplastic resin layer from the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, and resolution.

The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

The molecular weight of the plasticizer (for the molecular weight of the oligomer or polymer, refer to the weight average molecular weight (Mw). Hereinafter, the same applies in this paragraph) is preferably less than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and expresses plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyoxyethylene structure or a polyoxypropylene structure.

From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth) acrylate compound. From the viewpoints of compatibility, resolution, and adhesion of layers adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.

The (meth) acrylate compound used as the plasticizer includes, for example, the (meth) acrylate compounds described in the above-mentioned ethylenically unsaturated compounds. When the thermoplastic resin layer and the photosensitive resin layer are disposed in direct contact in the photosensitive transfer material, the thermoplastic resin layer and the photosensitive resin layer preferably contain the same (meth) acrylate compound, respectively. The reason for this is that the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth) acrylate compound, so that the diffusion of components between layers is suppressed and the storage stability is improved.

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize even in the exposed portion after exposure from the viewpoint of adhesion of the layer adjacent to the thermoplastic resin layer.

In one embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.

In a certain embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.

The thermoplastic resin layer may contain one or two or more plasticizers alone.

The content ratio of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion of the layer adjacent to the thermoplastic resin layer, and developability.

From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. The surfactant may be, for example, a surfactant that may be contained in the photosensitive resin layer, and the same preferable embodiment is also adopted.

The thermoplastic resin layer may contain one or two or more surfactants alone.

The content ratio of the surfactant is preferably 0.001 to 10 mass%, more preferably 0.01 to 3 mass%, relative to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include those that can be contained in the negative photosensitive resin layer described above.

The thermoplastic resin layer may contain one or two or more sensitizers alone.

The content ratio of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% with respect to the total mass of the thermoplastic resin layer, from the viewpoints of improvement of sensitivity to light sources, visibility of exposed portions, and visibility of non-exposed portions.

The thermoplastic resin layer may contain known additives as required in addition to the above components.

The thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese unexamined patent application publication No. 2014-85643. The contents of the above publications are incorporated into the present specification by reference.

The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion of the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less from the viewpoints of developability and resolution.

The method for forming the thermoplastic resin layer is not limited as long as the layer containing the above components can be formed. As a method for forming the thermoplastic resin layer, for example, a method of applying the thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition can be cited.

Examples of the thermoplastic resin composition include compositions containing the above components. In order to adjust the viscosity of the thermoplastic resin composition and to easily form the thermoplastic resin layer, the thermoplastic resin composition preferably contains a solvent.

The solvent contained in the thermoplastic resin composition is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the thermoplastic resin layer. The solvent may be any solvent that can be contained in the photosensitive resin composition, and the same preferable mode is also adopted.

The thermoplastic resin composition may contain one or two or more solvents alone.

The content ratio of the solvent in the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the thermoplastic resin composition.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer can be performed according to the above-described method for preparing the photosensitive resin composition and the method for forming the negative photosensitive resin layer. For example, a thermoplastic resin layer is formed by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent, mixing the obtained solutions in a predetermined ratio, thereby preparing a thermoplastic resin composition, then coating the obtained thermoplastic resin composition on the surface of a temporary support, and drying the coating film of the thermoplastic resin composition. After the photosensitive resin layer is formed on the protective film, a thermoplastic resin layer may be formed on the surface of the photosensitive resin layer.

[ protective film ]

The photosensitive transfer material preferably has a protective film.

In addition, the protective film is not included in the transfer layer.

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 polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, a polyethylene film, a polypropylene film or a polyethylene terephthalate film is preferable.

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.

From the viewpoints of conveyability, defect suppression of the resin pattern, and resolution, the surface of the protective film on the side opposite to the photosensitive resin layer side preferably has an arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side or less, and more preferably has an arithmetic average roughness Ra smaller than the surface of the protective film on the photosensitive resin layer side.

The surface of the protective film on the side opposite to the photosensitive resin layer side has an arithmetic average roughness Ra of preferably 300nm or less, more preferably 100nm or less, still more preferably 70nm or less, and particularly preferably 50nm or less, from the viewpoints of transportation and windability.

Further, from the viewpoint of further excellent resolution, the surface of the protective film on the photosensitive resin layer side has an arithmetic average roughness Ra of preferably 300nm or less, more preferably 100nm or less, still more preferably 70nm or less, and particularly preferably 50nm or less. The reason for this is considered to be that the Ra value of the surface of the protective film falls within 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 both surfaces are preferably 1nm or more, more preferably 10nm or more, particularly preferably 20nm or more.

The peeling force of the protective film is preferably smaller than the peeling force of the temporary support.

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.

The total thickness of the photosensitive transfer material is preferably 5 μm to 55. Mu.m, more preferably 10 μm to 50. Mu.m, particularly preferably 20 μm to 40. Mu.m. The total thickness of the photosensitive transfer material is measured by a method that is based on the thickness measurement method of each layer.

From the viewpoint of further exhibiting the effects of the present invention, the total thickness of the layers of the photosensitive transfer material excluding 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, the water-soluble resin layer, and the thermoplastic 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 used in 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 a layer structure in one embodiment of a photosensitive transfer material used in the present invention. The photosensitive transfer material 20 shown in fig. 1 has a structure in which a temporary support 11, a thermoplastic resin layer 13, a water-soluble resin layer 15, a photosensitive resin layer 17, and a protective film 19 are laminated in this order. The transfer layer 12 in fig. 1 is a thermoplastic resin layer 13, a water-soluble resin layer 15, and a photosensitive resin layer 17.

As a method for producing the photosensitive transfer material 20, for example, the following method can be mentioned: it comprises the following steps: a step of forming a thermoplastic resin layer 13 by applying a thermoplastic resin composition onto the surface of the temporary support 11 and then drying the coating film of the thermoplastic resin composition; a step of forming a water-soluble resin layer 15 by drying a coating film of the water-soluble resin layer composition after the water-soluble resin layer composition is coated on the surface of the thermoplastic resin layer 13; and a step of forming a photosensitive resin layer 16 by applying a photosensitive resin composition containing an ethylenically unsaturated compound to the surface of the water-soluble resin layer 15 and then drying the coating film of the photosensitive resin composition.

In the above manufacturing method, it is preferable to use: a thermoplastic resin composition containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents; a water-soluble resin layer composition containing at least one selected from the group consisting of water and water-miscible organic solvents; and a photosensitive resin composition containing a binder polymer, an ethylenically unsaturated compound, and at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. This can suppress the mixing of the components contained in the thermoplastic resin layer 13 and the components contained in the water-soluble resin layer 15 during the shelf life of the laminate having the coating film of the water-soluble resin layer composition and/or the coating film of the water-soluble resin layer composition applied to the surface of the thermoplastic resin layer 13, and can suppress the mixing of the components contained in the water-soluble resin layer 15 and the components contained in the photosensitive resin layer 16 during the shelf life of the laminate having the coating film of the water-soluble resin composition applied to the surface of the water-soluble resin layer 15.

The protective film 19 is pressed against the photosensitive resin layer 17 of the laminate manufactured by the above-described manufacturing method, thereby manufacturing the photosensitive transfer material 20.

As a method for producing the photosensitive transfer material used in the present invention, it is preferable to produce the photosensitive transfer material 20 including the temporary support 11, the thermoplastic resin layer 13, the water-soluble resin layer 15, the photosensitive resin layer 17, and the protective film 19 by including a step of providing the protective film 19 so as to be in contact with the 2 nd surface of the photosensitive resin layer 17.

After the photosensitive transfer material 20 is manufactured by the above manufacturing method, the photosensitive transfer material 20 can be wound up to manufacture and store a photosensitive transfer material in a roll form. The photosensitive transfer material in the form of a roll can be supplied as it is to a step of bonding the photosensitive transfer material to a substrate in a roll-to-roll manner described later.

< pigment >

The photosensitive resin layer may be a colored resin layer containing a pigment.

In recent years, a cover glass (cover glass) in which a black frame-like light shielding layer is formed on a rear surface peripheral edge portion of a transparent glass substrate or the like is sometimes mounted on a liquid crystal display window included in an electronic device in order to protect the liquid crystal display window. In order to form such a light shielding layer, a colored resin layer may be used.

The pigment may be appropriately selected according to a desired hue, and may be selected from black pigments, white pigments, and color pigments other than black and white. Among them, when forming a black-based pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, or the like) can be appropriately selected as long as the effect in the present invention is not impaired. Among them, carbon black, titanium carbide, iron oxide, titanium oxide, graphite, and the like are preferable as black pigment from the viewpoint of optical density, and carbon black is particularly preferable. As the carbon black, carbon black having at least a part of the surface coated with a resin is preferable from the viewpoint of surface resistance.

From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm in terms of the number average particle diameter.

The particle diameter is an average value obtained by obtaining the particle diameter of any 100 particles from a photographic image of pigment particles taken by an electron microscope, and obtaining a circle having the same area as the area of the pigment particles, and the number average particle diameter is an average value obtained by averaging the obtained 100 particle diameters.

As the pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of jp 2005-007765 a can be used as the white pigment. Specifically, among the white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable as the inorganic pigment, titanium oxide or zinc oxide is more preferable, and titanium oxide is further preferable. The inorganic pigment is preferably rutile-type or anatase-type titanium oxide, and particularly preferably rutile-type titanium oxide.

The surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more kinds of treatments. Thus, the catalytic activity of titanium oxide is suppressed, and heat resistance, gloss fading, and the like are improved.

From the viewpoint of reducing the thickness of the heated photosensitive resin layer, at least one of an alumina treatment and a zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both of the alumina treatment and the zirconia treatment are particularly preferable.

In addition, when the photosensitive resin layer is a colored resin layer, it is preferable that the photosensitive resin layer further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability. When the color pigment is contained, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility.

As the Color pigment, for example, examples thereof include Victoria pure blue BO (Color Index) (hereinafter, C.I.) 42595, gold amine (C.I. 41000), fat black (fat black) HB (C.I. 26150), monolite yellow (pigment yellow 12), permanent yellow (pigment yellow 17), permanent yellow HR (pigment yellow 83), permanent carmine (permanent carmine) FBB (C.I. pigment Red 146), herstellum red (hostaperm red) ESB (C.I. pigment Violet 19), permanent red (permanent ruby) FBH (C.I. pigment Red 11), fasten pink (pigment Red 81), mostenite fast blue (pigment Red monastral fast blue) (C.I. pigment Red 15), permanent yellow HR (C.I. pigment yellow 83), permanent carmine (FBB (C.I. pigment Red 149), permanent red C.C.C.I. pigment Red 1, C.C.C.C.15), C.C.C.1, C.9, C.C.1, C.15, C.C.1, C.9, C.15, C.1, C.9, C.15, C.1, C.9, C.15. Among them, c.i. pigment red 177 is preferred.

When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, further preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less, relative to the total mass of the photosensitive resin layer.

When the photosensitive resin layer contains a pigment other than a black pigment (white pigment and color pigment), the content of the pigment other than the black pigment is preferably 30 mass% or less, more preferably 1 mass% to 20 mass%, and still more preferably 3 mass% to 15 mass% with respect to the black pigment.

When the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion.

The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (vehicle) and dispersing it with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle means a medium portion for dispersing the pigment when the pigment dispersion is formed, and is in a liquid state, and includes a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.

The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as a kneader, a roll mill, an attritor (attritor), a super mill, a dissolver (distolver), a homomixer (homomixer), and a sand mill (sand mill). In addition, the fine grinding may be performed by mechanical grinding and by friction. For the disperser and the fine pulverization, a description of "pigment dictionary" (manufactured by kubang, first edition, kuku shop, 2000, page 438, page 310) can be referred to.

(electronic device and method for manufacturing the same)

The electronic device according to the present invention includes the laminate according to the present invention.

The method for manufacturing an electronic device according to the present invention is not particularly limited as long as it is a method for manufacturing an electronic device having the laminate according to the present invention.

The same applies to the specific embodiments of each step, the order of performing each step, and the like in the method for manufacturing an electronic device, as described in the above item of the "method for manufacturing a laminate".

As for the method of manufacturing an electronic device, a known method of manufacturing an electronic device may be referred to, in addition to the content of forming wiring for an electronic device by the above method.

The method for manufacturing an electronic device may include any step (other step) other than the above.

The electronic device is not particularly limited, and various wiring forming applications of a semiconductor package, a printed circuit board, a sensor substrate, a touch panel, an electromagnetic wave shielding material, a conductive film such as a film heater, a liquid crystal sealing material, and a structural object in the micro-machine or micro-electronics field can be suitably exemplified.

Among them, a touch panel is particularly suitable as an electronic device.

Further, as the electronic device, a flexible display device, particularly a flexible touch panel, can be suitably used.

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 shows an aligned frame. In the method for manufacturing a touch panel, for example, the photosensitive resin layer is exposed 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 where four corners are connected) 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 a wiring of a peripheral extraction portion is formed.

By the above-described method for manufacturing an electronic device, an electronic device having at least a wiring for an electronic device is manufactured, and preferably, for example, a touch panel having at least a wiring for a touch panel is manufactured.

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, a Touch panel 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, a Touch panel described in fig. 19 of japanese patent application laid-open publication No. 2013-168125, and a Touch panel described in fig. 1 and 5 of japanese patent application laid-open publication No. 2012-89102), an OGS (One Glass Solution: a monolithic glass solution), a TOL (Touch-on-Lens) type (for example, a Touch panel described in fig. 2 of japanese patent application laid-open publication No. 2013-54727), and various types of external type (for example, a so-called GG, g1·g2, GFF, GF2, GF1, G1F, and the like), and other configurations (for example, a Touch panel described in fig. 6 of japanese patent application laid-open publication No. 2013-164871).

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

Examples

Hereinafter, embodiments of the present invention will be described in further detail with reference to examples. The materials, amounts used, proportions, treatment contents, treatment orders, and the like shown in the following examples can be appropriately changed 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 references.

< evaluation of various physical Properties of substrate >

The glass transition temperature (Tg) of the substrate was measured using a solid viscoelasticity measuring machine RSA-G2 (TA Instrum ents Japan inc. Manufactured).

The total light transmittance of the substrate was measured with a haze meter NDH-4000 (NIPPON DENSHOKU INDUSTRI ES co., LTD) under D65 light source (wavelength 380nm to 780 nm).

In addition, as for the Coefficient of Thermal Expansion (CTE) and the dimensional change rate of the substrate, a thermal analyzer TMA7100 (manufactured by hitachi high-Tech Corporation) was used, and measurement was performed at a temperature ranging from 100 ℃ to 200 ℃ unless otherwise specified.

Example 1

< preparation of conductive substrate >

Silver nanowire ink synthesized by the following method was coated with a spin coater on a polyimide film TORMED TypeX (manufactured by I.S. T Corporation) substrate having a film thickness of 50 μm so that the wet film thickness became 5 μm, and dried at 100℃for 5 minutes to obtain a conductive substrate.

Synthesis of silver nanowire

Silver nanowires were obtained by the following method.

Propylene glycol (1, 2-propylene glycol) as a solvent, a copolymer of vinylpyrrolidone and diallyldimethylammonium nitrate (diallyldimethylammonium nitrate) as an organic protective agent (copolymer synthesis was performed with 99 mass% of vinylpyrrolidone and 1 mass% of diallyldimethylammonium nitrate, and each of silver nitrate, lithium chloride, potassium bromide, lithium hydroxide, aluminum nitrate nonahydrate, and the like was prepared with a weight average molecular weight of 130,000).

To 20.0g of propylene glycol at room temperature (23 ℃ C., the same applies below), 0.15g of propylene glycol solution containing 1% by mass of lithium chloride, 0.10g of propylene glycol solution containing 0.25% by mass of potassium bromide, 0.20g of propylene glycol solution containing 1% by mass of lithium hydroxide, 0.16g of propylene glycol solution containing 2% by mass of aluminum nitrate nonahydrate, and 0.26g of a copolymer of vinylpyrrolidone and diallyldimethylammonium nitrate were added and dissolved by stirring, thereby obtaining solution A. In a separate vessel, 0.21g of silver nitrate was added to 6g of propylene glycol and dissolved, to prepare a solution B. The concentration of silver nitrate in solution B was 0.20mol/L.

All solutions a and B were added to the solution a over 1 minute after heating them from normal temperature to 90 ℃ in an oil bath while stirring them at 300rpm with a stirrer coated with a fluororesin. After the addition of the solution B was completed, the stirring state was further maintained and maintained at 90 ℃ for 24 hours, and then, it was cooled to normal temperature. Silver nanowires are thus produced. The liquid in the synthesis reaction end stage of the silver nanowire is referred to as a reaction liquid.

< cleaning >

To the reaction solution cooled to room temperature, 20 times the amount of acetone was added, and the mixture was stirred for 10 minutes and then left to stand for 24 hours. After standing, the concentrate and supernatant were observed, and the supernatant fraction was carefully removed with a pipette to obtain the concentrate. The concentrate was added to 100g of pure water, stirred for 10 minutes, then acetone was added in an amount 20 times the total amount of the concentrate and 100g of pure water, and the mixture was left to stand still for 24 hours after stirring for 10 minutes. After standing, the concentrate and supernatant were observed, and the supernatant was carefully removed with a pipette to obtain a concentrate. The steps of adding the pure water, adding acetone, standing and removing the supernatant were performed 10 times. The cleaning was performed using a glass container coated with a fluorine resin.

The obtained concentrate was diluted with PVP (polyvinylpyrrolidone) having a molecular weight of 55,000, which was contained in pure water at 1 mass%, so that the silver nanowire content was adjusted to 0.01 mass%. Thus, a liquid containing silver nanowires after washing was obtained. At this time, a desired amount of silver nanowires was prepared so that the entire amount at this time became 5L. At the end of the cleaning process, the average length of the silver nanowires was 8.1 μm, the average diameter was 28.1nm, and the average aspect ratio was 8100/28.1≡288.

Cross-flow filtration-

The above-mentioned washed liquid containing silver nanowires (silver nanowire content 0.01 mass%) was subjected to cross-flow filtration using a porous ceramic filter to remove short length wires. This operation is referred to as "purification". The purification was performed while supplying pure water to the circulation path in the same amount as the liquid component discharged to the outside of the circulation path by the cross-flow filtration. After purification, cross-flow filtration was performed for a while in a state where the make-up water was stopped, thereby increasing the silver nanowire content in the liquid to 1 mass%. Thus, a silver nanowire dispersion in which silver nanowires are dispersed in pure water was obtained. The average length of silver nanowires in the dispersion was 14.6 μm, the average diameter was 28.9nm, and the average aspect ratio was 14600/28.9≡505.

< inking >

HEMC (hydroxyethyl methylcellulose; TOMOE ENGINEERING co., ltd. Manufactured) having a weight average molecular weight of 910,000 was prepared. The powder of HEMC was put into pure water strongly stirred by a stirrer, and then, the strong stirring was continued for 24 hours. The stirred liquid was filtered through a metal mesh having a mesh size of 100 μm to remove colloidal insoluble components, thereby obtaining an aqueous solution in which HEMC was dissolved.

As the adhesive, an emulsion of a water-soluble acrylic-urethane copolymer resin (manufactured by Konnikl ijke DSM N.V., neoPac. TM. E-125) was prepared.

To 1 vessel with a lid, the silver nanowire dispersion (medium is water) obtained by the cross-flow filtration, the HEMC aqueous solution, the water-soluble acrylic-urethane copolymer resin emulsion, and isopropyl alcohol were added, and after the lid was closed, the vessel was shaken up and down 100 times to mix them with stirring. In the composition of the mixture, the mixing amounts of the respective substances were adjusted so that the mass ratio of water/isopropyl alcohol was 80/20, and the HEMC component was 0.30 mass%, the water-soluble acrylic-urethane copolymer resin component was 0.15 mass%, and the metallic silver of the silver nanowires was 0.15 mass% with respect to the total amount of the entire mixture. The HEMC/silver mass ratio was 2.0. Thus, a silver nanowire ink was obtained. The silver nanowire ink had a viscosity of 33.1 mPas at a shear rate of 600 (1/s) and a surface tension of 32.3mN/m.

< preparation of photosensitive transfer Material >

On a temporary support (Lumirror 16FB40 (manufactured by tolay INDUSTRIES, INC., biaxially stretched PET film, thickness 16 μm)), the following thermoplastic resin composition was coated on the surface of the temporary support using a slit nozzle so that the coating width became 1.0m and the dry layer thickness became 3.0 μm. The formed coating film of the thermoplastic resin composition was dried at 80 ℃ for 40 seconds to form a thermoplastic resin layer.

The following water-soluble resin layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle so that the application width became 1.0m and the layer thickness after drying became 1.2. Mu.m. The coating film of the water-soluble resin layer composition was dried at 80 ℃ for 40 seconds to form a water-soluble resin layer.

The following photosensitive resin composition was applied to the surface of the formed water-soluble resin layer using a slit nozzle so that the application width became 1.0m and the layer thickness after drying became 5.0 μm, and dried at 100℃for 2 minutes to form a photosensitive resin layer. A protective film (Oji F-Tex co., ltd., manufactured by ltd., polypropylene film, thickness 30 μm) was attached to the photosensitive resin layer to prepare a photosensitive transfer material.

< composition of thermoplastic resin composition >

Propylene glycol monomethyl ether acetate solution of benzyl methacrylate, methacrylic acid and acrylic acid copolymer (solid content concentration 30.0%, mw30,000, acid value 153 mgKOH/g): 42.85 parts

NK Ester A-DCP (SHIN-NAKAMURA CHEMICAL CO, LTD.): 4.33 parts of

8UX-015A (Taisei Fine Chemical co., ltd.): 2.31 parts

Aromix TO-2349 (TOAGOSEI co., ltd.): 0.77 part

MEGAFACE F-552 (DIC Corporation): 0.03 part

Methyl ethyl ketone (SANKYO chemistry co., ltd.): 39.80 parts

Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO k.k.): 9.51 parts

A compound having the structure shown below (photoacid generator, a compound synthesized by a method described in paragraph 0227 of japanese patent application laid-open No. 2013-47765): 0.32 part

[ chemical formula 19]

A compound having the structure shown below (a dye that develops color by an acid): 0.08 part

[ chemical formula 20]

< composition of Water-soluble resin layer composition >

KURARAY POVAL PVA-205 (polyvinyl alcohol, KURARAY co., ltd.): 3.22 parts by mass

Polyvinylpyrrolidone K-30 (NIPPON shokubaci co., ltd.): 1.49 parts by mass

MEGAFACE F-444 (fluorosurfactant, manufactured by DIC Corporation): 0.0015 part by mass

Ion exchange water: 38.12 parts by mass

Methanol (Mitsubishi Gas Chemical Company, inc. Manufactured): 57.17 parts by mass

< composition of photosensitive resin composition >

Propylene glycol monomethyl ether acetate solution (solid content concentration: 30.0% by mass, ratio of monomers: 52% by mass/29% by mass/19% by mass, mw:70,000) of copolymer of styrene/methacrylic acid/methyl methacrylate: 23.4 parts by mass

BPE-500 (ethoxylated bisphenol a dimethacrylate, shin-Nakamura Chemical co., ltd.): 4.1 parts by mass

NK Ester HD-N (1, 6-hexanediol dimethacrylate, shin-Nakamura Chemical Co., ltd.): 2.2 parts by mass

B-CTM (2, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, photopolymerization initiator, KUROGANE KASEI co., manufactured by ltd.): 0.25 part by mass

SB-PI 701 (4, 4' -bis (diethylamino) benzophenone, sensitizer, available from SANYO transfer CO., LTD.): 0.04 part by mass

TDP-G (phenothiazine, kawaguchi Chemical Industry co., ltd.): 0.0175 part by mass

1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.0011 part by mass

Colorless crystal violet (Tokyo Chemical Industry co., ltd.): 0.051 mass portion

N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.02 part by mass

1,2, 4-triazole (Tokyo Chemical Industry co., ltd.: manufactured): 0.75 part by mass

MEGAFACEF-552 (fluorosurfactant, manufactured by DIC Corporation): 0.05 part by mass

Methyl ethyl ketone (SANKYO chemistry co., ltd.): 40.4 parts by mass

Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO k.k.): 26.7 parts by mass

Methanol (Mitsubishi Gas Chemical Company, inc. Manufactured): 2 parts by mass

< formation of conductive Pattern >

After the protective film was peeled off from the photosensitive transfer material, the photosensitive transfer material was bonded to the conductive substrate under lamination conditions of a roll temperature of 100 ℃, a linear pressure of 0.8MPa, and a linear velocity of 3.0 m/min.

The bonded photosensitive transfer material was subjected to pattern exposure by an exposure machine (M-1S, manufactured by MIKASA CO., LTD) with a glass mask having a line and space pattern with a line width of 100 μm, a lead-out terminal pattern connected thereto, and a 5cm square blanket pattern for measuring sheet resistance, adhered to the temporary support without peeling off the temporary support, and with the mask interposed therebetween. The exposure amount was 100mJ/cm at a wavelength of 365nm ² 。

After leaving to stand for 1 hour after exposure, the temporary support was peeled off, and the uncured portion was removed by spraying and blowing a developer (30 ℃ C., 1.0% aqueous potassium carbonate solution) to prepare a pattern (resist pattern) of a cured film of the photosensitive resin layer.

By blowing an aqueous solution of nitric acid (28 ℃,35.0 mass%) by spraying, a resin component (hydroxyethyl methylcellulose or the like) remains in the region where the resist pattern does not exist, and silver nanowires are removed.

Further, the remaining resist pattern was removed by spraying and blowing a tetramethyl ammonium hydroxide (TMAH) aqueous solution (2.38 mass%) at 40 ℃ to produce a conductive pattern (line and space pattern and blanket pattern). Along the lines of the line and space pattern, the entire length of 200 μm was observed with an optical microscope, and the line width of the portion where the silver nanowire was present was measured, taking the arithmetic average value of 10 lines as the line width of the conductive pattern.

< formation of lead-out Wiring portion >

For the lead-out wiring portion of the pattern, copper ink prepared by the following method was printed by an Inkjet (IJ) printing apparatus (DMP 2831, manufactured by Dimatix corporation), and dried at 120 ℃ for 30 minutes by a hot air dryer to produce a lead-out wiring pattern. Thereafter, the copper ink was sintered by calcining for 3 hours at 200℃under atmospheric pressure-100 kPa using a vacuum oven to obtain a laminate.

< preparation of copper ink >

To a 500mL three-necked flask equipped with a stirrer and a cooling tube, 2.5g of copper sulfate pentahydrate (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a copper raw material, 27mg of palladium acetate (manufactured by FUJIFILM Wako Pure Chemical Corporat ion) as an additive, 2.3g of sodium tartrate dihydrate (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a complexing agent, 0.1g of OLFINEE1010 (manufactured by Nissin Chemical co., ltd.) as an acetylene-based surfactant, 3.0g of sodium hydroxide, 40mg of Naticol1000 (manufactured by WEISHARDT corporation as a protective agent, collagen peptide having a weight average molecular weight of 2, 700), 200mL of pure water were charged, and stirred at room temperature (25 ℃) for 30 minutes. Then, the internal temperature of the reaction vessel was set to 45 ℃. 1.0g of hydrazine hydrate as a reducing agent was dissolved in 49g of water, and the obtained aqueous solution was added dropwise to the reaction vessel, and the reaction was further carried out for 2 hours.

As described above, collagen peptide-coated copper nanoparticles were obtained.

The average particle diameter of the collagen peptide coated copper nanoparticle is about 20nm.

20g of the above collagen peptide-coated copper nanoparticle, 64g of pure water, 10g of ethylene glycol, 6g of glycerin were mixed and treated with an ultrasonic homogenizer for 15 minutes to obtain a collagen peptide-coated copper nanoparticle dispersion. The collagen peptide-coated copper nanoparticle dispersion was used as the copper ink.

< shape stability of conductive Pattern after heating >

After the copper ink firing was performed, the line width of the conductive pattern was measured in the same manner as before the firing. The line width fluctuation ratio of the conductive pattern before and after sintering was obtained and judged based on the following criteria. Preferably, A or B is determined.

Line width variation rate of conductive pattern before and after heating= (|conductive pattern line width before heating-conductive pattern line width after heating|)/conductive pattern line width before heating

< evaluation criterion >

A: the line width variation of the conductive pattern before and after heating is less than 10%.

B: the line width variation ratio of the conductive pattern before and after heating is 10% or more and less than 20%.

C: the line width variation ratio of the conductive pattern before and after heating is 20% or more.

< bendability after Pattern formation >

The resistance value between the lead terminal portions of the fabricated laminate was measured using a resistance meter RM3548 (manufactured by HIOKI e.e. corporation). Thereafter, an OCA film NNXA (manufactured by gnze LIMITED) was attached to the silver nanowire-coated side of the substrate with a laminator, and then, 10,000 times of bending was performed at a bending angle of 180 ° and 50rpm with a bending tester 111 (manufactured by Allgood corporation). After the bending test, the OCA film was gradually peeled off while being heated at 50 to 70 ℃, thereby exposing the lead terminal pattern connected to the wire and the space, and the resistance value between the exposed lead terminals was measured in the same manner.

The minimum bending radius at which no resistance change of 10% or more was generated as compared with that before the bending test was obtained by decreasing the bending radius from 5.0mm to 0.5 mm.

After the bending test with the minimum bending radius, it was determined whether or not peeling occurred at the interface between the substrate and the conductive pattern. The judgment was made based on the following criteria. Preferably, A or B is determined.

< evaluation criterion >

A: no peeling was observed between the substrate and the conductive pattern.

B: peeling was observed between the substrate and the conductive pattern at less than 10% of the pattern length.

C: peeling was observed at 10% or more of the pattern length between the substrate and the conductive pattern.

Examples 2 to 5 and comparative example 1

A laminate was produced and evaluated in the same manner as in example 1, except that the base material was changed to the material described in table 1.

Example 6

After a base layer having a composition described below was formed in advance on the substrate of example 1, a photosensitive transfer material was applied thereto in the same manner as in example 1, and a conductive pattern was formed.

Composition of basal layer-

Benzyl methacrylate/methacrylic acid=60/40 mass% copolymer (molecular weight 12,000, propylene glycol monomethyl ether acetate 30 mass% solution): 3.52 parts

LIGHT ACRYLATE DPE-6A (Kyoeisha co., ltd.): 0.47 part

Irgacure OXE03 (manufactured by BASF Japan ltd): 0.01 part

Propylene glycol monomethyl ether acetate: 50.0 parts

Methyl ethyl ketone: 46.0 parts

The formation of the base layer is performed on the film. The composition for forming a base layer was applied onto a PET film (manufactured by Lumirror #100-S10, TORAY INDUSTRIES, INC.) using a spin coater (manufactured by MS-B100, MIKASA CO., LTD), and the coating conditions were determined such that the film thickness after drying was 30 nm. The conductive thin film was coated with the base layer under the same coating conditions as those described above. After drying with an oven at 100 ℃, 600mJ/cm was obtained by using an exposure machine (M-1S, MIKASA co., LTD) ² Is exposed to light. In addition, a post bake was performed with a convection oven at 150 ℃ for 30 minutes to form the base layer.

Comparative example 2

In ZeonorFilm (registered trademark) ZF16: the cycloolefin polymer substrate manufactured by Zeon Corporation was sputtered with a copper layer at a thickness of 150nm to form a conductive layer. A laminate was produced and evaluated in the same manner as in example 1, except that a substrate having a conductive layer was used, and etching of the conductive layer was performed as follows to form a conductive pattern.

The conductive substrate having the obtained resin pattern was sprayed with a copper etching solution (Cu-03, manufactured by kanto KAGAKU.) to thereby remove the conductive layer at the portion where the resin pattern was not present. Further, the remaining resin pattern was removed by spraying and blowing a tetramethyl ammonium hydroxide (TMAH) aqueous solution (2.38 mass%) at 40 ℃ to produce a conductive pattern.

TABLE 1

The manufacturers of the respective substrates described in table 1 except the above are as follows.

ZeonorFilm (registered trademark) ZF16: manufactured by Zeon Corporation: cycloolefin polymer base material

Teonex (registered trademark) TN8065S: teijn LIMITED manufacture: polyethylene naphthalate (PEN) substrates

Lumirror (registered trademark) U48: TORAY INDUSTRIES, INC. manufacture: polyethylene terephthalate substrate

PURE-ACE (registered trademark) D: teijn LIMITED manufacture: polycarbonate substrate

CP1 (registered trademark) Polyimide film: neXolve Holding Company LLC manufacture: polyimide substrate

As shown in table 1, the laminate of examples 1 to 6 was excellent in shape stability of the conductive pattern even after heating, and also small in bending radius and excellent in bending property, as compared with the laminate of comparative example 1.

In this example, it is considered that, by using a base material having a high glass transition temperature, expansion/contraction of the substrate during heating is less likely to occur, and thus, variation in pattern line width before and after heating is reduced.

In comparative example 2, the conductive pattern does not include a metal nano-body or a resin, and therefore the conductive pattern has good shape stability, but the resistance change at the time of the bending test is large, that is, the bending property is poor as a result.

In addition, when polyimide is used as the base material as a result of the unprecedented material, a phenomenon occurs in which separation between the base material and the conductive pattern is difficult to occur after the bending test. The peeling of the substrate from the conductive pattern is worse in the silver nanowire and the cycloolefin, and is worst between copper sputtering and cycloolefin. The reason for this is not completely clear, but it is assumed that the reason is that the polyimide substrate has a hydrophilic surface, and therefore the aqueous silver nanowire dispersion liquid has good coatability, and the adhesion between the substrate and the conductive pattern is relatively high. The minimum bending radius of the polyimide substrate itself is small, and is excellent in forming a bendable touch panel wiring, for example.

Example 7

< preparation of conductive substrate >

Silver nanowire ink (manufactured by GENESINK Corporation, tranDuctive (registered trademark) N70) was coated on a transparent polyimide film (manufactured by general type x, i.s.t. Corporation) having a thickness of 50 μm so that the film thickness of the coating film became 3 μm, and was dried with a convection oven at 80 ℃ for 1 minute. Thereafter, the conductive substrate having the conductive layer containing silver nanowires was dried with a convection oven at 120 ℃ for 2 minutes to fabricate a conductive substrate.

< formation of protective layer >

The prepared conductive substrate was coated with the composition 1 for forming a protective layer prepared with the composition described in table 2 using a spin coater (manufactured by MIKASA co., LTD, MS-B150) so that the dry film thickness became 30nm. The coated film was dried with an oven at 100 ℃. Next, an exposure machine (M-1S, MIKASA CO., LTD) was used at 600mJ/cm ² Exposure is performed by the exposure amount of (a). Thereafter, a convection oven at 150℃was used for 30 minutes post-baking to cure it, to form a protective layer. Thus, a conductive substrate with a protective layer was produced.

< production of conductive Pattern/lead-out Wiring >

The photosensitive transfer material was laminated on the produced conductive substrate with the protective layer in the same manner as in example 1, and a conductive pattern was formed. After patterning, the sheet resistance of the blanket pattern portion was measured with a resistance meter (Napson Corporation manufactured EC-80P) and found to be 75.1 Ω/≡. Thereafter, in the same manner as in example 1, formation of a take-out wiring portion using copper ink was performed.

< shape stability of conductive Pattern after heating >

Evaluation was performed in the same manner as in example 1.

< bendability after Pattern formation >

Evaluation was performed in the same manner as in example 1.

< measurement of sulfur atom weight/silver atom weight >

The laminate formed with the conductive pattern and the protective layer was cut in a direction perpendicular to the surface of the substrate using a dicing machine (Leica Microsystems manufactured UC 7), and a dicing sheet was obtained in which the conductive pattern and the protective layer were exposed in cross section. For this slice, elemental quantification was performed using a scanning transmission electron microscope (manufactured by Thermo Fisher Scientific k.k., talosF 200X) under conditions of an acceleration voltage of 200kV and a probe current of 0.7 nA. Similarly, the relative mass ratio of the amount of sulfur atoms contained in the protective layer to the amount of silver atoms (metal atoms) contained in the conductive pattern was obtained by measuring the amount of sulfur atoms in only the conductive pattern and subtracting this value from the baseline.

< measurement of elastic modulus of protective layer >

The laminate formed with the conductive pattern and the protective layer was cut in a direction perpendicular to the surface of the substrate using a dicing machine (Leica Microsystems manufactured UC 7), and a dicing sheet was obtained in which the conductive pattern and the protective layer were exposed in cross section. For the protective layer portion of the cross section, AFM (manufactured by Bruker Japan k.k. division ICON) was used, in peak force QNM (Quantitative Nanoscale Mechan ical: quantitative nanomechanical) mode, probe: the elastic modulus was measured under RTESPA-300 (300 kHz, 40N/m).

Further, the exposure machine (M-1S, MIKASA CO., LTD) was used at 1000mJ/cm ² Exposing the laminate. After exposure, measurement of elastic modulus was performed again, and the change in elastic modulus before and after exposure (post-exposure elastic modulus/pre-exposure elastic modulus, marked as a percentage) was evaluated.

Further, after the laminate was heated with a convection oven at 100℃for 120 minutes, the elastic modulus was measured again. After that, the change in elastic modulus before and after heating (elastic modulus after heating/elastic modulus before heating, expressed as a percentage) was evaluated.

< evaluation of moist Heat resistance of laminate >

OCA (manufactured by 3M Japan Limited, CEF 1904) and further a polyester film (manufactured by TOYOBO co., ltd., a4160, thickness 50 μm) were attached to both sides of the laminate having the conductive pattern/protective layer formed thereon. The sample piece was placed in a wet type constant temperature bath (manufactured by ESPEC Corp., SH-221) and kept at a temperature of 55.+ -. 2 ℃ and a humidity of 93.+ -. 3RH% for 300 hours. For the samples before and after the test, the sheet resistance of the rubber pattern portion was measured by a resistance meter (manufactured by Napson Corporation, EC-80P). Then, the wet heat resistance was evaluated based on the following evaluation criteria, with the rate of change in the sheet resistance value (modulus of elasticity after heating/modulus of elasticity before heating, marked as a percentage). The conductive substrate is preferably evaluated as B or more.

< evaluation criterion >

A: the area resistance change rate before and after the test was 5% or less.

B: the area resistance change rate before and after the test is more than 5% and less than 10%.

C: the area resistance change rate before and after the test is more than 10%.

The details of each component used for forming the protective layer are as follows.

XA-1: benzyl methacrylate/methacrylic acid (=70/30 mass%) copolymer

(30% by mass propylene glycol monomethyl ether acetate solution having a molecular weight of 30,000)

XB-1: LIGHT ACRYLATE DPE-6A (manufactured by Kyoeisha Co., LTD.)

XC-1: irgacure OXE02 (manufactured by BASF Japan Ltd.)

XE-1:2, 5-dimercapto-1, 3, 4-thiadiazole

(Tokyo Chemical Industry Co., ltd.)

XE-2: 2-naphthalenethiol (Tokyo Chemical Industry co., ltd.: manufactured)

XE-3: 2-amino-5- (benzylthio) -1,3, 4-thiadiazole (Tokyo Chemical Industry co., ltd. & gt, manufactured by

XE-4: 2-mercaptobenzimidazole (Tokyo Chemical Industry Co., ltd.)

XE-5:2, 5-bis (octyldisulfide) -1,3, 4-thiadiazole

(manufactured by alfa chemistry)

XE-6: 3-mercapto-1, 2, 4-triazole (Tokyo Chemical Industry co., ltd.: manufactured)

XE-7: 1-dodecyl mercaptan (Tokyo Chemical Industry Co., ltd.)

XE-8: benzothiazole (Tokyo Chemical Industry co., ltd.)

XF-1: propylene glycol monomethyl ether acetate

(SANKYO CHEMICAL CO., LTD. Manufactured)

XF-2: methyl ethyl ketone (SANKYO CHEMICAL CO., LTD.)

Examples 8 to 27

In example 7, a laminate was produced and evaluated in the same manner as in example 7, except that a protective layer having a composition changed to those described in tables 2 to 3 was formed. The results are shown in tables 2 to 3.

Example 28

After preparing the composition for forming a protective layer with the composition described in table 3, the composition for forming a protective layer was spin-coated and dried in the same manner as in example 7, and then a protective layer was formed without exposure and post baking. Except for this, laminate production and evaluation were performed in the same manner as in example 7. The results are shown in Table 3.

TABLE 2

TABLE 3

In the laminate of the present invention, by providing the protective layer containing the sulfur-containing compound, the resistance value of the conductive layer does not significantly increase even after exposure to a humid and hot environment, and a laminate excellent in reliability can be obtained.

Symbol description

11-temporary support, 12-transfer layer, 13-thermoplastic resin layer, 15-water-soluble resin layer, 17-photosensitive resin layer, 19-protective film, 20-photosensitive transfer material, GR-light shielding portion (non-image portion), EX-exposure portion (image portion), DL-aligned frame.

Claims

1. A laminate, comprising:

a substrate; and

A conductive pattern comprising metal nano-bodies and a resin,

the total light transmittance of the substrate is 75% or more,

the glass transition temperature of the substrate is above 120 ℃.

2. The laminate according to claim 1, wherein,

the glass transition temperature of the substrate is above 200 ℃.

3. The laminate according to claim 1 or 2, wherein,

the substrate has a coefficient of thermal expansion of 10X 10 in Kelvin at 100 ℃ to 200 DEG C ^-6 Above 50×10 ^-6 The following is given.

4. The laminate according to claim 1 or 2, wherein,

the dimensional change rate of the base material at 100-200 ℃ is more than-1% and less than +1%.

5. The laminate according to claim 1 or 2, wherein,

the substrate is a polyimide substrate.

6. The laminate according to claim 1 or 2, wherein,

the metal nano-body is a metal nano-wire.

7. The laminate according to claim 1 or 2, wherein,

the metal nano-bodies are nano-particles with the aspect ratio of 1:1-1:10 and the sphere equivalent diameter of 1 nm-200 nm.

8. The laminate according to claim 1 or 2, further comprising a protective layer on a side of the conductive pattern opposite to the side having the substrate.

9. The laminate according to claim 8, wherein,

the protective layer contains sulfur atoms, and the mass ratio of the amount of sulfur atoms contained in the protective layer to the amount of metal atoms contained in the conductive pattern is greater than 0.10% and 20% or less.

10. The laminate according to claim 9, wherein,

the sulfur atom contained in the protective layer contains a sulfur atom derived from a thiol compound or a thioether compound.

11. The laminate according to claim 10, wherein,

the thiol compound or the thioether compound is a compound having an aromatic ring or a heteroaromatic ring.

12. The laminate according to claim 8, wherein,

the elastic modulus of the protective layer is 4000 MPa-7000 MPa.

13. The laminate according to claim 8, wherein,

with a high-pressure mercury lamp at 1000mJ/cm ² The elastic modulus of the protective layer before and after exposure of the protective layer changes by less than 10%.

14. The laminate according to claim 8, wherein,

the elastic modulus of the protective layer changes by less than 10% after heating at 100 ℃ for 120 minutes.

15. The laminate according to claim 1 or 2, further having a base layer between the substrate and the conductive pattern.

16. The laminate according to claim 15, wherein,

the base layer contains any one of acrylic resin and styrene-acrylic resin.

17. The laminate according to claim 1 or 2, further comprising a nonconductive pattern on at least a portion of the substrate between the conductive patterns.

18. The laminate according to claim 17, wherein,

the conductive pattern and the nonconductive pattern include a resin having the same structural unit.

19. An electronic device provided with the laminate according to claim 1 or 2.